WO2020171030A1 - Silver plating solution composition - Google Patents
Silver plating solution composition Download PDFInfo
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- WO2020171030A1 WO2020171030A1 PCT/JP2020/006153 JP2020006153W WO2020171030A1 WO 2020171030 A1 WO2020171030 A1 WO 2020171030A1 JP 2020006153 W JP2020006153 W JP 2020006153W WO 2020171030 A1 WO2020171030 A1 WO 2020171030A1
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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
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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
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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
- C23C18/52—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 using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
Definitions
- the electroless plating method is used for surface modification of a wide range of materials because it can form a uniform film on an independent pattern and is easy to operate. Further, the electroless plating method is roughly classified into a substitution deposition type in which a metal is deposited on the surface of a plating target due to a difference in ionization tendency and a reduction deposition type in which a metal is deposited on the surface of a plating target by the action of a reducing agent. ..
- a substitution precipitation type that contains a cyanide compound or ammonia (Non-Patent Document 1), but the former is highly toxic and the latter is explosive silver.
- the silver plating solution composition of the present invention does not contain a cyanide compound and an ammonia compound as additional components. Further, the silver plating solution composition of the present invention preferably does not contain a reducing agent as an additional component.
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
Provided is a novel silver plating solution composition containing: (A) a water-soluble thiosulfate compound; (B) a silver ion source; and (C) water.
Description
本発明は、銀めっき液組成物、該組成物を用いた銀めっき方法、および、該方法により銀めっき皮膜が形成された銀めっき処理品に関する。
The present invention relates to a silver plating solution composition, a silver plating method using the composition, and a silver-plated product having a silver plating film formed by the method.
半導体分野における接合材料としてはんだは古くから用いられており、近年、より高い電圧および大きな電流の制御が可能なことで着目されているパワー半導体の分野においても、はんだが接合材料として用いられる。しかしながら、パワー半導体の高機能化が進むと共に、接合材料にかかる電圧および電流が一層増大していることから、接合材料としてのはんだが、耐熱性等の要求に必ずしも応えられなくなりつつあった。
Solder has been used as a joining material in the field of semiconductors for a long time, and in recent years, solder is also used as a joining material in the field of power semiconductors, which is attracting attention because it can control higher voltage and larger current. However, as the performance of power semiconductors has advanced and the voltage and current applied to the bonding material have further increased, solder as a bonding material has not always been able to meet the requirements for heat resistance and the like.
はんだに代わる接合材料としては、高い耐熱性および高い放熱特性を有する銀（たとえば、銀焼結材）が有用である。他方、半導体素子の電極材料は銅またはアルミニウムが用いられていることが多く、当該電極と接合材料としての銀とを高い信頼性で接合させるためには、電極表面を銀で被覆することが必要となる。ところが、電極表面を直接銀で被覆した場合には、電極の保護および密着性の確保が十分に達成できないため、電極上にニッケルバリア層を形成し、当該ニッケルバリア層を銀で被覆することで、銀を用いた接合材料と電極とを接合させることが一般的になりつつある。このような接合を実現するためには、ニッケル上に銀を製膜する技術が必要となる。
As a joining material to replace solder, silver (for example, silver sintered material) having high heat resistance and high heat dissipation properties is useful. On the other hand, the electrode material of the semiconductor element is often copper or aluminum, and it is necessary to coat the electrode surface with silver in order to bond the electrode and silver as a bonding material with high reliability. Becomes However, if the electrode surface is directly coated with silver, protection of the electrode and securing of adhesiveness cannot be sufficiently achieved, so it is necessary to form a nickel barrier layer on the electrode and coat the nickel barrier layer with silver. It is becoming common to bond a bonding material using silver and an electrode. In order to realize such joining, a technique for forming a silver film on nickel is required.
無電解めっき法は、独立パターン上に均一な皮膜を形成でき、かつ操作性も容易であることから幅広い材質の表面改質に用いられる。さらに、無電解めっき法は、イオン化傾向の差によりめっき対象の表面に金属を析出させる置換析出型、および、還元剤の作用によりめっき対象の表面に金属を析出させる還元析出型に大別される。従来から使用されている無電解銀めっき液には、シアン化合物あるいはアンモニアを含有する置換析出型のものがあった（非特許文献１）が、前者は毒性が高いこと、後者は爆発性の銀化合物（雷銀）を生成することから実用的とはいえなかった。現在実用化されている置換析出型の銀めっき液は、銅表面を被覆するためのものがほとんどであり（特許文献１～３）、ニッケル表面を被覆するための置換析出型の銀めっき液としては、錯化剤として亜硫酸塩やイミド基、アミド基を有する有機化合物を含有する、導電性粉末用の銀めっき液（特許文献４）がわずかに知られている程度である。
The electroless plating method is used for surface modification of a wide range of materials because it can form a uniform film on an independent pattern and is easy to operate. Further, the electroless plating method is roughly classified into a substitution deposition type in which a metal is deposited on the surface of a plating target due to a difference in ionization tendency and a reduction deposition type in which a metal is deposited on the surface of a plating target by the action of a reducing agent. .. Among the electroless silver plating solutions that have been conventionally used, there is a substitution precipitation type that contains a cyanide compound or ammonia (Non-Patent Document 1), but the former is highly toxic and the latter is explosive silver. It is not practical because it produces a compound (thunder silver). Most of the substitution-precipitation type silver plating solutions currently in practical use are for coating the copper surface (Patent Documents 1 to 3), and are used as substitution-precipitation type silver plating solutions for coating the nickel surface. Is slightly known as a silver plating solution for conductive powder (Patent Document 4) containing an organic compound having a sulfite salt, an imide group or an amide group as a complexing agent.
本発明の課題は、新規な銀めっき液組成物、特に、銀よりもイオン化傾向の高い金属またはその合金に銀めっきするための新規な銀めっき液組成物、を提供することである。
An object of the present invention is to provide a novel silver plating solution composition, particularly a novel silver plating solution composition for silver plating a metal or its alloy having a higher ionization tendency than silver.
