JP6942791B2 - Electrolytic silver plating solution - Google Patents
Electrolytic silver plating solution Download PDFInfo
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- JP6942791B2 JP6942791B2 JP2019509812A JP2019509812A JP6942791B2 JP 6942791 B2 JP6942791 B2 JP 6942791B2 JP 2019509812 A JP2019509812 A JP 2019509812A JP 2019509812 A JP2019509812 A JP 2019509812A JP 6942791 B2 JP6942791 B2 JP 6942791B2
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/46—Electroplating: Baths therefor from solutions of silver
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/64—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of silver
Description
本発明は電解銀めっき液に関する。具体的には、高光沢・高反射率のめっき皮膜を得られる電解銀めっき液であって、銀源としてシアン化物を用いた電解銀めっき液に関する。さらには、高い硬度のめっき皮膜を得られる電解銀めっき液であって、銀源としてシアン化物を用いた電解銀めっき液に関する。 The present invention relates to an electrolytic silver plating solution. Specifically, the present invention relates to an electrolytic silver plating solution capable of obtaining a plating film having high gloss and high reflectance, which uses a cyanide as a silver source. Further, the present invention relates to an electrolytic silver plating solution that can obtain a plating film having a high hardness and that uses a cyanide as a silver source.
銀はその白い光沢から古来より宝飾品に多用されてきた。銀は貴金属の中では比較的産出量が多く、安価であるため、現代においてもシルバーアクセサリや食器など装飾用途に銀めっきが施されている。また、銀は室温における電気伝導率が金属で最大であるため、銀めっきはＩＣやトランジスタなど電子デバイス向けのリードフレームや基板などにも多く用いられている。さらに、銀は可視光線の反射率が全金属中最大であるために、ＬＥＤに代表される発光装置用のリードフレームや各種基板上には多くの場合銀めっきが施される。その他、軸受部品や銀の抗菌性を利用した用途にも銀めっきが用いられている。 Silver has been widely used in jewelry since ancient times because of its white luster. Since silver is a relatively large amount of precious metals and is inexpensive, it is still silver-plated for decorative purposes such as silver accessories and tableware. Further, since silver has the highest electrical conductivity of metal at room temperature, silver plating is often used for lead frames and substrates for electronic devices such as ICs and transistors. Further, since silver has the highest visible light reflectance among all metals, silver plating is often applied to lead frames for light emitting devices typified by LEDs and various substrates. In addition, silver plating is also used for bearing parts and applications that utilize the antibacterial properties of silver.
従来、銀めっきにより、光沢のある平滑な皮膜を析出させるため、様々な取り組みがなされてきた。例えば、特許文献１や特許文献２には、硫黄を含有する光沢剤の製造方法が記載されている。しかし、これらは得られるめっき皮膜の光沢度や反射特性について何ら検討されていない。 Conventionally, various efforts have been made to deposit a glossy and smooth film by silver plating. For example, Patent Document 1 and Patent Document 2 describe a method for producing a brightener containing sulfur. However, no studies have been conducted on the glossiness and reflection characteristics of the obtained plating film.
一方、銀皮膜の反射率を高めるために、特許文献３には銀めっきの結晶サイズを調整する技術が、特許文献４には高い反射率の銀めっき皮膜が得られる銀めっき液の技術が記載されている。しかし、これら従来の技術では、めっき前の下地の表面粗さや光沢度に銀めっき膜の光沢度・反射率が大きく影響を受ける。 On the other hand, in order to increase the reflectance of the silver film, Patent Document 3 describes a technique for adjusting the crystal size of silver plating, and Patent Document 4 describes a technique for a silver plating solution that can obtain a silver plating film with high reflectance. Has been done. However, in these conventional techniques, the glossiness and reflectance of the silver plating film are greatly affected by the surface roughness and glossiness of the base before plating.
