JP4308969B2 - Plating film, decorative product including the same, and method of manufacturing plating film - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、めっき皮膜、それを備えた装飾品及びめっき皮膜の製造方法に関する。さらに詳しくは、優れた耐変色性を有する金及び銅の組成からなるピンクゴールドの色調を有するめっき皮膜、それを備えた美麗な外観（色調）を長期間保持し得る装飾品及びめっき皮膜の効率的な製造方法に関する。
【０００２】
【従来の技術】
近年、その表面に金属部分を有する、工芸品、家具什器、時計、電気・電子機器等の装飾品は、そのピンクゴールドといわれる色調の豪華さ及び美麗さ等から、金及び銅の組成からなるめっき皮膜を備えてなるものが多く用いられている。このようなめっき皮膜は、通常、金の単相、銅の単相及び金と銅との固溶体相をそれぞれ所定の割合で含有するものであり、生地の表面にめっき皮膜を形成した後に、その後処理として、アルカリ性溶液、酸性溶液、及び水に浸漬させることにより洗浄し、乾燥を行うことにより得られるものである。
【０００３】
しかしながら、このような従来のめっき皮膜は、電圧をかけることによりめっき金属を強制的に析出させること、及び結晶構造が下地金属の影響を受けること等の理由のため、固溶体相の含有割合が小さく、金及び銅のそれぞれの単相部分があるものであり、かつ銅成分は、結晶として存在するよりも、むしろ粒界に多く存在するものと推定されるものである。このことは、後述する図１（めっき皮膜のＸ線回折による解析結果を示すチャート図）から裏付けられる。すなわち、図１における２つのピークのうち、右側のピークは固溶体相のピークを、左側のピークは金相のピークをそれぞれ示すが、めっき皮膜中の固溶体相のピーク値が比較的小さいこと、かつ金相のピークがあることから、固溶体相の含有割合が小さいものであることがわかる。また、金相のピークがあり、かつ後述するように、めっき膜を硝酸に浸漬することにより銅が溶出することから、金及び銅のそれぞれの単相部分があるものであることがわかる。更に、銅が硝酸により溶出すること、かつ銅相のピークが確認されないことから、銅は、結晶として存在するよりも、むしろ粒界に多く存在するものと推定されることがわかる。このようなめっき膜は、大気中又は酸化雰囲気下に放置されることにより、銅の単相部分が酸化して、ピンクゴールドの色調を有するめっき皮膜の色むらや変色を生じさせ、装飾品としての価値を著しく減じてしまうという問題があった。
【０００４】
【発明が解決しようとする課題】
本発明は、上述の問題に鑑みてなされたものであり、優れた耐変色性を有する金及び銅の組成からなるピンクゴールドの色調を有するめっき皮膜、それを備えた美麗な外観（色調）を長期間保持し得る装飾品及びめっき皮膜の効率的な製造方法を提供することを目的とする。
【０００５】
【課題を解決するための手段】
本発明者等は、上記目的を達成するため、鋭意研究した結果、銅成分の溶出量を減少させることにより、また、生地の表面に形成したピンクゴールドの色調を有するめっき皮膜を特定の条件で加熱処理を施して金の単相及び銅の単相を固溶体化し、皮膜表面の銅の単相を減少させることにより、満足し得るピンクゴールドの色調を有するめっき皮膜、それを備えた装飾品及びその製造方法が得られることを見出し、本発明を完成させた。すなわち、本発明は、以下のめっき皮膜、それを備えた装飾品及びめっき皮膜の製造方法を提供するものである。
【０００６】
［１］生地の表面に金６０〜８０重量％及び銅４０〜２０重量％の組成からなるピンクゴールドの色調を有するめっき皮膜を形成した後に、このめっき皮膜を備えた生地を、４００〜５５０℃の温度で５分間以上、非酸化性雰囲気条件下で加熱処理し、この雰囲気下で室温まで徐冷することによって得られた、金６０〜８０重量％及び銅４０〜２０重量％の組成からなるピンクゴールドの色調を有するめっき皮膜であって、２５℃にて５分間浸漬の条件で硝酸に浸漬したときの銅成分の溶出量が単位面積当たり３μｇ以下であることを特徴とするめっき皮膜。
【０００７】