本発明者らは、かかる課題を解決すべく鋭意検討を重ねたところ、（Ａ）水溶性チオ硫酸化合物、（Ｂ）銀イオン源および（Ｃ）水を含有する銀めっき液組成物を用いることで、銀よりもイオン化傾向の高い金属またはその合金に良好に銀めっきすることが可能となることを見い出し、本発明を完成するに至った。
The inventors of the present invention have made extensive studies in order to solve such problems, and as a result, use a silver plating solution composition containing (A) a water-soluble thiosulfate compound, (B) a silver ion source, and (C) water. Then, it has been found that it is possible to satisfactorily silver-plat a metal or its alloy having a higher ionization tendency than silver, and the present invention has been completed.
すなわち、本発明は以下に関する。
[１] （Ａ）水溶性チオ硫酸化合物、（Ｂ）銀イオン源および（Ｃ）水を含有する、銀めっき液組成物。
[２] 銀イオン源として水溶性銀化合物を含有する、前記[１]に記載の銀めっき液組成物。
[３] ｐＨが３～１４である、前記[１]または[２]に記載の銀めっき液組成物。
[４] ｐＨ調整剤を含有する、前記[１]～[３]のいずれか一つに記載の銀めっき液組成物。
[５] キレート剤を含有する、前記[１]～[４]のいずれか一つに記載の銀めっき液組成物。 That is, the present invention relates to the following.
[1] A silver plating solution composition containing (A) a water-soluble thiosulfate compound, (B) a silver ion source, and (C) water.
[2] The silver plating solution composition according to the above [1], which contains a water-soluble silver compound as a silver ion source.
[3] The silver plating solution composition according to the above [1] or [2], which has a pH of 3 to 14.
[4] The silver plating solution composition according to any one of the above [1] to [3], which contains a pH adjuster.
[5] The silver plating solution composition according to any one of the above [1] to [4], which contains a chelating agent.
[１] （Ａ）水溶性チオ硫酸化合物、（Ｂ）銀イオン源および（Ｃ）水を含有する、銀めっき液組成物。
[２] 銀イオン源として水溶性銀化合物を含有する、前記[１]に記載の銀めっき液組成物。
[３] ｐＨが３～１４である、前記[１]または[２]に記載の銀めっき液組成物。
[４] ｐＨ調整剤を含有する、前記[１]～[３]のいずれか一つに記載の銀めっき液組成物。
[５] キレート剤を含有する、前記[１]～[４]のいずれか一つに記載の銀めっき液組成物。 That is, the present invention relates to the following.
[1] A silver plating solution composition containing (A) a water-soluble thiosulfate compound, (B) a silver ion source, and (C) water.
[2] The silver plating solution composition according to the above [1], which contains a water-soluble silver compound as a silver ion source.
[3] The silver plating solution composition according to the above [1] or [2], which has a pH of 3 to 14.
[4] The silver plating solution composition according to any one of the above [1] to [3], which contains a pH adjuster.
[5] The silver plating solution composition according to any one of the above [1] to [4], which contains a chelating agent.
[６] 銀よりもイオン化傾向の高い金属またはその合金のめっきのための、前記[１]～[５]のいずれか一つに記載の銀めっき液組成物。
[７] 置換析出型である、前記[１]～[６]のいずれか一つに記載の銀めっき液組成物。
[８] 前記[１]～[７]のいずれか一つに記載の銀めっき液組成物に、銀よりもイオン化傾向の高い金属またはその合金を浸漬する工程を含む、銀めっき方法。
[９] 銀めっき液組成物の温度が２０～６０℃の範囲で、銀よりもイオン化傾向の高い金属またはその合金を浸漬する、前記[８]に記載の銀めっき方法。
[１０] 前記[８]または[９]に記載の方法により銀めっき皮膜が形成された、銀めっき処理品。 [6] The silver plating solution composition according to any one of the above [1] to [5], for plating a metal or its alloy having a higher ionization tendency than silver.
[7] The silver plating solution composition according to any one of the above [1] to [6], which is a substitution precipitation type.
[8] A silver plating method comprising a step of immersing a metal or an alloy thereof having a higher ionization tendency than silver in the silver plating solution composition according to any one of [1] to [7].
[9] The silver plating method according to the above [8], wherein a metal or an alloy thereof having a higher ionization tendency than silver is immersed in the temperature of the silver plating solution composition in the range of 20 to 60°C.
[10] A silver-plated product having a silver-plated film formed by the method described in [8] or [9] above.
[７] 置換析出型である、前記[１]～[６]のいずれか一つに記載の銀めっき液組成物。
[８] 前記[１]～[７]のいずれか一つに記載の銀めっき液組成物に、銀よりもイオン化傾向の高い金属またはその合金を浸漬する工程を含む、銀めっき方法。
[９] 銀めっき液組成物の温度が２０～６０℃の範囲で、銀よりもイオン化傾向の高い金属またはその合金を浸漬する、前記[８]に記載の銀めっき方法。
[１０] 前記[８]または[９]に記載の方法により銀めっき皮膜が形成された、銀めっき処理品。 [6] The silver plating solution composition according to any one of the above [1] to [5], for plating a metal or its alloy having a higher ionization tendency than silver.
[7] The silver plating solution composition according to any one of the above [1] to [6], which is a substitution precipitation type.
[8] A silver plating method comprising a step of immersing a metal or an alloy thereof having a higher ionization tendency than silver in the silver plating solution composition according to any one of [1] to [7].
[9] The silver plating method according to the above [8], wherein a metal or an alloy thereof having a higher ionization tendency than silver is immersed in the temperature of the silver plating solution composition in the range of 20 to 60°C.
[10] A silver-plated product having a silver-plated film formed by the method described in [8] or [9] above.
本発明の銀めっき液組成物により、銀よりもイオン化傾向の高い金属またはその合金に良好に銀めっきすることができる。
With the silver plating solution composition of the present invention, a metal or its alloy having a higher ionization tendency than silver can be excellently silver-plated.
以下、本発明について、本発明の好適な実施態様に基づき、詳細に説明する。
本発明は、（Ａ）水溶性チオ硫酸化合物、（Ｂ）銀イオン源および（Ｃ）水を含有する、銀めっき液組成物に関する。 Hereinafter, the present invention will be described in detail based on preferred embodiments of the present invention.
The present invention relates to a silver plating solution composition containing (A) a water-soluble thiosulfate compound, (B) a silver ion source, and (C) water.
本発明は、（Ａ）水溶性チオ硫酸化合物、（Ｂ）銀イオン源および（Ｃ）水を含有する、銀めっき液組成物に関する。 Hereinafter, the present invention will be described in detail based on preferred embodiments of the present invention.
