JP5467445B1 - Decorative silver alloy - Google Patents
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Abstract
【課題】美麗な色調と優れた加工特性とを保持しつつ、耐塩化特性、及び耐硫化特性にも優れた銀合金を提供する。
【解決手段】本発明の銀合金は、銀（Ａｇ）を主成分とし、ゲルマニウム（Ｇｅ）と、錫（Ｓｎ）と、を含む組成を有し、更にアルミニウム（Ａｌ）又はランタン（Ｌａ）の何れかを含むことを特徴とする。
【選択図】なしProvided is a silver alloy having excellent color resistance and sulfidation resistance while maintaining a beautiful color tone and excellent processing characteristics.
A silver alloy of the present invention has a composition containing silver (Ag) as a main component, germanium (Ge), and tin (Sn), and further made of aluminum (Al) or lanthanum (La). One of them is included.
[Selection figure] None
Description
本発明は、美麗な色調と優れた加工特性とを保持しつつ、耐塩化特性、及び耐硫化特性にも優れた銀合金に関する。 The present invention relates to a silver alloy that retains a beautiful color tone and excellent processing characteristics, and also has excellent chlorination resistance and sulfidation resistance.
従来、銀或いは銀合金は、その美麗な色調と優れた加工特性とを有するため、装身具や美術工芸品、食器などに使用されている。例えば広く知られている装飾用の銀合金としては、銀−銅（Ａｇ−Ｃｕ）合金であるが、この銀−銅合金に、亜鉛（Ｚｎ）や錫（Ｓｎ）、インジウム（Ｉｎ）等の元素をそれぞれ添加して硬度特性を向上した三元銀合金も知られている。 Conventionally, silver or a silver alloy has been used in jewelry, arts and crafts, tableware, and the like because of its beautiful color and excellent processing characteristics. For example, a well-known decorative silver alloy is a silver-copper (Ag-Cu) alloy, and zinc (Zn), tin (Sn), indium (In), etc. There are also known ternary silver alloys in which the respective elements are added to improve the hardness characteristics.
これらの銀合金は、大気、海水、汗などに含まれている硫化物や塩化物と反応することにより表面が褐色又は黒色に変色するという欠点があった。
一般的に、銀−亜鉛（Ａｇ−Ｚｎ）合金、銀−アルミニウム（Ａｇ−Ａｌ）合金、銀−カドミニウム（Ａｇ−Ｃｄ）合金などは、硫化に伴う変色（黒変）を抑えることができる銀合金として知られ、Ａｇ−Ａｕ−Ｐｔ合金やＡｇ−Ｚｎ−Ｉｎ−Ｓｎ合金などは、耐変色性を有する銀合金として知られているが、その他にも例えば特許文献１〜３に記載の銀合金も提案されている。
特許文献１に記載の耐変色性銀合金は、銀−ゲルマニウム（Ａｇ−Ｇｅ）合金に、亜鉛（Ｚｎ）とガリウム（Ｇａ）の何れかを必須成分として含み、更にインジウム（Ｉｎ）、錫（Ｓｎ）、アルミニウム（Ａｌ）、パラジウム（Ｐｄ）、カドミウム（Ｃｄ）の一種以上を含んでもよいことが記載されている。
特許文献２に記載の耐硫化性銀合金は、銀にプラチナ（Ｐｔ）かパラジウム（Ｐｄ）の何れか又は両方を必須成分とし、さらにインジウム（Ｉｎ）、亜鉛（Ｚｎ）、錫（Ｓｎ）の何れか一種以上を含んでもよいことが記載されている。
特許文献３に記載の銀合金は、銀−ゲルマニウム（Ａｇ−Ｇｅ）合金であって、この銀合金に、典型金属元素、半金属元素、遷移金属元素の少なくとも一種を含むことが記載されている。
These silver alloys have the disadvantage that the surface turns brown or black by reacting with sulfides and chlorides contained in the atmosphere, seawater, sweat, and the like.