［２］前記金成分及び銅成分に加えて、さらに金属光沢剤を、金成分及び銅成分の合計１００重量部に対して１０重量部以下含有することを特徴とする前記［１］に記載のめっき皮膜。
【０００８】
［３］前記金属光沢剤が、コバルト、ニッケル、アンチモン、セレン、パラジウム、スズ、インジウム、銀、カドミウム、鉄、及び亜鉛からなる群から選ばれる少なくとも１種を含むものである前記［２］に記載のめっき皮膜。
【０００９】
［４］前記［１］〜［３］のいずれかに記載のめっき皮膜をその生地の表面に備えてなる装飾品。
【００１０】
［５］前記生地が、耐熱性金属材料からなるものである前記［４］に記載の装飾品。
【００１１】
［６］生地の表面に金６０〜８０重量％及び銅４０〜２０重量％の組成からなるピンクゴールドの色調を有するめっき皮膜を形成した後に、このめっき皮膜を備えた生地を、４００〜５５０℃の温度で５分間以上、非酸化性雰囲気条件下で加熱処理し、この雰囲気下で室温まで徐冷することを特徴とするめっき皮膜の製造方法。
【００１２】
［７］前記めっき皮膜が、金成分及び銅成分に加えて、さらに金属光沢剤を、金成分及び銅成分の合計１００重量部に対して１０重量部以下含有するものである前記［６］に記載のめっき皮膜の製造方法。
【００１３】
［８］前記金属光沢剤が、コバルト、ニッケル、アンチモン、セレン、パラジウム、スズ、インジウム、銀、カドミウム、鉄、及び亜鉛からなる群から選ばれる少なくとも１種を含むものである前記［７］に記載のめっき皮膜の製造方法。
【００１４】
［９］前記生地が、耐熱性金属材料からなるものである前記［６］〜［８］のいずれかに記載のめっき皮膜の製造方法。
【００１５】
【発明の実施の形態】
以下、本発明のめっき皮膜、それを備えた装飾品及びめっき皮膜の製造方法の実施の形態を具体的に説明する。
Ｉ．めっき皮膜
本発明のめっき皮膜は、生地の表面に金６０〜８０重量％及び銅４０〜２０重量％の組成からなるピンクゴールドの色調を有するめっき皮膜を形成した後に、このめっき皮膜を備えた生地を、４００〜５５０℃の温度で５分間以上、非酸化性雰囲気条件下で加熱処理し、この雰囲気下で室温まで徐冷することによって得られた、金６０〜８０重量％及び銅４０〜２０重量％の組成からなるピンクゴールドの色調を有するめっき皮膜であって、２５℃にて５分間浸漬の条件で硝酸に浸漬したときの銅成分の溶出量が単位面積当たり３μｇ以下であることを特徴とするものである。
【００１６】
以下、さらに具体的に説明する。
１．組成
本発明のめっき皮膜は、生地の表面に金６０〜８０重量％及び銅４０〜２０重量％の組成からなるピンクゴールドの色調を有するめっき皮膜を形成した後に、このめっき皮膜を備えた生地を、４００〜５５０℃の温度で５分間以上、非酸化性雰囲気条件下で加熱処理し、この雰囲気下で室温まで徐冷することによって得られた、通常、金６０〜８０重量％及び銅４０〜２０重量％の組成からなるピンクゴールドの色調を有するものである。また、本発明のめっき皮膜は、厚付け性，光沢性向上のため、前記金成分及び銅成分に加えて、さらに金属光沢剤を、金成分及び銅成分の合計１００重量部に対して、１０重量部以下含有することが好ましく、５重量部以下含有することがさらに好ましい。
【００１７】
このような金属光沢剤としては特に制限はないが、例えば、コバルト、ニッケル、アンチモン、セレン、パラジウム、スズ、インジウム、銀、カドミウム、鉄、及び亜鉛からなる群から選ばれる少なくとも１種を含むものを挙げることができる。好ましくは、銀、カドミウム、パラジウム、コバルト、インジウム、又はセレンを含むものを挙げることができる。具体的には、シアン化銀、シアン化カドミウム、塩化パラジウム、硫酸コバルト、硫酸インジウム、亜セレン酸ナトリウム等を好適例として挙げることができる。
【００１８】
２．銅成分の溶出量
本発明のめっき皮膜は、２５℃にて５分間浸漬の条件で硝酸に浸漬したときの銅成分の溶出量が単位面積当たり３μｇ以下のものである。
銅成分の溶出量が単位面積当たり３μｇを超えると、めっき皮膜を２ヶ月間放置した場合、又は大気中、１５０℃のオーブン内で２５時間放置した場合、目視で認識できる程めっき皮膜の変色が著しい。
以下、銅成分の溶出量の測定方法について具体的に説明する。