The present invention relates to a silver plating solution composition containing (A) a water-soluble thiosulfate compound, (B) a silver ion source, and (C) water.
本発明の銀めっき液組成物に用いられる（Ａ）水溶性チオ硫酸化合物は、後述する銀イオン源と混合されることで、チオ硫酸銀錯体を形成する。たとえば、水溶性チオ硫酸化合物としてのチオ硫酸ナトリウムと銀イオン源としての塩化銀とを水に添加すると、下記（１）式に従ってチオ硫酸銀錯体を形成する。
The water-soluble thiosulfate compound (A) used in the silver plating solution composition of the present invention forms a silver thiosulfate complex when mixed with a silver ion source described later. For example, when sodium thiosulfate as a water-soluble thiosulfate compound and silver chloride as a silver ion source are added to water, a silver thiosulfate complex is formed according to the following formula (1).
水溶性チオ硫酸化合物としては、水溶性のチオ硫酸化合物であれば特に制限されないが、チオ硫酸のアルカリ金属塩およびチオ硫酸のアルカリ土類金属塩が好ましく、チオ硫酸のアルカリ金属塩がより好ましく、チオ硫酸ナトリウムが特に好ましい。
水溶性チオ硫酸化合物の濃度は、特に制限されないが、０．１～２０００ｍｍｏｌ／Ｌであることが好ましく、１～１０００ｍｍｏｌ／Ｌであることがより好ましく、１０～５００ｍｍｏｌ／Ｌであることが特に好ましい。 The water-soluble thiosulfate compound is not particularly limited as long as it is a water-soluble thiosulfate compound, but is preferably an alkali metal salt of thiosulfate and an alkaline earth metal salt of thiosulfate, more preferably an alkali metal salt of thiosulfate, Sodium thiosulfate is particularly preferred.
The concentration of the water-soluble thiosulfate compound is not particularly limited, but is preferably 0.1 to 2000 mmol/L, more preferably 1 to 1000 mmol/L, and particularly preferably 10 to 500 mmol/L. ..
水溶性チオ硫酸化合物の濃度は、特に制限されないが、０．１～２０００ｍｍｏｌ／Ｌであることが好ましく、１～１０００ｍｍｏｌ／Ｌであることがより好ましく、１０～５００ｍｍｏｌ／Ｌであることが特に好ましい。 The water-soluble thiosulfate compound is not particularly limited as long as it is a water-soluble thiosulfate compound, but is preferably an alkali metal salt of thiosulfate and an alkaline earth metal salt of thiosulfate, more preferably an alkali metal salt of thiosulfate, Sodium thiosulfate is particularly preferred.
The concentration of the water-soluble thiosulfate compound is not particularly limited, but is preferably 0.1 to 2000 mmol/L, more preferably 1 to 1000 mmol/L, and particularly preferably 10 to 500 mmol/L. ..
本発明の銀めっき液組成物に用いられる（Ｂ）銀イオン源としては、水中で銀イオンを発生する水溶性銀化合物であれば特に制限されないが、塩化銀、臭化銀、ヨウ化銀、硝酸銀および硫酸銀が好ましく、塩化銀、臭化銀およびヨウ化銀がより好ましく、塩化銀が特に好ましい。
銀イオン源の濃度は、特に制限されないが、０．０１～１０００ｍｍｏｌ／Ｌであることが好ましく、０．１～５００ｍｍｏｌ／Ｌであることがより好ましく、１～１００ｍｍｏｌ／Ｌであることが特に好ましい。 The (B) silver ion source used in the silver plating solution composition of the present invention is not particularly limited as long as it is a water-soluble silver compound that generates silver ions in water, but silver chloride, silver bromide, silver iodide, Silver nitrate and silver sulfate are preferable, silver chloride, silver bromide and silver iodide are more preferable, and silver chloride is particularly preferable.
The concentration of the silver ion source is not particularly limited, but is preferably 0.01 to 1000 mmol/L, more preferably 0.1 to 500 mmol/L, and particularly preferably 1 to 100 mmol/L. ..
銀イオン源の濃度は、特に制限されないが、０．０１～１０００ｍｍｏｌ／Ｌであることが好ましく、０．１～５００ｍｍｏｌ／Ｌであることがより好ましく、１～１００ｍｍｏｌ／Ｌであることが特に好ましい。 The (B) silver ion source used in the silver plating solution composition of the present invention is not particularly limited as long as it is a water-soluble silver compound that generates silver ions in water, but silver chloride, silver bromide, silver iodide, Silver nitrate and silver sulfate are preferable, silver chloride, silver bromide and silver iodide are more preferable, and silver chloride is particularly preferable.
The concentration of the silver ion source is not particularly limited, but is preferably 0.01 to 1000 mmol/L, more preferably 0.1 to 500 mmol/L, and particularly preferably 1 to 100 mmol/L. ..
本発明の銀めっき液組成物は、（Ｃ）水を含有する。水は、（Ａ）水溶性チオ硫酸化合物および（Ｂ）銀イオン源ならびに下記の含有しうる追加成分以外の残部を形成する。
The silver plating solution composition of the present invention contains (C) water. Water forms the balance other than (A) the water-soluble thiosulfate compound and (B) the source of silver ions and the additional components that may be contained below.
本発明の銀めっき液組成物のｐＨは、特に制限されないが、１～１４であることが好ましく、３～１４であることが特に好ましい。かかるｐＨの範囲において、上記（１）式に従って形成されたチオ硫酸銀錯体とめっき対象となる金属との間で電子が速やかに授受され、銀めっきが良好に進行する。たとえば、ニッケルをめっき対象とした場合には、下記（２）式に従ってニッケルが溶解するとともに銀が析出することにより、銀めっき皮膜が形成される。
本発明の銀めっき液組成物は、置換析出型の銀めっき液組成物ということもできる。 The pH of the silver plating solution composition of the present invention is not particularly limited, but is preferably 1 to 14 and particularly preferably 3 to 14. In such a pH range, electrons are rapidly exchanged between the silver thiosulfate complex formed according to the above formula (1) and the metal to be plated, and silver plating proceeds well. For example, when nickel is to be plated, nickel is dissolved according to the following equation (2) and silver is deposited to form a silver plating film.
The silver plating solution composition of the present invention can also be referred to as a displacement-precipitation type silver plating solution composition.