上記事情から、従来の技術では、より光沢のある平滑な銀めっきを得るために、平滑な下地を用意しなければならない。しかし、実際のめっき工程では被めっき物の傷などの欠陥の対策として無光沢の銅もしくはニッケルめっきを施すことが一般的である。そこで、無光沢外観の下地にも、安定した高光沢・高反射率の銀皮膜が得られる銀めっき液の開発が望まれている。 Due to the above circumstances, in the prior art, a smooth substrate must be prepared in order to obtain a glossier and smoother silver plating. However, in the actual plating process, it is common to apply matte copper or nickel plating as a countermeasure against defects such as scratches on the object to be plated. Therefore, it is desired to develop a silver plating solution capable of obtaining a stable silver film having high gloss and high reflectance even on a base having a matte appearance.
そこで、本発明の目的は無光沢外観の下地にも、高光沢・高反射率の銀皮膜が得られる電解銀めっき液を提供することにある。さらには、高い硬度のめっき皮膜を得られる電解銀めっき液を提供することにある。 Therefore, an object of the present invention is to provide an electrolytic silver plating solution capable of obtaining a silver film having high gloss and high reflectance even on a base having a matte appearance. Another object of the present invention is to provide an electrolytic silver plating solution capable of obtaining a plating film having a high hardness.
本発明者は鋭意研究の結果、電解銀めっき液に飽和脂肪酸及び／又はその塩を添加することにより、無光沢外観の下地にも高光沢・高反射率の銀皮膜が得られることを見出した。さらには、電解銀めっき液に所定の濃度でセレン化合物を添加することにより、高い硬度のめっき皮膜を得られることを見出し、本発明を完成するに至った。上記課題を解決する本発明は、以下に記載するものである。 As a result of diligent research, the present inventor has found that by adding saturated fatty acids and / or salts thereof to the electrolytic silver plating solution, a silver film having high gloss and high reflectance can be obtained even on a base having a matte appearance. .. Furthermore, they have found that a plating film having a high hardness can be obtained by adding a selenium compound to an electrolytic silver plating solution at a predetermined concentration, and have completed the present invention. The present invention that solves the above problems is described below.
［１］ シアン化銀錯体、
電気伝導塩、
セレン化合物、
飽和脂肪酸及び／又はその塩
を含有することを特徴とする電解銀めっき液。[1] Silver cyanide complex,
Electrically conductive salt,
Selenium compound,
An electrolytic silver plating solution containing saturated fatty acid and / or a salt thereof.
［２］ 前記シアン化銀錯体が、シアン化銀、シアン化銀カリウム、シアン化銀ナトリウムから選ばれる少なくとも１種を含有する［１］に記載の電解銀めっき液。 [2] The electrolytic silver plating solution according to [1], wherein the silver cyanide complex contains at least one selected from silver cyanide, silver potassium cyanide, and sodium silver cyanide.
［３］ 前記シアン化銀錯体の濃度が、銀換算で１０〜１００ｇ／Ｌである［１］に記載の電解銀めっき液。 [3] The electrolytic silver plating solution according to [1], wherein the concentration of the silver cyanide complex is 10 to 100 g / L in terms of silver.
［４］ 前記電気伝導塩が、シアン塩、リン酸塩、硝酸塩、クエン酸塩、酒石酸塩から選ばれる少なくとも１種を含有する［１］に記載の電解銀めっき液。 [4] The electrolytic silver plating solution according to [1], wherein the electrically conductive salt contains at least one selected from cyanate, phosphate, nitrate, citrate, and tartrate.
［５］ 前記電気伝導塩の濃度が、５〜２５０ｇ／Ｌである［１］に記載の電解銀めっき液。 [5] The electrolytic silver plating solution according to [1], wherein the concentration of the electrically conductive salt is 5 to 250 g / L.
［６］ 前記セレン化合物が、セレノシアン酸、セレン酸、亜セレン酸、及びそれらの塩から選ばれる少なくとも１種を含有する［１］に記載の電解銀めっき液。 [6] The electrolytic silver plating solution according to [1], wherein the selenium compound contains at least one selected from selenic acid, selenic acid, selenous acid, and salts thereof.