まず、２５℃にて６０％硝酸に５分間浸漬する。その後、硝酸に溶解した銅の質量をＩＣＰ発光分光分析により測定する。
【００１９】
ＩＩ．めっき皮膜を備えた装飾品
本発明の装飾品は、前述のめっき皮膜をその生地の表面に備えてなるものである。
本発明に用いられる生地としては、その表面にめっき処理が可能な金属部分を含むものであれば特に制限はないが、熱処理温度によっては、生地の元素がめっき皮膜中に拡散したり、生地が変形したりすることがある点から、例えば、耐熱性金属材料からなるものを好適例として挙げることができる。このような耐熱性金属材料としては、例えば、ステンレス、チタン、真鍮等を挙げることができる。
本発明の装飾品は、前述のめっき皮膜をその生地の表面に備えてなるものであるため、金及び銅を主組成とするめっき皮膜特有の美麗なピンクゴールドの色調を有すると共に、大気中又は酸化雰囲気下の条件で長期間使用しても色むらや色変化を生ずることがなく、その美麗さを保持することができ、装飾品としての価値を減ずることがない。
【００２０】
ＩＩＩ．めっき皮膜の製造方法本発明のめっき皮膜の製造方法は、生地の表面に金６０〜８０重量％及び銅４０〜２０重量％の組成からなるピンクゴールドの色調を有するめっき皮膜を形成した後に、このめっき皮膜を備えた生地を、４００〜５５０℃の温度で５分間以上、非酸化性雰囲気条件下で加熱処理し、この雰囲気下で室温まで徐冷することを特徴とするものである。
【００２１】
以下、各ステップごとに、さらに詳細に説明する。
１．皮膜の形成本発明においては、生地の表面に通常、金６０〜８０重量％及び銅４０〜２０重量％の組成からなるピンクゴールドの色調を有するめっき皮膜を形成する。このめっき皮膜は、厚付け性、光沢性向上のため、前記金成分及び銅成分に加えて、さらに金属光沢剤を、金成分及び銅成分の合計１００重量部に対して、１０重量部以下含有することが好ましく、５重量部以下含有することがさらに好ましい。このような金属光沢剤としては、前述の本発明のめっき皮膜に用いたものを同様に用いることができる。生地としては、耐熱性金属材料からなるものを好適例として挙げることができる。このような耐熱性金属材料としては、前述の本発明の装飾品に用いたものを同様に用いることができる。なお、皮膜の形成は、通常のめっき操作と同じようにして行うことができる。
【００２２】
２．加熱処理
本発明においては、上述のようにして形成したピンクゴールドの色調を有するめっき皮膜を備えた生地を、加熱温度が通常１５０〜６００℃、好ましくは３００〜６００℃、さらに好ましくは４００〜５５０℃で、加熱時間が通常５分間以上、好ましくは１０〜１２０分間、さらに好ましくは、２０〜８０分間、非酸化性雰囲気条件下で加熱処理し、この雰囲気下で室温まで徐冷する。加熱温度が１５０℃未満であると、耐変色性の改善が不十分となり、６００℃を超えると、熱処理後表面に曇りが出る。また、加熱時間が５分間未満であると、耐変色性の改善が不十分となり、１２０分間を超えると、めっき皮膜の表面に曇り（微小なレベルの肌荒れ）が発生する場合があり、装飾品として用いることができない場合がある。ここで、「非酸化性雰囲気条件下」とは、雰囲気ガス内に酸素が存在しない状態であることを意味し、具体的には、アルゴン、窒素を炉内に充填した後、そのガスを流通するようにすることを挙げることができる。また、「雰囲気下で室温まで徐冷する」の具体例としては、熱処理終了後炉内に放置し、熱処理時の雰囲気を流通して冷却速度2.5℃/minにて室温まで降温することを挙げることができる。
【００２３】
３．後処理
本発明においては、必要に応じて、上述の加熱処理の後に、従来から汎用されている後処理として、アルカリ性溶液、酸性溶液、及び水に浸漬させることにより洗浄し、乾燥を行ってもよい。
【００２４】
このような方法によって、２５℃にて５分間浸漬浸の条件で硝酸に浸漬したときの銅成分の溶出量が単位面積当たり３μｇ以下のめっき皮膜を得ることができる。なお、銅成分の溶出量の測定方法は、前述のめっき皮膜における場合と同様である。
【００２５】
【実施例】
以下に本発明を実施例により具体的に説明するが、本発明はこれら実施例に何等限定されるものではない。
【００２６】
実施例１