本発明の銀めっき液組成物は、置換析出型の銀めっき液組成物ということもできる。 The pH of the silver plating solution composition of the present invention is not particularly limited, but is preferably 1 to 14 and particularly preferably 3 to 14. In such a pH range, electrons are rapidly exchanged between the silver thiosulfate complex formed according to the above formula (1) and the metal to be plated, and silver plating proceeds well. For example, when nickel is to be plated, nickel is dissolved according to the following equation (2) and silver is deposited to form a silver plating film.
The silver plating solution composition of the present invention can also be referred to as a displacement-precipitation type silver plating solution composition.
本発明の銀めっき液組成物は、ｐＨ調整剤を含有してもよい。ｐＨ調整剤としては、既知の酸性化合物および塩基性化合物を使用することができる。酸性化合物としては、特に制限されないが、塩酸、硫酸、硝酸、過塩素酸などの無機鉱酸、および、メタンスルホン酸、酢酸、クエン酸などの有機酸が好ましく、塩酸および硝酸がより好ましく、塩酸が特に好ましい。塩基性化合物としては、特に制限されないが、水酸化ナトリウム、水酸化カリウムなどの無機塩基、および、水酸化テトラメチルアンモニウム、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、エチレンジアミン、ジエチレントリアミンなどの有機塩基が好ましく、水酸化ナトリウム、水酸化カリウムおよび水酸化テトラメチルアンモニウムがより好ましく、水酸化ナトリウムが特に好ましい。
The silver plating solution composition of the present invention may contain a pH adjuster. As the pH adjuster, known acidic compounds and basic compounds can be used. The acidic compound is not particularly limited, but inorganic inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and perchloric acid, and organic acids such as methanesulfonic acid, acetic acid and citric acid are preferable, hydrochloric acid and nitric acid are more preferable, and hydrochloric acid is hydrochloric acid. Is particularly preferable. The basic compound is not particularly limited, but inorganic bases such as sodium hydroxide and potassium hydroxide, and organic bases such as tetramethylammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine and diethylenetriamine are preferable. , Sodium hydroxide, potassium hydroxide and tetramethylammonium hydroxide are more preferable, and sodium hydroxide is particularly preferable.
本発明の銀めっき液組成物は、キレート剤を含有することが好ましい。上記式（２）に示されるとおり、本発明の銀めっき液組成物を用いた場合、銀が析出する際にめっき対象となる金属が溶解するが、キレート剤が存在することで溶解した金属が捕捉され、銀めっき液組成物の汚染や性能の劣化の抑制がされるため好ましい。
The silver plating solution composition of the present invention preferably contains a chelating agent. As shown in the above formula (2), when the silver plating solution composition of the present invention is used, the metal to be plated is dissolved when silver is deposited, but the dissolved metal is caused by the presence of the chelating agent. It is preferable because it is captured and the contamination of the silver plating solution composition and the deterioration of the performance are suppressed.
キレート剤としては、特に制限されないが、エチレンジアミン四酢酸（ＥＤＴＡ）、ジエチレントリアミン五酢酸（ＤＴＰＡ）、シクロヘキサンジアミン四酢酸（ＣｙＤＴＡ）、ニトリロ三酢酸（ＮＴＡ）などのアミノカルボン酸キレート剤、および、エチレンジアミン四酢酸テトラメチレンホスホン酸（ＥＤＴＭＰ）、ニトリロトリスメチレンホスホン酸（ＮＴＭＰ）などのアミノホスホン酸キレート剤が好ましく、アミノカルボン酸キレート剤がより好ましく、エチレンジアミン四酢酸が特に好ましい。
キレート剤の濃度は、特に制限されないが、１～２５００ｍｍｏｌ／Ｌであることが好ましく、５～１０００ｍｍｏｌ／Ｌであることがより好ましく、１０～２００ｍｍｏｌ／Ｌであることが特に好ましい。 The chelating agent is not particularly limited, but an aminocarboxylic acid chelating agent such as ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), cyclohexanediaminetetraacetic acid (CyDTA), nitrilotriacetic acid (NTA), and ethylenediaminetetraacetic acid. Aminophosphonic acid chelating agents such as acetic acid tetramethylenephosphonic acid (EDTMP) and nitrilotrimesmethylenephosphonic acid (NTMP) are preferable, aminocarboxylic acid chelating agents are more preferable, and ethylenediaminetetraacetic acid is particularly preferable.
The concentration of the chelating agent is not particularly limited, but is preferably 1 to 2500 mmol/L, more preferably 5 to 1000 mmol/L, and particularly preferably 10 to 200 mmol/L.
キレート剤の濃度は、特に制限されないが、１～２５００ｍｍｏｌ／Ｌであることが好ましく、５～１０００ｍｍｏｌ／Ｌであることがより好ましく、１０～２００ｍｍｏｌ／Ｌであることが特に好ましい。 The chelating agent is not particularly limited, but an aminocarboxylic acid chelating agent such as ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), cyclohexanediaminetetraacetic acid (CyDTA), nitrilotriacetic acid (NTA), and ethylenediaminetetraacetic acid. Aminophosphonic acid chelating agents such as acetic acid tetramethylenephosphonic acid (EDTMP) and nitrilotrimesmethylenephosphonic acid (NTMP) are preferable, aminocarboxylic acid chelating agents are more preferable, and ethylenediaminetetraacetic acid is particularly preferable.
The concentration of the chelating agent is not particularly limited, but is preferably 1 to 2500 mmol/L, more preferably 5 to 1000 mmol/L, and particularly preferably 10 to 200 mmol/L.
たとえば、ニッケルをめっき対象とし、エチレンジアミン四酢酸をキレート剤とした場合には、溶解したニッケルは下記（３）式に従って捕捉される。
For example, when nickel is the plating target and ethylenediaminetetraacetic acid is the chelating agent, the dissolved nickel is captured according to the following formula (3).
本発明の銀めっき液組成物は、他の追加成分、たとえば、既知の結晶調整剤成分や平滑剤成分、界面活性剤成分をさらに含有することができる。
The silver plating solution composition of the present invention may further contain other additional components such as known crystal modifier component, leveling agent component, and surfactant component.
本発明の銀めっき液組成物は、安全性の観点から、シアン化合物およびアンモニア化合物を追加成分として含有しないことが好ましい。また、本発明の銀めっき液組成物は、還元剤を追加成分として含有しないことが好ましい。
From the viewpoint of safety, it is preferable that the silver plating solution composition of the present invention does not contain a cyanide compound and an ammonia compound as additional components. Further, the silver plating solution composition of the present invention preferably does not contain a reducing agent as an additional component.