In general, silver-zinc (Ag-Zn) alloy, silver-aluminum (Ag-Al) alloy, silver-cadmium (Ag-Cd) alloy, and the like can suppress discoloration (black discoloration) due to sulfidation. Known as alloys, Ag—Au—Pt alloy, Ag—Zn—In—Sn alloy, etc. are known as silver alloys having discoloration resistance. Alloys have also been proposed.
The discoloration-resistant silver alloy described in Patent Document 1 contains zinc (Zn) or gallium (Ga) as an essential component in a silver-germanium (Ag—Ge) alloy, and further contains indium (In), tin ( It is described that one or more of Sn), aluminum (Al), palladium (Pd), and cadmium (Cd) may be included.
The sulfide-resistant silver alloy described in Patent Document 2 contains platinum (Pt) or palladium (Pd) as an essential component in silver, and further contains indium (In), zinc (Zn), and tin (Sn). It is described that any one or more of them may be included.
The silver alloy described in Patent Document 3 is a silver-germanium (Ag—Ge) alloy, and it is described that the silver alloy contains at least one of a typical metal element, a semimetal element, and a transition metal element. .
しかしながら、前記特許文献１に記載の銀合金では、充分な耐硫化特性、耐塩化特性を有するものではなく、空気中に存在する微量の硫化物や塩化物と反応し、美麗な銀白色を消失して変色してしまうという問題があった。実際のところ、後述する［実施例］の欄にて示すように銀−ゲルマニウム−亜鉛（Ａｇ−Ｇｅ−Ｚｎ）合金では、充分な耐硫化特性、耐塩化特性が得られないことが確認され、更にアルミニウム（Ａｌ）を加えたＡｇ−Ｚｎ−Ｇｅ−Ａｌ合金でも充分な耐硫化特性、耐塩化特性が得られないことが確認された。
また、前記特許文献２に記載の銀合金は、銀よりも更に高価なプラチナを用いるか、加工に難があるパラジウムを用いるものであり、原材料費が嵩むとか、製品化した後のコストが高くなる等の問題を招くものである。
さらに、特許文献３に記載の銀合金は、多数の組み合わせ例を包含するものであり、特に四元以上の多元合金では膨大な組み合わせ例を権利範囲に含めているが、その実施例にて例証されているのは、Ａｇ−Ｇｅ二元合金、及び該合金に、Ｐｄ，Ｃｕ，Ｎｄ，Ｚｎ，Ｓｃ，Ｙをそれぞれ添加した三元合金、Ａｇ−Ｇｅ−Ｃｕ合金に、Ｐｄ，Ｎｄ，Ｚｎ，Ｓｃ，Ｙをそれぞれ添加した四元合金しか記載されていない。しかし、Ａｇ−Ｇｅ合金では充分な耐硫化特性が得られないことは、前記特許文献１にも説明されているとおりであって、Ａｇ−Ｇｅ−Ｚｎ合金でも耐硫化特性、耐塩化特性が認められないことは、後述する［実施例］の欄にて示すとおりである。
また、このように先行技術を見ても、耐硫化にはある程度の効果のある銀合金の報告はいくつもあるが、耐塩化にも充分に効果のある銀合金に関する情報が少なく、従来の技術では耐塩化に対して充分に効果の出ている銀合金があるとは言い難い。
耐塩化特性を重要視する理由は、銀合金を原料とする指輪やネックレス等の装飾品を長時間身に付ける場合には、人体の汗に含まれる塩化物による変色が起こる場合があるからである。銀製品の光沢を保つためには硫化による変色を防ぐのと同じように塩化物による変色を防ぐ必要がある。
However, the silver alloy described in Patent Document 1 does not have sufficient sulfidation resistance and chlorination resistance, and it reacts with a small amount of sulfides and chlorides present in the air to disappear a beautiful silver white color. Then, there was a problem of discoloration. Actually, as shown in the column of [Example] described later, it was confirmed that the silver-germanium-zinc (Ag-Ge-Zn) alloy does not provide sufficient sulfidation resistance and chlorination resistance, Furthermore, it was confirmed that even an Ag—Zn—Ge—Al alloy to which aluminum (Al) was added could not obtain sufficient sulfidation resistance and chlorination resistance.