ステンレス製の装飾部材を生地として、その表面に通常のめっき操作と同じようにして、金７５重量％、銅２５重量％のめっき皮膜を形成した。次に、得られためっき皮膜を電気炉を用い、アルゴン雰囲気下４００℃で６０分間、加熱処理し、熱処理終了後炉内に放置し、熱処理時の雰囲気を流通して冷却速度2.5℃/minにて室温まで降温するようにして徐冷し、加熱処理後のめっき皮膜を備えた装飾部材を得た。
この加熱処理後のめっき皮膜を２５℃にて５分間浸漬の条件で硝酸に浸漬したときの銅成分の溶出量は、単位面積当たり３μｇであった。加熱条件及び銅成分の溶出量をまとめて表１に示す。
【００２７】
処理前後のめっき皮膜の組成（金及び銅の固溶体の含有割合の大小）を判定するために、加熱処理前後のめっき皮膜を備えた装飾部材についてそれぞれＸ線回折による解析を行った。図１は、加熱処理前のめっき皮膜のＸ線回折による解析結果を示すチャート図である。前述のように、このめっき皮膜は、その中の固溶体相の含有割合が比較的小さく、銅の単相の割合が大きいことがわかる。また、図２は、加熱処理後のめっき皮膜のＸ線回折による解析結果を示すチャート図である。図２に示すように、金及び銅の固溶体の含有割合（ピーク値）のみが顕著に現れ、固溶体が増加していることがわかる。従って、銅の単相の含有割合（ピーク値）は減少していることが推定される。
【００２８】
また、加熱処理前後のめっき皮膜の、所定時間経過後の色むらや色変化の発生を判定するため、前記加熱処理前後のめっき皮膜を備えた装飾部材をそれぞれ、大気中、１５０℃のオーブン内で２５時間放置し、ピンクゴールドの色調を有するめっき皮膜の色調の変化を観察し、加熱処理前後のめっき皮膜と放置後のそれぞれの色調をプロットした結果を図３に示す。図３の横軸は色度（ａ＊：赤方向、−ａ＊：緑方向）を示し、縦軸は色度（ｂ＊黄方向、−ｂ＊：青方向）を示す。図３に示すように、加熱処理後のめっき皮膜（実線で示す）は、加熱処理前のめっき皮膜（破線で示す）よりもピンクゴールドの色調の変化が小さいことがわかる。
【００２９】
実施例２〜４、比較例１〜２及び参考例１
実施例１において、生地、めっき皮膜の組成及び加熱条件（加熱温度及び加熱時間）を表１に示すものに変えたこと以外は、実施例１と同様にして、めっき皮膜を備えた装飾部材を得た。それぞれの銅成分の溶出量及び大気中、１５０℃のオーブン内で２５時間放置した後のめっき皮膜の外観（色調）を表１に示す。なお、色調に変化がなかったものは、○で、また色の変化が認められたものを×で示した。
【００３０】
【表１】
【発明の効果】
以上説明したように、本発明によって、優れた耐変色性を有する金及び銅の組成からなるピンクゴールドの色調を有するめっき皮膜、それを備えた美麗な外観を長期間保持し得る装飾品及びめっき皮膜の効率的な製造方法を提供することができる。
【００３２】
【図面の簡単な説明】
【図１】加熱処理前のめっき皮膜のＸ線回折による解析結果を示すチャート図である。
【図２】加熱処理後のめっき皮膜のＸ線回折による解析結果を示すチャート図である。
【図３】加熱処理前後のめっき皮膜を備えた装飾部材をそれぞれ、大気中、１５０℃のオーブン内で２５時間放置し、めっき皮膜の色調の変化を観察した結果を示す説明図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a plating film, a decorative article including the plating film, and a method for manufacturing the plating film. More specifically, a plating film having a color tone of pink gold made of gold and copper having excellent discoloration resistance, and the efficiency of a decorative product and a plating film that can maintain a beautiful appearance (color tone) for a long period of time. Relates to a typical manufacturing method.