本発明の銀めっき液組成物は、上記（２）式に示されるとおり、当該組成物中に形成されるチオ硫酸銀錯体と電子の授受が可能な金属またはその合金、すなわち、銀よりもイオン化傾向の高い金属またはその合金をめっき対象とすることができる。よって、本発明の銀めっき液組成物は、銀よりもイオン化傾向の高い金属またはその合金のめっきのための銀めっき液組成物、好ましくは、ニッケル、銅、スズ、コバルトまたはその合金のめっきのための銀めっき液組成物、より好ましくは、ニッケル、銅、またはその合金のめっきのための銀めっき液組成物、特に好ましくは、ニッケルまたはニッケル合金のための銀めっき液組成物として用いることができる。
The silver plating solution composition of the present invention is, as shown in the above formula (2), a metal capable of giving and receiving electrons to and from a silver thiosulfate complex formed in the composition, or an alloy thereof, that is, ionized rather than silver. A metal or an alloy thereof having a high tendency can be plated. Therefore, the silver plating solution composition of the present invention is a silver plating solution composition for plating a metal or an alloy thereof having a higher ionization tendency than silver, preferably nickel, copper, tin, cobalt or an alloy thereof. For use as a silver plating solution composition, more preferably as a silver plating solution composition for plating nickel, copper, or an alloy thereof, particularly preferably as a silver plating solution composition for nickel or a nickel alloy. it can.
本発明の銀めっき液組成物のめっき対象となる金属またはその合金の形状は、特に制限されないが、板状および膜状（厚膜状または薄膜状）が好ましく、膜状がより好ましい。
The shape of the metal or its alloy to be plated by the silver plating solution composition of the present invention is not particularly limited, but a plate shape and a film shape (thick film shape or thin film shape) are preferable, and a film shape is more preferable.
また、本発明は、本発明の銀めっき液組成物に、銀よりもイオン化傾向の高い金属またはその合金を浸漬する工程を含む、銀めっき方法にも関する。銀よりもイオン化傾向の高い金属またはその合金としては、ニッケル、銅、スズ、コバルトまたはその合金が好ましく、ニッケル、銅、またはその合金がより好ましく、ニッケルまたはニッケル合金が特に好ましい。
本発明の銀めっき方法における、銀よりもイオン化傾向の高い金属またはその合金を浸漬する銀めっき液組成物の温度は、特に制限されないが、１０～９０℃であることが好ましく、２０～６０℃であることが特に好ましい。 The present invention also relates to a silver plating method including a step of immersing a metal or an alloy thereof having a higher ionization tendency than silver in the silver plating solution composition of the present invention. As a metal or an alloy thereof having a higher ionization tendency than silver, nickel, copper, tin, cobalt or an alloy thereof is preferable, nickel, copper or an alloy thereof is more preferable, and nickel or a nickel alloy is particularly preferable.
In the silver plating method of the present invention, the temperature of the silver plating solution composition for immersing the metal or its alloy having a higher ionization tendency than silver is not particularly limited, but is preferably 10 to 90°C, and preferably 20 to 60°C. Is particularly preferable.
本発明の銀めっき方法における、銀よりもイオン化傾向の高い金属またはその合金を浸漬する銀めっき液組成物の温度は、特に制限されないが、１０～９０℃であることが好ましく、２０～６０℃であることが特に好ましい。 The present invention also relates to a silver plating method including a step of immersing a metal or an alloy thereof having a higher ionization tendency than silver in the silver plating solution composition of the present invention. As a metal or an alloy thereof having a higher ionization tendency than silver, nickel, copper, tin, cobalt or an alloy thereof is preferable, nickel, copper or an alloy thereof is more preferable, and nickel or a nickel alloy is particularly preferable.
In the silver plating method of the present invention, the temperature of the silver plating solution composition for immersing the metal or its alloy having a higher ionization tendency than silver is not particularly limited, but is preferably 10 to 90°C, and preferably 20 to 60°C. Is particularly preferable.
本発明の銀めっき方法により形成される銀めっき皮膜の厚さは、特に制限されないが、０．００１～３μｍであることが好ましく、０．００５～２μｍであることがより好ましく、０．０１～１μｍであることが特に好ましい。
The thickness of the silver plating film formed by the silver plating method of the present invention is not particularly limited, but is preferably 0.001 to 3 μm, more preferably 0.005 to 2 μm, and 0.01 to Particularly preferably, it is 1 μm.
さらに、本発明は、本発明の銀めっき方法により銀めっき皮膜が形成された、銀めっき処理品にも関する。
Further, the present invention also relates to a silver-plated product having a silver plating film formed by the silver plating method of the present invention.
次に、本発明の銀めっき液組成物について、以下に記載する実施例によってさらに詳細に説明するが、本発明はこれらに限定されるものではない。
Next, the silver plating solution composition of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
[チオ硫酸銀錯体の形成の確認]
本発明の銀めっき液組成物中にチオ硫酸銀錯体が形成されていることを確認するために、以下の評価を行った。
５０ｍｍｏｌ／Ｌ濃度のチオ硫酸ナトリウム水溶液に対して２０ｍｍｏｌ／Ｌ濃度となる量の塩化銀を加え、室温下でよく撹拌し無色透明の均一溶液（チオ硫酸ナトリウムと塩化銀との混合水溶液）を得た。また、参照試料として、５０ｍｍｏｌ／Ｌ濃度のチオ硫酸ナトリウム水溶液を得た。これら２種の水溶液を、それぞれ、体積比で１００倍に希釈したものを分析試料とし、アニオン型イオンクロマトグラフィー（島津製作所製カラムＩＣ－Ａ１、同社製電気伝導度検出器ＣＤＤ－６Ａ）を使用して分析を行った。結果を表１および図１に示す。図１における実線のチャートはチオ硫酸ナトリウムと塩化銀との混合水溶液の結果を表し、破線のチャートはチオ硫酸ナトリウム水溶液の結果を表す。 [Confirmation of formation of silver thiosulfate complex]
The following evaluations were performed in order to confirm that a silver thiosulfate complex was formed in the silver plating solution composition of the present invention.