In addition, the silver alloy described in Patent Document 2 uses platinum that is more expensive than silver, or palladium that is difficult to process, which increases raw material costs or increases the cost after commercialization. This causes problems such as.
Furthermore, the silver alloy described in Patent Document 3 includes a large number of combination examples. In particular, a quaternary or higher multi-element alloy includes an enormous combination example within the scope of rights. What is described is an Ag—Ge binary alloy, a ternary alloy obtained by adding Pd, Cu, Nd, Zn, Sc, Y to the alloy, and an Ag—Ge—Cu alloy, Pd, Nd, Zn. Only quaternary alloys to which, Sc and Y are added are described. However, the fact that sufficient sulfidation resistance cannot be obtained with an Ag-Ge alloy is as described in Patent Document 1, and sulfidation and chlorination resistance are recognized even with an Ag-Ge-Zn alloy. This is not shown in the “Example” column described later.
In view of the prior art as described above, there are a number of reports on silver alloys that have a certain effect on sulfidation resistance, but there is little information on silver alloys that are sufficiently effective on chlorination resistance. Then, it cannot be said that there are silver alloys that are sufficiently effective against chlorination.
The reason for emphasizing chloride resistance is that when wearing jewelry such as rings and necklaces made of silver alloy for a long time, discoloration due to chloride contained in human sweat may occur. is there. In order to maintain the luster of silver products, it is necessary to prevent discoloration due to chloride in the same way as discoloration due to sulfuration.
そこで、本発明では、美麗な色調と優れた加工特性とを保持しつつ、耐塩化特性、及び耐硫化特性にも優れた銀合金を提供することを目的とする。 Therefore, an object of the present invention is to provide a silver alloy having excellent chlorination resistance and sulfidation resistance while maintaining a beautiful color tone and excellent processing characteristics.
本発明は、上記に鑑み提案されたもので、Ａｇ（銀）９０〜９５ｗｔ％と、Ｇｅ（ゲルマニウム）と、Ｓｎ（錫）とを併せて３．３〜９．９ｗｔ％と、２．５ｗｔ％よりも少ないＡｌ（アルミニウム）とからなるＡｇ−Ｇｅ−Ｓｎ−Ａｌ四元合金であることを特徴とする装飾用銀合金に関するものである。 The present invention has been proposed in view of the above, and Ag (silver) 90 to 95 wt% , Ge (germanium), and Sn (tin) are combined to 3.3 to 9.9 wt% and 2.5 wt%. It is related with the silver alloy for decoration characterized by being an Ag-Ge-Sn-Al quaternary alloy which consists of Al (aluminum) less than% .
また、本発明は、銀９０〜９５ｗｔ％と、ゲルマニウムと錫とを併せて３．３〜９．９ｗｔ％と、ランタン０．１〜０．５ｗｔ％とからなるＡｇ−Ｇｅ−Ｓｎ−Ｌａ四元合金であることを特徴とする装飾用銀合金をも提案する。 In addition, the present invention relates to Ag-Ge-Sn-La four comprising 90 to 95 wt% of silver, 3.3 to 9.9 wt% of germanium and tin, and 0.1 to 0.5 wt% of lanthanum. We also propose a decorative silver alloy, which is an original alloy .
本発明は、美麗な色調と優れた加工特性とを保持しつつ、耐塩化特性、及び耐硫化特性にも優れた銀合金を提供するものである。
そのため、銀の含有割合が大きく、即ち高品位の銀製品として各種の用途、例えば腕時計用外装部品、指輪、腕輪等の高級装飾品や食器類などにも広く適用することができ、しかも加工性にも優れているため、極めて実用的価値が高いものである。本発明品は特に耐塩化特性を従来の銀合金よりもさらに向上させた。
そのため、例えばこの銀合金を原料とする指輪やネックレス等の装飾品を長時間身に付けても、人体の汗に含まれる塩化物により時計や指輪、腕輪等が塩化（変色）して装飾価値を著しく損なうような不都合を生ずることがない。
The present invention provides a silver alloy that retains a beautiful color tone and excellent processing characteristics, and also has excellent chlorination resistance and sulfidation resistance.