[0002]
[Prior art]
In recent years, ornaments such as crafts, furniture fixtures, watches, electrical / electronic devices, etc., which have a metal part on the surface, are composed of gold and copper due to the luxury and beauty of the color called pink gold. Many are provided with a plating film. Such a plating film usually contains a single phase of gold, a single phase of copper, and a solid solution phase of gold and copper at a predetermined ratio, and after forming the plating film on the surface of the fabric, The treatment is obtained by immersing in an alkaline solution, an acidic solution, and water, followed by drying.
[0003]
However, such a conventional plating film has a small content ratio of the solid solution phase because of forcibly depositing the plating metal by applying a voltage and that the crystal structure is affected by the base metal. It is assumed that there is a single phase portion of each of gold and copper, and that the copper component is present in a large amount at grain boundaries rather than as crystals. This is supported by FIG. 1 described later (a chart showing an analysis result by X-ray diffraction of the plating film). That is, of the two peaks in FIG. 1, the right peak indicates the solid solution phase peak, and the left peak indicates the gold phase peak, but the peak value of the solid solution phase in the plating film is relatively small, and Since there is a peak of the gold phase, it can be seen that the content ratio of the solid solution phase is small. Moreover, since there exists a peak of a gold phase and copper elutes by immersing a plating film in nitric acid so that it may mention later, it turns out that there exists each single phase part of gold | metal | money and copper. Furthermore, since copper elutes with nitric acid and the peak of the copper phase is not confirmed, it can be seen that copper is presumed to be present in large amounts at grain boundaries rather than as crystals. As such a plating film is left in the atmosphere or in an oxidizing atmosphere, the single phase portion of copper is oxidized, causing unevenness or discoloration of the plating film having a color tone of pink gold. There was a problem of significantly reducing the value of.
[0004]
[Problems to be solved by the invention]
The present invention has been made in view of the above-mentioned problems, and has a plating film having a color tone of pink gold composed of gold and copper having excellent discoloration resistance, and a beautiful appearance (color tone) including the same. An object is to provide a decorative article that can be maintained for a long period of time and an efficient method for producing a plating film.
[0005]
[Means for Solving the Problems]
As a result of diligent research to achieve the above object, the present inventors have reduced the elution amount of the copper component, and the plating film having a color tone of pink gold formed on the surface of the fabric under specific conditions. A plating film having a satisfactory pink gold color tone by applying a heat treatment to form a solid solution of the single phase of gold and the single phase of copper and reducing the single phase of copper on the surface of the coating, and a decorative article including the same The present inventors have found that a production method can be obtained and completed the present invention. That is, the present invention provides the following plating film, a decorative product including the same, and a method for producing the plating film.
[0006]
[1] After forming a plating film having a color tone of pink gold composed of 60 to 80% by weight of gold and 40 to 20% by weight of copper on the surface of the cloth, the cloth having this plating film is formed at 400 to 550 ° C. It consists of a composition of 60 to 80% by weight of gold and 40 to 20% by weight of copper obtained by heat-treating at a temperature of 5 minutes or more under non-oxidizing atmosphere conditions and gradually cooling to room temperature in this atmosphere. A plating film having a color tone of pink gold, wherein the elution amount of a copper component when immersed in nitric acid at 25 ° C. for 5 minutes is 3 μg or less per unit area.
[0007]
[2] In addition to the gold component and the copper component, the metal brightening agent is further contained in an amount of 10 parts by weight or less with respect to a total of 100 parts by weight of the gold component and the copper component. Plating film.
[0008]
[3] The metal brightener according to [2], wherein the metal brightener contains at least one selected from the group consisting of cobalt, nickel, antimony, selenium, palladium, tin, indium, silver, cadmium, iron, and zinc. Plating film.
[0009]
[4] A decorative article provided with the plating film according to any one of [1] to [3] on the surface of the cloth.
[0010]
[5] The decorative article according to [4], wherein the fabric is made of a heat-resistant metal material.