To the 50 mmol/L sodium thiosulfate aqueous solution, 20 mmol/L concentration of silver chloride was added and well stirred at room temperature to obtain a colorless transparent homogeneous solution (mixed aqueous solution of sodium thiosulfate and silver chloride). It was As a reference sample, an aqueous solution of sodium thiosulfate having a concentration of 50 mmol/L was obtained. Anion type ion chromatography (Shimadzu column IC-A1, company conductivity detector CDD-6A) was used as an analytical sample by diluting these two types of aqueous solutions 100 times by volume. And analyzed. The results are shown in Table 1 and FIG. The solid line chart in FIG. 1 represents the result of a mixed aqueous solution of sodium thiosulfate and silver chloride, and the broken line chart represents the result of a sodium thiosulfate aqueous solution.
本発明の銀めっき液組成物中にチオ硫酸銀錯体が形成されていることを確認するために、以下の評価を行った。
５０ｍｍｏｌ／Ｌ濃度のチオ硫酸ナトリウム水溶液に対して２０ｍｍｏｌ／Ｌ濃度となる量の塩化銀を加え、室温下でよく撹拌し無色透明の均一溶液（チオ硫酸ナトリウムと塩化銀との混合水溶液）を得た。また、参照試料として、５０ｍｍｏｌ／Ｌ濃度のチオ硫酸ナトリウム水溶液を得た。これら２種の水溶液を、それぞれ、体積比で１００倍に希釈したものを分析試料とし、アニオン型イオンクロマトグラフィー（島津製作所製カラムＩＣ－Ａ１、同社製電気伝導度検出器ＣＤＤ－６Ａ）を使用して分析を行った。結果を表１および図１に示す。図１における実線のチャートはチオ硫酸ナトリウムと塩化銀との混合水溶液の結果を表し、破線のチャートはチオ硫酸ナトリウム水溶液の結果を表す。 [Confirmation of formation of silver thiosulfate complex]
The following evaluations were performed in order to confirm that a silver thiosulfate complex was formed in the silver plating solution composition of the present invention.
To the 50 mmol/L sodium thiosulfate aqueous solution, 20 mmol/L concentration of silver chloride was added and well stirred at room temperature to obtain a colorless transparent homogeneous solution (mixed aqueous solution of sodium thiosulfate and silver chloride). It was As a reference sample, an aqueous solution of sodium thiosulfate having a concentration of 50 mmol/L was obtained. Anion type ion chromatography (Shimadzu column IC-A1, company conductivity detector CDD-6A) was used as an analytical sample by diluting these two types of aqueous solutions 100 times by volume. And analyzed. The results are shown in Table 1 and FIG. The solid line chart in FIG. 1 represents the result of a mixed aqueous solution of sodium thiosulfate and silver chloride, and the broken line chart represents the result of a sodium thiosulfate aqueous solution.
表１から明らかなように、チオ硫酸ナトリウム水溶液と塩化銀との混合水溶液からは、添加した塩化銀とほぼ同一濃度のＣｌ－イオンが遊離イオンとして検出され、添加した塩化銀とほぼ同一濃度分だけ減少した値としてＳ２Ｏ３
２－イオンが検出された。この結果から、チオ硫酸ナトリウムと塩化銀との混合水溶液中で上記（１）式に従う反応が生じ、チオ硫酸銀錯体が形成されたことは明らかである。また、同様のことが、図１におけるＣｌ－（保持時間：約２．５分）およびＳ２Ｏ３
２－（保持時間：約８分）の各ピーク面積の増減からも確認することができた。
As is clear from Table 1, in the mixed aqueous solution of sodium thiosulfate aqueous solution and silver chloride, Cl − ions having almost the same concentration as the added silver chloride were detected as free ions, and the concentration of the same concentration as the added silver chloride was almost the same. The S 2 O 3 2− ion was detected as a value decreased only by the above. From this result, it is clear that the reaction according to the above formula (1) occurred in a mixed aqueous solution of sodium thiosulfate and silver chloride to form a silver thiosulfate complex. The same thing can be confirmed from the increase and decrease of the peak areas of Cl − (retention time: about 2.5 minutes) and S 2 O 3 2− (retention time: about 8 minutes) in FIG. It was
［銀めっき液組成物の調製］
（実施例１～２）
チオ硫酸ナトリウム、塩化銀およびエチレンジアミン四酢酸を水に溶解させ、得られた水溶液に対して水酸化ナトリウム水溶液を添加することでｐＨを調整し、表２に示す成分濃度およびｐＨをそれぞれ有する実施例１および２の銀めっき液組成物を得た。 [Preparation of silver plating solution composition]
(Examples 1 and 2)
Examples in which sodium thiosulfate, silver chloride and ethylenediaminetetraacetic acid were dissolved in water and the pH was adjusted by adding an aqueous sodium hydroxide solution to the obtained aqueous solution, and the component concentrations and pHs shown in Table 2 were obtained. The silverplating solution compositions 1 and 2 were obtained.
（実施例１～２）
チオ硫酸ナトリウム、塩化銀およびエチレンジアミン四酢酸を水に溶解させ、得られた水溶液に対して水酸化ナトリウム水溶液を添加することでｐＨを調整し、表２に示す成分濃度およびｐＨをそれぞれ有する実施例１および２の銀めっき液組成物を得た。 [Preparation of silver plating solution composition]
(Examples 1 and 2)
Examples in which sodium thiosulfate, silver chloride and ethylenediaminetetraacetic acid were dissolved in water and the pH was adjusted by adding an aqueous sodium hydroxide solution to the obtained aqueous solution, and the component concentrations and pHs shown in Table 2 were obtained. The silver
［銀めっき皮膜の形成と評価］
（実施例３）
縦２ｃｍ×横１ｃｍ×厚み０．１ｍｍの銅圧延板に対して、非特許文献１に記載された下記の工程Ａに従い、無電解ニッケル皮膜を形成させた。なお、無電解ニッケルめっきは、次亜リン酸を還元剤とするめっき浴を使用した。 [Formation and evaluation of silver plating film]
(Example 3)
An electroless nickel film was formed on a rolled copper plate having a length of 2 cm, a width of 1 cm, and a thickness of 0.1 mm according to the following step A described in Non-Patent Document 1. The electroless nickel plating used a plating bath containing hypophosphorous acid as a reducing agent.