［７］ 前記セレン化合物の濃度が、セレン換算で０．１〜２００ｍｇ／Ｌである［１］に記載の電解銀めっき液。 [7] The electrolytic silver plating solution according to [1], wherein the concentration of the selenium compound is 0.1 to 200 mg / L in terms of selenium.
［８］ 前記飽和脂肪酸及び／又はその塩が、デカン酸、ウンデカン酸、ラウリン酸、トリデカン酸、ミリスチン酸、ペンタデカン酸、パルミチン酸、ヘプタデカン酸、ステアリン酸、ノナデカン酸、アラキジン酸、及びそれらの塩から選ばれる少なくとも１種を含有する［１］に記載の電解銀めっき液。 [8] The saturated fatty acids and / or salts thereof are decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, and salts thereof. The electrolytic silver plating solution according to [1], which contains at least one selected from.
［９］ 前記飽和脂肪酸及び／又はその塩の濃度が、０．０１〜２０ｇ／Ｌである［１］に記載の電解銀めっき液。 [9] The electrolytic silver plating solution according to [1], wherein the concentration of the saturated fatty acid and / or a salt thereof is 0.01 to 20 g / L.
本発明の電解銀めっき液は無光沢外観の下地にも、安定して高光沢・高反射率の銀皮膜が得られる。これにより、平滑な下地を用意する必要がなくなり、コスト削減につながる。また、安定した性能が得られることから、製造歩留まりの向上も可能である。
所定の濃度でセレン化合物を添加すると、上記効果の他に、高い硬度のめっき皮膜が得られるという効果が得られる。The electrolytic silver plating solution of the present invention can stably obtain a silver film having high gloss and high reflectance even on a base having a matte appearance. This eliminates the need to prepare a smooth base, which leads to cost reduction. Moreover, since stable performance can be obtained, it is possible to improve the manufacturing yield.
When the selenium compound is added at a predetermined concentration, in addition to the above effects, an effect of obtaining a plating film having a high hardness can be obtained.
以下、本発明の電解銀めっき液を構成する各成分について説明する。
本発明の電解銀めっき液は、銀塩としてシアン化銀錯体と、電気伝導塩と、セレン塩と、飽和脂肪酸塩を含有する。Hereinafter, each component constituting the electrolytic silver plating solution of the present invention will be described.
The electrolytic silver plating solution of the present invention contains a silver cyanide complex, an electrically conductive salt, a selenium salt, and a saturated fatty acid salt as silver salts.
［シアン化銀錯体］
本発明の電解銀めっき液には、銀源として公知のシアン化銀錯体を制限なく使用することができる。シアン化銀錯体としては、シアン化銀、シアン化銀カリウム、シアン化銀ナトリウムが例示される。これらは単独で用いてもよく、２種類以上を併用してもよい。[Silver cyanide complex]
In the electrolytic silver plating solution of the present invention, a silver cyanide complex known as a silver source can be used without limitation. Examples of the silver cyanide complex include silver cyanide, silver potassium cyanide, and sodium silver cyanide. These may be used alone or in combination of two or more.
シアン化銀錯体の配合量は銀イオン濃度として、１０〜１００ｇ／Ｌであることが好ましく、２０〜７０ｇ／Ｌであることがより好ましい。銀イオン濃度が１０ｇ／Ｌ未満である場合、析出効率が低下するうえ、所望の銀膜厚を得られなくなる場合がある。一方、銀イオン濃度が１００ｇ／Ｌを超える場合、被めっき物によるめっき液の持ち出しによる銀塩のロスが多くなり経済的ではない。 The blending amount of the silver cyanide complex is preferably 10 to 100 g / L and more preferably 20 to 70 g / L as the silver ion concentration. When the silver ion concentration is less than 10 g / L, the precipitation efficiency is lowered and the desired silver film thickness may not be obtained. On the other hand, when the silver ion concentration exceeds 100 g / L, the loss of silver salt due to the removal of the plating solution by the object to be plated increases, which is not economical.