[0011]
[6] After forming a plating film having a pink gold color tone composed of 60 to 80% by weight of gold and 40 to 20% by weight of copper on the surface of the cloth, the cloth provided with this plating film is subjected to 400 to 550 ° C. A method for producing a plating film, comprising heat-treating at a temperature of 5 minutes or more under non-oxidizing atmosphere conditions and gradually cooling to room temperature in this atmosphere.
[0012]
[7] In the above [6], the plating film further contains a metallic brightener in addition to the gold component and the copper component, in addition to 10 parts by weight or less with respect to a total of 100 parts by weight of the gold component and the copper component. The manufacturing method of the plating film of description.
[0013]
[8] The above-mentioned [7], wherein the metallic brightener contains at least one selected from the group consisting of cobalt, nickel, antimony, selenium, palladium, tin, indium, silver, cadmium, iron, and zinc. A method for producing a plating film.
[0014]
[9] The method for producing a plating film according to any one of [6] to [8], wherein the cloth is made of a heat-resistant metal material.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the plating film of the present invention, a decorative article including the plating film, and a method of manufacturing the plating film will be specifically described.
I. Plating Film The plating film of the present invention is a cloth provided with this plating film after forming a plating film having a color tone of pink gold composed of 60 to 80% by weight of gold and 40 to 20% by weight of copper on the surface of the cloth. Was heated at 400 to 550 ° C. for 5 minutes or more under non-oxidizing atmosphere conditions, and was gradually cooled to room temperature in this atmosphere, and 60 to 80% by weight of gold and 40 to 20% of copper were obtained. A plating film having a pink gold color tone composed of a weight percent composition, wherein the elution amount of a copper component when immersed in nitric acid at 25 ° C. for 5 minutes is 3 μg or less per unit area It is what.
[0016]
More specific description will be given below.
1. Composition The plating film of the present invention is obtained by forming a plating film having a color of pink gold having a composition of 60 to 80% by weight of gold and 40 to 20% by weight of copper on the surface of the cloth, and then forming the cloth having this plating film. Obtained by heating at 400 to 550 ° C. for 5 minutes or more under non-oxidizing atmosphere conditions and gradually cooling to room temperature in this atmosphere, usually 60 to 80% by weight of gold and 40 to 40% of copper. It has a color tone of pink gold having a composition of 20% by weight. In addition to the gold component and the copper component, the plating film of the present invention further contains a metal brightening agent in addition to the gold component and the copper component in order to improve the thickness and glossiness. The content is preferably not more than 5 parts by weight, and more preferably not more than 5 parts by weight.
[0017]
Such a metallic brightener is not particularly limited, but includes, for example, at least one selected from the group consisting of cobalt, nickel, antimony, selenium, palladium, tin, indium, silver, cadmium, iron, and zinc. Can be mentioned. Preferably, the thing containing silver, cadmium, palladium, cobalt, indium, or selenium can be mentioned. Specific examples include silver cyanide, cadmium cyanide, palladium chloride, cobalt sulfate, indium sulfate, sodium selenite, and the like.
[0018]
2. Elution amount of copper component The plating film of the present invention has an elution amount of copper component of 3 μg or less per unit area when immersed in nitric acid at 25 ° C. for 5 minutes.
When the elution amount of the copper component exceeds 3 μg per unit area, when the plating film is left for 2 months or when it is left in an oven at 150 ° C. for 25 hours, the plating film is discolored to the extent that it can be visually recognized. It is remarkable.
Hereinafter, the measuring method of the elution amount of a copper component is demonstrated concretely.
First, it is immersed in 60% nitric acid at 25 ° C. for 5 minutes. Thereafter, the mass of copper dissolved in nitric acid is measured by ICP emission spectroscopic analysis.
[0019]
II. Decorative product provided with a plating film The decorative product of the present invention comprises the above-described plating film on the surface of the cloth.
The fabric used in the present invention is not particularly limited as long as it contains a metal part that can be plated on the surface, but depending on the heat treatment temperature, the material of the fabric may diffuse into the plating film, For example, a material made of a heat-resistant metal material can be cited as a suitable example because it may be deformed. Examples of such a heat resistant metal material include stainless steel, titanium, brass, and the like.