（実施例３）
縦２ｃｍ×横１ｃｍ×厚み０．１ｍｍの銅圧延板に対して、非特許文献１に記載された下記の工程Ａに従い、無電解ニッケル皮膜を形成させた。なお、無電解ニッケルめっきは、次亜リン酸を還元剤とするめっき浴を使用した。 [Formation and evaluation of silver plating film]
(Example 3)
An electroless nickel film was formed on a rolled copper plate having a length of 2 cm, a width of 1 cm, and a thickness of 0.1 mm according to the following step A described in Non-Patent Document 1. The electroless nickel plating used a plating bath containing hypophosphorous acid as a reducing agent.
次いで、無電解ニッケル皮膜が形成された前記銅圧延板を、３０℃に保たれた実施例１の銀めっき液組成物に３０分間浸漬することによって、白色無光沢の銀めっき皮膜を無電解ニッケル皮膜上にさらに形成させた。
Next, the rolled copper sheet having the electroless nickel coating formed thereon was immersed in the silver plating solution composition of Example 1 kept at 30° C. for 30 minutes to form a white matte silver-plated coating with electroless nickel. Further formed on the film.
得られた銀めっき皮膜の膜厚を蛍光Ｘ線膜厚計（日立ハイテクサイエンス製、ＦＴ９５００Ｘ）で測定したところ、０．３７μｍであった。また、得られた銀めっき皮膜に対し、ＪＩＳ Ｈ８５０４「めっきの密着性試験方法」に基づきテープテストにて評価したところ、剥離は発生せず密着性は良好であった。
The film thickness of the obtained silver plating film was measured by a fluorescent X-ray film thickness meter (FT9500X, manufactured by Hitachi High-Tech Science), and it was 0.37 μm. Further, the obtained silver plating film was evaluated by a tape test based on JIS H8504 “Plating adhesion test method”. As a result, peeling did not occur and adhesion was good.
（実施例４）
アルミニウム皮膜が形成された縦１．５ｃｍ×横１．５ｃｍ×厚み０．８ｍｍのシリコンウェハに対して、非特許文献２に記載された下記の工程Ｂに従い、無電解ニッケル皮膜を形成させた。なお、無電解ニッケルめっきは、次亜リン酸を還元剤とするめっき浴を使用した。 (Example 4)
According to the following step B described inNon-Patent Document 2, an electroless nickel film was formed on a silicon wafer having a length of 1.5 cm×width 1.5 cm×thickness 0.8 mm on which an aluminum film was formed. The electroless nickel plating used a plating bath containing hypophosphorous acid as a reducing agent.
アルミニウム皮膜が形成された縦１．５ｃｍ×横１．５ｃｍ×厚み０．８ｍｍのシリコンウェハに対して、非特許文献２に記載された下記の工程Ｂに従い、無電解ニッケル皮膜を形成させた。なお、無電解ニッケルめっきは、次亜リン酸を還元剤とするめっき浴を使用した。 (Example 4)
According to the following step B described in
次いで、アルミニウム皮膜上に無電解ニッケル皮膜が形成された前記シリコンウェハを、３０℃に保たれた実施例２の銀めっき液組成物に３０分間浸漬することによって、白色無光沢の銀めっき皮膜を無電解ニッケル皮膜上にさらに形成させた。
Then, the silicon wafer having the electroless nickel film formed on the aluminum film was immersed in the silver plating solution composition of Example 2 kept at 30° C. for 30 minutes to form a white matte silver plating film. It was further formed on the electroless nickel film.
得られた銀めっき皮膜の膜厚を蛍光Ｘ線膜厚計（日立ハイテクサイエンス製、ＦＴ９５００Ｘ）で測定したところ、０．３５μｍであった。また、得られた銀めっき皮膜に対し、ＪＩＳ Ｈ８５０４「めっきの密着性試験方法」に基づきテープテストにて評価したところ、剥離は発生せず密着性は良好であった。
The thickness of the obtained silver plating film was measured with a fluorescent X-ray film thickness meter (FT9500X, manufactured by Hitachi High-Tech Science), and it was 0.35 μm. Further, the obtained silver plating film was evaluated by a tape test based on JIS H8504 “Plating adhesion test method”. As a result, peeling did not occur and adhesion was good.
（実施例５）
銅皮膜が形成された縦１．５ｃｍ×横１．５ｃｍ×厚み０．８ｍｍのシリコンウェハを使用し、上記の工程Ａに従い、無電解ニッケル皮膜を形成させた。なお、無電解ニッケルめっきは、次亜リン酸を還元剤とするめっき浴を使用した。 (Example 5)
Using a silicon wafer having a length of 1.5 cm×width 1.5 cm×thickness 0.8 mm on which a copper coating was formed, an electroless nickel coating was formed according to the above step A. The electroless nickel plating used a plating bath containing hypophosphorous acid as a reducing agent.
銅皮膜が形成された縦１．５ｃｍ×横１．５ｃｍ×厚み０．８ｍｍのシリコンウェハを使用し、上記の工程Ａに従い、無電解ニッケル皮膜を形成させた。なお、無電解ニッケルめっきは、次亜リン酸を還元剤とするめっき浴を使用した。 (Example 5)
Using a silicon wafer having a length of 1.5 cm×width 1.5 cm×thickness 0.8 mm on which a copper coating was formed, an electroless nickel coating was formed according to the above step A. The electroless nickel plating used a plating bath containing hypophosphorous acid as a reducing agent.
次いで、銅皮膜上に無電解ニッケル皮膜が形成された前記シリコンウェハを、３０℃に保たれた実施例２の銀めっき液組成物に６０分間浸漬することによって、白色無光沢の銀めっき皮膜を無電解ニッケル皮膜上にさらに形成させた。
Then, the silicon wafer having an electroless nickel film formed on the copper film was dipped in the silver plating solution composition of Example 2 kept at 30° C. for 60 minutes to form a white matte silver plating film. It was further formed on the electroless nickel film.
得られた銀めっき皮膜の膜厚を蛍光Ｘ線膜厚計（日立ハイテクサイエンス製、ＦＴ９５００Ｘ）で測定したところ、０．４１μｍであった。また、得られた銀めっき皮膜に対し、ＪＩＳ Ｈ８５０４「めっきの密着性試験方法」に基づきテープテストにて評価したところ、剥離は発生せず密着性は良好であった。
When the film thickness of the obtained silver plating film was measured by a fluorescent X-ray film thickness meter (FT9500X, manufactured by Hitachi High-Tech Science), it was 0.41 μm. Further, the obtained silver plating film was evaluated by a tape test based on JIS H8504 “Plating adhesion test method”. As a result, peeling did not occur and adhesion was good.