［電気伝導塩］
本発明の電解銀めっき液に配合される電気伝導塩は、水溶液中で電気伝導性を有するものであれば特に種類は問わないが、工業的に安定して使用することや電解銀めっき液を経済的に製造するために、シアン塩、りん酸塩、硝酸塩、クエン酸塩、酒石酸から選ばれる少なくとも１種を含有することが好ましい。その他、可溶性有機酸塩なども好ましい。これらは単独で用いてもよく、２種類以上を併用してもよい。シアン塩としては、シアン化カリウムやシアン化ナトリウムなどが例示される。りん酸塩としては、りん酸カリウム、りん酸ナトリウム、りん酸アンモニウム、ピロリン酸カリウムなどが例示される。硝酸塩としては、硝酸カリウム、硝酸ナトリウム、硝酸アンモニウムなどが例示される。クエン酸塩としては、クエン酸カリウム、クエン酸ナトリウム、クエン酸アンモニウムなどが例示される。酒石酸としては、酒石酸カリウム、酒石酸ナトリウム、酒石酸ナトリウムカリウムなどが例示される。[Electrical conductive salt]
The electrically conductive salt blended in the electrolytic silver plating solution of the present invention may be of any type as long as it has electrical conductivity in an aqueous solution, but it can be used industrially stably and the electrolytic silver plating solution can be used. For economical production, it is preferable to contain at least one selected from cyanate, phosphate, nitrate, citrate and tartrate. In addition, soluble organic acid salts and the like are also preferable. These may be used alone or in combination of two or more. Examples of the cyanide include potassium cyanide and sodium cyanide. Examples of the phosphate include potassium phosphate, sodium phosphate, ammonium phosphate, potassium pyrophosphate and the like. Examples of the nitrate include potassium nitrate, sodium nitrate, ammonium nitrate and the like. Examples of the citrate include potassium citrate, sodium citrate, ammonium citrate and the like. Examples of tartaric acid include potassium tartrate, sodium tartrate, and potassium sodium tartrate.
本発明の電解銀めっき液の電気伝導塩の濃度は、５〜２５０ｇ／Ｌであることが好ましく、５０〜１５０ｇ／Ｌであることがより好ましい。電気伝導塩の濃度が５ｇ／Ｌ未満である場合、めっき液の電気抵抗が高くなりすぎ、適切な陰極電流密度によるめっき製造ができない場合がある。 The concentration of the electrically conductive salt in the electrolytic silver plating solution of the present invention is preferably 5 to 250 g / L, more preferably 50 to 150 g / L. If the concentration of the electrically conductive salt is less than 5 g / L, the electrical resistance of the plating solution becomes too high, and plating production with an appropriate cathode current density may not be possible.
［セレン化合物］
本発明の電解銀めっき液に配合されるセレン化合物は、セレンを含有する化合物であって、特にセレノシアン酸及びその塩、セレン酸及びその塩、亜セレン酸及びその塩が好ましい。セレノシアン酸及びその塩としては、セレノシアン酸、セレノシアン酸カリウムが例示される。セレン酸及びその塩としては、セレン酸、セレン酸カリウム、セレン酸ナトリウムが例示される。亜セレン酸及びその塩としては、亜セレン酸、亜セレン酸カリウム、亜セレン酸ナトリウム、二酸化セレンなどが例示される。これらは単独で用いてもよく、２種類以上を併用してもよい。[Selenium compound]
The selenium compound to be blended in the electrolytic silver plating solution of the present invention is a selenium-containing compound, and selenic acid and its salt, selenic acid and its salt, selenous acid and its salt are particularly preferable. Examples of selenosian acid and salts thereof include selenosian acid and potassium selenosianate. Examples of selenic acid and salts thereof include selenic acid, potassium selenate, and sodium selenate. Examples of selenous acid and salts thereof include selenous acid, potassium selenate, sodium selenite, selenium dioxide and the like. These may be used alone or in combination of two or more.