Since the decorative article of the present invention is provided with the above-described plating film on the surface of the fabric, it has a beautiful pink gold color tone peculiar to a plating film mainly composed of gold and copper, and in the atmosphere or Even if it is used for a long time under an oxidizing atmosphere, color unevenness and color change do not occur, the beauty can be maintained, and the value as a decorative product is not reduced.
[0020]
III. Method for Producing Plating Film The method for producing a plating film according to the present invention comprises forming a plating film having a color of pink gold having a composition of 60 to 80% by weight of gold and 40 to 20% by weight of copper on the surface of the fabric. The cloth provided with the plating film is heat-treated at a temperature of 400 to 550 ° C. for 5 minutes or more under a non-oxidizing atmosphere condition, and gradually cooled to room temperature in this atmosphere.
[0021]
Hereinafter, each step will be described in more detail.
1. Formation of Film In the present invention, a plated film having a color tone of pink gold , usually composed of 60 to 80% by weight of gold and 40 to 20% by weight of copper , is formed on the surface of the fabric. This plating film contains 10 parts by weight or less of a metal brightening agent in addition to the gold component and the copper component in addition to the gold component and the copper component in order to improve the thickness and gloss. It is preferable to contain 5 parts by weight or less. As such a metallic brightener, those used for the above-described plating film of the present invention can be similarly used. A suitable example of the fabric is one made of a heat-resistant metal material. As such a refractory metal material, those used in the above-described decorative product of the present invention can be used in the same manner. The formation of the film can be performed in the same manner as a normal plating operation.
[0022]
2. Heat treatment In the present invention, the heating temperature of the cloth provided with the plating film having the color tone of pink gold formed as described above is usually 150 to 600 ° C, preferably 300 to 600 ° C, more preferably 400 to 550. At a temperature of 5 ° C., the heating time is usually 5 minutes or longer, preferably 10 to 120 minutes, more preferably 20 to 80 minutes, under non-oxidizing atmosphere conditions, and gradually cooled to room temperature in this atmosphere. When the heating temperature is less than 150 ° C., the discoloration resistance is not sufficiently improved. When the heating temperature exceeds 600 ° C., the surface becomes cloudy after the heat treatment. If the heating time is less than 5 minutes, the discoloration resistance is not sufficiently improved. If the heating time is longer than 120 minutes, the surface of the plating film may become cloudy (a minute level of rough skin). It may not be used as Here, “non-oxidizing atmosphere condition” means that oxygen is not present in the atmosphere gas. Specifically, after filling the furnace with argon and nitrogen, the gas is circulated. You can mention what to do. As a specific example of “slow cooling to room temperature in an atmosphere”, it is allowed to stand in the furnace after the heat treatment is completed, and the temperature is lowered to room temperature at a cooling rate of 2.5 ° C./min through the atmosphere during the heat treatment. be able to.
[0023]
3. Post-treatment In the present invention, if necessary, after the above-described heat treatment, as a post-treatment that has been widely used conventionally, it may be washed by immersing it in an alkaline solution, an acidic solution, and water and dried. Good.
[0024]
By such a method, it is possible to obtain a plating film having an elution amount of a copper component of 3 μg or less per unit area when immersed in nitric acid at 25 ° C. for 5 minutes. In addition, the measuring method of the elution amount of a copper component is the same as that of the case in the above-mentioned plating film.
[0025]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[0026]
Example 1
A stainless steel decorative member was used as a cloth, and a plating film of 75% by weight of gold and 25% by weight of copper was formed on the surface in the same manner as a normal plating operation. Next, the obtained plating film was heat-treated at 400 ° C. for 60 minutes in an argon atmosphere using an electric furnace, left in the furnace after completion of the heat treatment, and passed through the atmosphere during the heat treatment to cool at a cooling rate of 2.5 ° C./min. The decorative member provided with the plating film after the heat treatment was obtained by gradually cooling it so that the temperature was lowered to room temperature.
When the plating film after this heat treatment was immersed in nitric acid at 25 ° C. for 5 minutes, the elution amount of the copper component was 3 μg per unit area. Table 1 summarizes the heating conditions and the elution amount of the copper component.