Therefore, the silver content is large, that is, it can be widely applied to various uses as high-quality silver products, for example, high-grade decorations such as wristwatch exterior parts, rings, bracelets, and tableware, and processability. Therefore, it has extremely high practical value. In particular, the product of the present invention has further improved chloride resistance compared to conventional silver alloys.
Therefore, for example, even if you wear a ring or necklace made of this silver alloy as a raw material for a long time, the watch, ring, bracelet, etc. are salified (discolored) by chloride contained in the sweat of the human body. Inconveniences that significantly impair the performance.
また、銀９０〜９５ｗｔ％と、ゲルマニウムと錫とを併せて３．３〜９．９ｗｔ％と、残部をアルミニウム又はランタンとした銀合金の場合には、当該範囲にて銀装飾品に適した色調のバリエーションを有する高品位の銀合金製品とすることができる。 Further, in the case of a silver alloy in which 90 to 95 wt% silver, 3.3 to 9.9 wt% of germanium and tin are combined, and the balance is aluminum or lanthanum, it is suitable for a silver ornament in the above range. A high-grade silver alloy product having color variations can be obtained.
本発明の銀合金は、Ａｇ（銀）を主成分とし、Ｇｅ（ゲルマニウム）と、Ｓｎ（錫）と、を含む組成を有し、更にＡｌ（アルミニウム）又はＬａ（ランタン）の何れかを含むものであって、具体的にはＡｇ−Ｇｅ−Ｓｎ−Ａｌ四元合金か、Ａｇ−Ｇｅ−Ｓｎ−Ｌａ四元合金となる。 The silver alloy of the present invention has a composition containing Ag (silver) as a main component, Ge (germanium), and Sn (tin), and further contains either Al (aluminum) or La (lanthanum). Specifically, it is an Ag—Ge—Sn—Al quaternary alloy or an Ag—Ge—Sn—La quaternary alloy.
本発明の銀合金に用いるゲルマニウム（Ｇｅ）は、原子番号３２の元素であり、炭素族の元素の一つであるが、銀合金とすることにより、ある程度の耐硫化性を付与することができる。しかし、単に銀にゲルマニウムを合金させただけでは、即ち銀−ゲルマニウム（Ａｇ−Ｇｅ）合金では、充分な耐塩化特性や耐硫化特性を発揮することができないことは、前述のように特許文献１にも説明されているとおりである。 Germanium (Ge) used in the silver alloy of the present invention is an element having an atomic number of 32 and is one of carbon group elements. However, by using a silver alloy, a certain degree of sulfur resistance can be imparted. . However, as described above, Patent Document 1 shows that sufficient silver-germanium (Ag-Ge) alloy cannot exhibit sufficient chlorination resistance and sulfidation resistance simply by alloying germanium with silver. Is also explained.
本発明の銀合金に用いる錫（Ｓｎ）は、原子番号５０の元素であり、典型元素の中の炭素族元素に分類されるが、銀合金とすることにより、ある程度の耐硫化性を付与することができる。
しかし、単に銀−ゲルマニウム合金に錫を合金させただけでは、即ち銀−ゲルマニウム−錫（Ａｇ−Ｇｅ−Ｓｎ）合金では、充分な耐塩化特性や耐硫化特性を発揮することができないことは、後述する［実施例］の欄の比較例３の結果からも明らかである。
Tin (Sn) used in the silver alloy of the present invention is an element having an atomic number of 50, and is classified as a carbon group element among typical elements. By using a silver alloy, a certain degree of sulfur resistance is imparted. be able to.
However, simply tin-alloying a silver-germanium alloy, that is, a silver-germanium-tin (Ag-Ge-Sn) alloy cannot exhibit sufficient chlorination resistance and sulfidation resistance. It is clear from the result of Comparative Example 3 in the “Example” column described later.