本発明の電解銀めっき液のセレン化合物の濃度は、セレン濃度として０．１〜２００ｍｇ／Ｌであることが好ましい。セレン化合物の配合量が上記濃度から外れると、光沢のある銀皮膜を得られなかったり、適切な陰極電流密度によるめっき製造ができない場合がある。
光沢性が優れる銀皮膜を得るためのセレン濃度は、０．１〜２００ｍｇ／Ｌであることが好ましい。この範囲でセレン化合物を含有する場合、光沢性が優れる銀皮膜を得ることができる。０．１ｍｇ／Ｌ未満の場合、銀皮膜の光沢性が十分に向上しない場合がある。２００ｍｇ／Ｌを超える場合、経済的に不利となる。光沢性を向上させる観点からは、セレン濃度は０．１〜８０ｍｇ／Ｌであっても良く、経済的には１〜１０ｍｇ／Ｌであることが好ましい。
皮膜硬度が高い銀皮膜を得るためのセレン濃度は、３０〜２００ｍｇ／Ｌであることが好ましい。この範囲でセレン化合物を含有する場合、光沢性が優れ、かつ皮膜硬度が高い銀皮膜を得ることができる。８０ｍｇ／Ｌ未満の場合、銀皮膜の硬度が十分に向上しない場合がある。２００ｍｇ／Ｌを超える場合、経済的に不利となる。皮膜硬度及び光沢性を向上させる観点からは、セレン濃度は５０〜１８０ｍｇ／Ｌであってあることがより好ましく、経済的には８０〜１６０ｍｇ／Ｌであることがさらに好ましい。The concentration of the selenium compound in the electrolytic silver plating solution of the present invention is preferably 0.1 to 200 mg / L as the selenium concentration. If the blending amount of the selenium compound deviates from the above concentration, a glossy silver film may not be obtained, or plating production with an appropriate cathode current density may not be possible.
The selenium concentration for obtaining a silver film having excellent gloss is preferably 0.1 to 200 mg / L. When a selenium compound is contained in this range, a silver film having excellent gloss can be obtained. If it is less than 0.1 mg / L, the glossiness of the silver film may not be sufficiently improved. If it exceeds 200 mg / L, it is economically disadvantageous. From the viewpoint of improving the glossiness, the selenium concentration may be 0.1 to 80 mg / L, and economically preferably 1 to 10 mg / L.
The selenium concentration for obtaining a silver film having a high film hardness is preferably 30 to 200 mg / L. When the selenium compound is contained in this range, a silver film having excellent glossiness and high film hardness can be obtained. If it is less than 80 mg / L, the hardness of the silver film may not be sufficiently improved. If it exceeds 200 mg / L, it is economically disadvantageous. From the viewpoint of improving the film hardness and glossiness, the selenium concentration is more preferably 50 to 180 mg / L, and economically more preferably 80 to 160 mg / L.
［飽和脂肪酸（塩）］
本発明の電解銀めっき液に配合される飽和脂肪酸及び／又はその塩（以下、「飽和脂肪酸（塩）」と略記する）は、炭素数１０〜２０の飽和脂肪酸及び／又はその塩であって、具体的にはデカン酸、ウンデカン酸、ラウリン酸、トリデカン酸、ミリスチン酸、ペンタデカン酸、パルミチン酸、ヘプタデカン酸、ステアリン酸、ノナデカン酸、アラキジン酸、及びこれらの塩などが例示される。これらは単独で用いてもよく、２種類以上を併用してもよい。[Saturated fatty acids (salts)]
The saturated fatty acid and / or a salt thereof (hereinafter, abbreviated as "saturated fatty acid (salt)") blended in the electrolytic silver plating solution of the present invention is a saturated fatty acid having 10 to 20 carbon atoms and / or a salt thereof. Specific examples thereof include decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanic acid, arachidic acid, and salts thereof. These may be used alone or in combination of two or more.