[0027]
In order to determine the composition of the plating film before and after the treatment (the content ratio of the solid solution of gold and copper), the decorative member provided with the plating film before and after the heat treatment was analyzed by X-ray diffraction. FIG. 1 is a chart showing an analysis result by X-ray diffraction of a plating film before heat treatment. As described above, this plating film has a relatively small solid solution phase content and a large copper single phase ratio. FIG. 2 is a chart showing an analysis result by X-ray diffraction of the plated film after the heat treatment. As shown in FIG. 2, only the content ratio (peak value) of the solid solution of gold and copper appears prominently, and it can be seen that the solid solution is increased. Therefore, it is estimated that the content rate (peak value) of the single phase of copper is decreasing.
[0028]
In addition, in order to determine the occurrence of uneven color and color change after a predetermined time of the plating film before and after the heat treatment, each of the decorative members provided with the plating film before and after the heat treatment is placed in an oven at 150 ° C. in the atmosphere. FIG. 3 shows the result of observing the change in the color tone of the plating film having a pink gold color tone and plotting the color tone before and after the heat treatment and the color tone after being left standing. The horizontal axis of FIG. 3 indicates chromaticity (a *: red direction, -a *: green direction), and the vertical axis indicates chromaticity (b * yellow direction, -b *: blue direction). As shown in FIG. 3, it can be seen that the plating film after heat treatment (shown by a solid line) has a smaller change in color tone of pink gold than the plating film before heat treatment (shown by a broken line).
[0029]
Examples 2 to 4, Comparative Examples 1 to 2 and Reference Example 1
In Example 1, the decorative member provided with the plating film was obtained in the same manner as in Example 1 except that the material, the composition of the plating film and the heating conditions (heating temperature and heating time) were changed to those shown in Table 1. Obtained. Table 1 shows the elution amount of each copper component and the appearance (color tone) of the plating film after being left in the oven at 150 ° C. for 25 hours. In addition, the thing in which the color tone did not change was shown by (circle), and the thing in which the color change was recognized was shown by x.
[0030]
[Table 1]
【The invention's effect】
As described above, according to the present invention, a plating film having a color tone of pink gold composed of gold and copper having excellent discoloration resistance, and a decorative article and a plating that can maintain a beautiful appearance for a long time. An efficient method for producing a film can be provided.
[0032]
[Brief description of the drawings]
FIG. 1 is a chart showing an analysis result by X-ray diffraction of a plating film before heat treatment.
FIG. 2 is a chart showing an analysis result by X-ray diffraction of a plated film after heat treatment.
FIG. 3 is an explanatory diagram showing the results of observing changes in the color tone of the plating film after leaving the decorative members provided with the plating film before and after the heat treatment in the atmosphere at 150 ° C. for 25 hours.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12322399A JP4308969B2 (en) | 1999-04-28 | 1999-04-28 | Plating film, decorative product including the same, and method of manufacturing plating film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12322399A JP4308969B2 (en) | 1999-04-28 | 1999-04-28 | Plating film, decorative product including the same, and method of manufacturing plating film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000319794A JP2000319794A (en) | 2000-11-21 |
| JP4308969B2 true JP4308969B2 (en) | 2009-08-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12322399A Expired - Lifetime JP4308969B2 (en) | 1999-04-28 | 1999-04-28 | Plating film, decorative product including the same, and method of manufacturing plating film |
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| JP (1) | JP4308969B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106835217A (en) * | 2017-03-17 | 2017-06-13 | 湖北吉和昌化工科技有限公司 | Imitation gold plating bright property dispersant and preparation method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011117023A (en) * | 2009-12-01 | 2011-06-16 | Seiko Epson Corp | Method of manufacturing ornament, ornament and clock |
| ITFI20120103A1 (en) * | 2012-06-01 | 2013-12-02 | Bluclad Srl | GALVANIC BATHROOMS FOR THE ACHIEVEMENT OF A LEAGUE OF LOW-CARATHED GOLD AND GALVANIC PROCESS THAT USES THESE BATHROOMS. |
| JP2013224965A (en) * | 2013-07-23 | 2013-10-31 | Seiko Epson Corp | Decorative article and timepiece |
-
1999
- 1999-04-28 JP JP12322399A patent/JP4308969B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106835217A (en) * | 2017-03-17 | 2017-06-13 | 湖北吉和昌化工科技有限公司 | Imitation gold plating bright property dispersant and preparation method thereof |
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| JP2000319794A (en) | 2000-11-21 |
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