実施例５で得られた銀めっき皮膜の表面ＳＥＭ（走査電子顕微鏡）像（日立ハイテクサイエンス製、Ｓ－４８００）を図２に示す。また、銅皮膜上に無電解ニッケル皮膜が形成され、さらにその上に銀めっき皮膜が形成された前記シリコンウェハをＦＩＢ（収束イオンビーム）加工した、断面ＳＩＭ（走査イオン顕微鏡）像（日立ハイテクサイエンス製、ＦＢ－２２００）を図３に示す。図２および３から、銀めっき皮膜が無電解ニッケル皮膜上に緻密に形成されていることが確認された。
A surface SEM (scanning electron microscope) image (S-4800, manufactured by Hitachi High-Tech Science) of the silver plating film obtained in Example 5 is shown in FIG. Further, a cross-sectional SIM (scanning ion microscope) image obtained by FIB (focused ion beam) processing of the silicon wafer on which an electroless nickel film is formed on the copper film and a silver plating film is further formed thereon (Hitachi High-Tech Science) Manufactured by FB-2200) is shown in FIG. From FIGS. 2 and 3, it was confirmed that the silver plating film was densely formed on the electroless nickel film.
実施例１～５の結果から、本発明の銀めっき液組成物は、銀よりもイオン化傾向の高い金属またはその合金に対して良好な銀めっき皮膜を形成できることが確認された。
From the results of Examples 1 to 5, it was confirmed that the silver plating solution composition of the present invention can form a good silver plating film on a metal or its alloy having a higher ionization tendency than silver.
Claims (10)
- （Ａ）水溶性チオ硫酸化合物、（Ｂ）銀イオン源および（Ｃ）水を含有する、銀めっき液組成物。 A silver plating solution composition containing (A) a water-soluble thiosulfate compound, (B) a silver ion source, and (C) water.
- 銀イオン源として水溶性銀化合物を含有する、請求項１に記載の銀めっき液組成物。 The silver plating solution composition according to claim 1, which contains a water-soluble silver compound as a silver ion source.
- ｐＨが３～１４である、請求項１または２に記載の銀めっき液組成物。 The silver plating solution composition according to claim 1 or 2, which has a pH of 3 to 14.
- ｐＨ調整剤を含有する、請求項１～３のいずれか一項に記載の銀めっき液組成物。 The silver plating solution composition according to any one of claims 1 to 3, which contains a pH adjuster.
- キレート剤を含有する、請求項１～４のいずれか一項に記載の銀めっき液組成物。 The silver plating solution composition according to any one of claims 1 to 4, which contains a chelating agent.
- 銀よりもイオン化傾向の高い金属またはその合金のめっきのための、請求項１～５のいずれか一項に記載の銀めっき液組成物。 The silver plating solution composition according to any one of claims 1 to 5 for plating a metal or an alloy thereof having a higher ionization tendency than silver.
- 置換析出型である、請求項１～６のいずれか一項に記載の銀めっき液組成物。 The silver plating solution composition according to any one of claims 1 to 6, which is a substitution precipitation type.
- 請求項１～７のいずれか一項に記載の銀めっき液組成物に、銀よりもイオン化傾向の高い金属またはその合金を浸漬する工程を含む、銀めっき方法。 A silver plating method, which comprises a step of immersing a metal or an alloy thereof having a higher ionization tendency than silver in the silver plating solution composition according to any one of claims 1 to 7.
- 銀めっき液組成物の温度が２０～６０℃の範囲で、銀よりもイオン化傾向の高い金属またはその合金を浸漬する、請求項８に記載の銀めっき方法。 The silver plating method according to claim 8, wherein a metal or an alloy thereof having a higher ionization tendency than silver is immersed in the temperature of the silver plating solution composition in the range of 20 to 60°C.
- 請求項８または９に記載の方法により銀めっき皮膜が形成された、銀めっき処理品。 A silver-plated product having a silver-plated film formed by the method according to claim 8 or 9.
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| JP2019027492A JP7249804B6 (en) | 2019-02-19 | 2019-02-19 | Silver plating solution composition |
| JP2019-027492 | 2019-02-19 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002266079A (en) * | 2001-03-09 | 2002-09-18 | Shin Etsu Chem Co Ltd | Method for manufacturing silver coated conductive powder, silver coated conductive powder and electroless plating bath for coating conductive powder |
| JP2005199581A (en) * | 2004-01-16 | 2005-07-28 | Daiwa Fine Chemicals Co Ltd (Laboratory) | Method for producing plated foam for preventing electromagnetic wave interference, plated foam for preventing electromagnetic wave interference produced by the method, and electromagnetic wave interference preventing material produced by using the foam |
| JP2007116077A (en) * | 2005-09-26 | 2007-05-10 | Hitachi Chem Co Ltd | Pretreatment of copper surface and wiring substrate using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS60100679A (en) * | 1983-11-04 | 1985-06-04 | C Uyemura & Co Ltd | Method for coating silver to metallic material |
| US5322553A (en) * | 1993-02-22 | 1994-06-21 | Applied Electroless Concepts | Electroless silver plating composition |
| HK1093002A2 (en) * | 2006-11-16 | 2007-02-16 | Jing Li Fang | Alkalescent chemical silver plating solution |
-
2019
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002266079A (en) * | 2001-03-09 | 2002-09-18 | Shin Etsu Chem Co Ltd | Method for manufacturing silver coated conductive powder, silver coated conductive powder and electroless plating bath for coating conductive powder |
| JP2005199581A (en) * | 2004-01-16 | 2005-07-28 | Daiwa Fine Chemicals Co Ltd (Laboratory) | Method for producing plated foam for preventing electromagnetic wave interference, plated foam for preventing electromagnetic wave interference produced by the method, and electromagnetic wave interference preventing material produced by using the foam |
| JP2007116077A (en) * | 2005-09-26 | 2007-05-10 | Hitachi Chem Co Ltd | Pretreatment of copper surface and wiring substrate using the same |
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| JP2020132940A (en) | 2020-08-31 |
| TW202041713A (en) | 2020-11-16 |
| JP7249804B2 (en) | 2023-03-31 |
| JP7249804B6 (en) | 2023-04-21 |
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