本発明の電解銀めっき液の飽和脂肪酸（塩）の濃度は０．０１〜２０ｇ／Ｌであることが好ましく、０．１〜５ｇ／Ｌであることがより好ましい。飽和脂肪酸（塩）の濃度が０．０１ｇ／Ｌ未満である場合、下地膜の表面粗さが銀めっき膜の光沢に影響する。飽和脂肪酸（塩）の濃度が２０ｇ／Ｌを超える場合、沈殿が生じる恐れがあるほか、めっき液の粘度が上昇しすぎることにより、適切な陰極電流密度によるめっき製造ができなかったり、めっき液の持ち出し量が増加する場合がある。 The concentration of the saturated fatty acid (salt) in the electrolytic silver plating solution of the present invention is preferably 0.01 to 20 g / L, more preferably 0.1 to 5 g / L. When the concentration of saturated fatty acid (salt) is less than 0.01 g / L, the surface roughness of the base film affects the gloss of the silver-plated film. If the concentration of saturated fatty acid (salt) exceeds 20 g / L, precipitation may occur, and the viscosity of the plating solution may increase too much, making it impossible to manufacture plating with an appropriate cathode current density, or the plating solution. The amount taken out may increase.
［その他の成分］
本発明の電解銀めっき液においては、上記成分の他に、粘度を低下させ、銀皮膜のムラ発生を抑制するために、本発明の目的を損なわない範囲で界面活性剤などの成分を含有させることができる。界面活性剤としては、ポリオキシエチレンアルキルエーテル硫酸ナトリウムなどの陰イオン性界面活性剤や、ポリオキシエチレンアルキルエーテル縮合物などの非イオン性界面活性剤が例示される。[Other ingredients]
In the electrolytic silver plating solution of the present invention, in addition to the above components, in order to reduce the viscosity and suppress the occurrence of unevenness of the silver film, a component such as a surfactant is contained within a range that does not impair the object of the present invention. be able to. Examples of the surfactant include anionic surfactants such as polyoxyethylene alkyl ether sodium sulfate and nonionic surfactants such as polyoxyethylene alkyl ether condensates.
本発明の電解銀めっき液は、ｐＨ６〜１４で使用することが好ましく、ｐＨ８〜１３で使用することがより好ましい。ｐＨが６未満である場合、陰極電流効率が低下し、得られる皮膜が十分な膜厚にならない。ｐＨが１４を超える場合、得られる皮膜の外観が悪化する。 The electrolytic silver plating solution of the present invention is preferably used at pH 6 to 14, and more preferably at pH 8 to 13. If the pH is less than 6, the cathode current efficiency is reduced and the resulting film is not sufficiently thick. If the pH exceeds 14, the appearance of the resulting film will deteriorate.
本発明の電解銀めっき液の液温は、１０〜６０℃が好ましく、２０〜４０℃がより好ましい。めっき浴の液温が上記の範囲を外れると、陰極電流効率が低下したり、めっき浴の安定性を損なったりするため好ましくない。 The liquid temperature of the electrolytic silver plating solution of the present invention is preferably 10 to 60 ° C, more preferably 20 to 40 ° C. If the liquid temperature of the plating bath is out of the above range, the efficiency of the cathode current is lowered and the stability of the plating bath is impaired, which is not preferable.
本発明の電解銀めっき液を用いる場合の電流密度は、めっき液の組成や液温、その他の条件を勘案して設定される。例えば、めっき液を液温２０〜３０℃で使用する場合、電流密度は３〜１５Ａ／ｄｍ２に設定することが好ましい。適切な電流密度に設定されない場合、めっき外観やめっき皮膜の特性に異常が生じるおそれがある。また、めっき浴が不安定になり、めっき液成分の分解が生じる場合がある。
The current density when the electrolytic silver plating solution of the present invention is used is set in consideration of the composition of the plating solution, the liquid temperature, and other conditions. For example, when the plating solution is used at a liquid temperature of 20 to 30 ° C., the current density is preferably set to 3 to 15 A / dm 2. If the current density is not set appropriately, abnormalities may occur in the appearance of the plating and the characteristics of the plating film. In addition, the plating bath may become unstable and the plating solution components may be decomposed.
以下、実施例によって本発明を具体的に説明する。本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples. The present invention is not limited to these examples.
（実施例１〜１２、比較例１〜５）
被めっき物としては０．１ｄｍ２の銅板を用いた。まず、これに、アルカリ系の脱脂液で脱脂処理を施した後、希硫酸で中和した。その後、シアン浴により無光沢の銅めっきを約１μｍ施した。その後、シアン系ストライク浴により銀めっきを約０．１μｍ施した。(Examples 1 to 12, Comparative Examples 1 to 5)
A 0.1 dm 2 copper plate was used as the object to be plated. First, this was degreased with an alkaline degreasing solution and then neutralized with dilute sulfuric acid. Then, a matte copper plating of about 1 μm was applied in a cyan bath. Then, about 0.1 μm of silver plating was applied in a cyan-based strike bath.
表１、２に記載する組成で、実施例１〜１２、比較例１〜５のめっき液を調製した。調製しためっき液１Ｌ中に被めっき物を浸漬し、表１、２に記載する条件下で、銀膜厚が４μｍになるまで電解銀めっき操作を行い、清浄な純水で洗浄した後、乾燥した。なお、表１中のセレン化合物の濃度はセレン換算量である。 The plating solutions of Examples 1 to 12 and Comparative Examples 1 to 5 were prepared with the compositions shown in Tables 1 and 2. The object to be plated is immersed in 1 L of the prepared plating solution, electrolytic silver plating is performed until the silver film thickness reaches 4 μm under the conditions shown in Tables 1 and 2, washed with clean pure water, and then dried. bottom. The concentration of the selenium compound in Table 1 is a selenium equivalent amount.
以上のようにして得られた実施例１〜１２、比較例１〜５の銀皮膜について光沢度と反射率を計測した。ここでいう光沢度とは、日本電色工業株式会社製のデンシトメーター ＮＤ−１１で測定される数値である。また、ここでいう反射率とは、コニカミノルタセンシング株式会社製分光測色計 ＣＭ−２６００ｄで測定した４５０ｎｍのＳＣＩ測定値である。測定結果は表１及び２に示す。 The glossiness and reflectance of the silver films of Examples 1 to 12 and Comparative Examples 1 to 5 obtained as described above were measured. The glossiness referred to here is a numerical value measured by a densitometer ND-11 manufactured by Nippon Denshoku Industries Co., Ltd. The reflectance here is a 450 nm SCI measurement value measured by a spectrocolorimeter CM-2600d manufactured by Konica Minolta Sensing Co., Ltd. The measurement results are shown in Tables 1 and 2.
実施例１〜１２で得られた銀皮膜はいずれも光沢度が２．０以上、反射率が９８％以上であった。色調は銀白色で、ムラがなく良好な外観であった。浴安定性も良好であった。 The silver films obtained in Examples 1 to 12 had a glossiness of 2.0 or more and a reflectance of 98% or more. The color tone was silvery white, and the appearance was even and good. The bath stability was also good.
比較例１〜５で得られた銀皮膜はいずれも光沢度が１．８に満たず、反射率も９７％以下であった。色調は銀白色で、ムラがなく良好な外観であった。浴安定性も良好であった。比較例６で得られた銀皮膜はヤケ外観で非常に脆いめっき皮膜となった。浴安定性は良好であった。 The silver films obtained in Comparative Examples 1 to 5 had a glossiness of less than 1.8 and a reflectance of 97% or less. The color tone was silvery white, and the appearance was even and good. The bath stability was also good. The silver film obtained in Comparative Example 6 was a very brittle plating film with a discolored appearance. The bath stability was good.
（実施例１３〜２４、比較例７〜１１、参考例１〜２）
被めっき物としては０．１ｄｍ２の銅板を用いた。まず、これに、アルカリ系の脱脂液で脱脂処理を施したあと、希硫酸で中和した。その後、シアン浴により無光沢の銅めっきを約１μｍ施した。その後、シアン系ストライク浴により銀めっきを約０．１μｍ施した。(Examples 13 to 24, Comparative Examples 7 to 11, Reference Examples 1 to 2)
A 0.1 dm 2 copper plate was used as the object to be plated. First, this was degreased with an alkaline degreasing solution and then neutralized with dilute sulfuric acid. Then, a matte copper plating of about 1 μm was applied in a cyan bath. Then, about 0.1 μm of silver plating was applied in a cyan-based strike bath.
表３、４に記載する組成で、実施例１３〜２４、比較例７〜１１、参考例１〜２のめっき液を調製した。調製されためっき液１Ｌ中に被めっき物を浸漬し、表３、４に記載する条件下で、銀膜厚が２０μｍになるまで電解銀めっき操作を行い、清浄な純水で洗浄した後、乾燥した。 The plating solutions of Examples 13 to 24, Comparative Examples 7 to 11, and Reference Examples 1 to 2 were prepared with the compositions shown in Tables 3 and 4. The object to be plated is immersed in 1 L of the prepared plating solution, electrolytic silver plating is performed under the conditions shown in Tables 3 and 4 until the silver film thickness reaches 20 μm, and the mixture is washed with clean pure water. It was dry.
以上のようにして得られた実施例１３〜２４、比較例７〜１１、参考例１〜２の銀皮膜について硬度を計測した。硬度の測定は、めっきの直後及びめっきの６ヶ月後に行った。
ここでいう硬度とは、ミツトヨ製微小硬さ試験機 ＭＶＫ−Ｈ３００ を用いて試験力１０ｇで１０秒保持した際に得られるマイクロビッカース硬さであり、５回測定して最小値および最大値を除いた３回分の結果を平均したものである。
参考例１、２で得られた銀皮膜の光沢度はそれぞれ２．０５、 ２．０２であり、光沢には優れるものの硬度特性は得られなかった。
The hardness of the silver films of Examples 13 to 24, Comparative Examples 7 to 11, and Reference Examples 1 and 2 obtained as described above was measured. The hardness was measured immediately after plating and 6 months after plating.
The hardness referred to here is the Micro Vickers hardness obtained when the Mitutoyo micro-hardness tester MVK-H300 is used to hold the test force at 10 g for 10 seconds, and the minimum and maximum values are measured 5 times. It is the average of the results of the three times excluding.
The glossiness of the silver films obtained in Reference Examples 1 and 2 was 2.05 and 2.02, respectively, and although the glossiness was excellent, the hardness characteristics could not be obtained.
Claims (1)
シアン塩、リン酸塩、硝酸塩、クエン酸塩、酒石酸塩から選ばれる少なくとも１種を含有する電気伝導塩を５〜２５０ｇ／Ｌと、
セレノシアン酸、セレン酸、亜セレン酸、及びそれらの塩から選ばれる少なくとも１種を含有するセレン化合物をセレン換算で０．１〜２００ｍｇ／Ｌと、
デカン酸、ウンデカン酸、ラウリン酸、トリデカン酸、ミリスチン酸、ペンタデカン酸、パルミチン酸、ヘプタデカン酸、ステアリン酸、ノナデカン酸、アラキジン酸、及びそれらの塩から選ばれる少なくとも１種を含有する飽和脂肪酸及び／又はその塩を０．０１〜２０ｇ／Ｌと、
を含有することを特徴とする電解銀めっき液。 A silver cyanide complex containing at least one selected from silver cyanide, silver potassium cyanide, and sodium silver cyanide is 10 to 100 g / L in terms of silver .
An electrically conductive salt containing at least one selected from cyanate, phosphate, nitrate, citrate, and tartrate is 5 to 250 g / L.
A selenium compound containing at least one selected from selenosian acid, selenic acid, selenous acid, and salts thereof is contained in an amount of 0.1 to 200 mg / L in terms of selenium .
Saturated fatty acids and / or containing at least one selected from decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecaneic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecane acid, aradecic acid, and salts thereof. Or its salt is 0.01 to 20 g / L,
An electrolytic silver plating solution characterized by containing.
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