本発明の銀合金に用いるアルミニウム（Ａｌ）は、原子番号１３の元素であり、前記ゲルマニウム（Ｇｅ）及び錫（Ｓｎ）と共に銀合金（Ａｇ−Ｇｅ−Ｓｎ−Ａｌ）とすることにより、飛躍的に耐塩化特性や耐硫化特性が向上することが見出された。
特にこのＡｌを含むＡｇ−Ｇｅ−Ｓｎ−Ａｌ合金は、加工性の面においてＬａを含むＡｇ−Ｇｅ−Ｓｎ−Ｌａ合金よりも優れていることが後述する［実施例］の評価にて確認されている。但し、このＡｌの含有割合は、２．５ｗｔ％より少ないことが望ましい。
Aluminum (Al) used in the silver alloy of the present invention is an element having an atomic number of 13, and is dramatically improved by using a silver alloy (Ag—Ge—Sn—Al) together with the germanium (Ge) and tin (Sn). It has been found that the chloride resistance and sulfuration resistance are improved.
In particular, the evaluation of [Example] described later confirms that the Ag-Ge-Sn-Al alloy containing Al is superior to the Ag-Ge-Sn-La alloy containing La in terms of workability. ing. However, the Al content is preferably less than 2.5 wt%.
また、本発明の銀合金に用いるランタン（Ｌａ）は、原子番号５７の元素であり、希土類元素の一つであるが、前記ゲルマニウム（Ｇｅ）及び錫（Ｓｎ）と共に銀合金（Ａｇ−Ｇｅ−Ｓｎ−Ｌａ）とすることにより、飛躍的に耐塩化特性や耐硫化特性が向上することが見出された。
なお、このＬａを含むＡｇ−Ｇｅ−Ｓｎ−Ｌａ合金では、後述する［実施例］にて圧延加工にて割れが観察されたが、熱間圧延を行ったり、圧延前に適切な焼きなましを行うことで、圧延時のバリや割れを抑えることは一般的な熱処理技術で対応可能である。
また、冷間圧延で割れが発生するような銀合金組成の場合でも、圧延工程を必要としない型を用いた鋳込みで最終製品形状を作製することは可能であり、適切な製造形態を選択することにより対応することができる。
In addition, lanthanum (La) used in the silver alloy of the present invention is an element having an atomic number of 57 and is one of rare earth elements, but together with the germanium (Ge) and tin (Sn), a silver alloy (Ag—Ge—) is used. It was found that by using Sn-La), the chloride resistance and the sulfur resistance were dramatically improved.
In addition, in the Ag—Ge—Sn—La alloy containing La, cracks were observed in the rolling process in [Example] described later. However, hot rolling or appropriate annealing is performed before rolling. Thus, it is possible to cope with burr and cracking during rolling with a general heat treatment technique.
In addition, even in the case of a silver alloy composition that causes cracks in cold rolling, it is possible to produce the final product shape by casting using a mold that does not require a rolling process, and select an appropriate manufacturing form. It can respond by doing.
なお、当然のことながら、銀−ゲルマニウム−錫（Ａｇ−Ｇｅ−Ｓｎ）三元合金に加える元素は限定されるものであり、例えば前記三元合金に銅（Ｃｕ）を追加配合した四元合金（Ａｇ−Ｇｅ−Ｓｎ−Ｃｕ）では後述する［実施例］の欄の比較例５の結果からも明らかであり、チタン（Ｔｉ）を追加配合した四元合金（Ａｇ−Ｇｅ−Ｓｎ−Ｔｉ）では後述する［実施例］の欄の比較例１０の結果からも明らかであり、何等有効な配合効果は得られない。 Of course, the elements to be added to the silver-germanium-tin (Ag-Ge-Sn) ternary alloy are limited. For example, a quaternary alloy in which copper (Cu) is added to the ternary alloy. (Ag—Ge—Sn—Cu) is also apparent from the results of Comparative Example 5 in the “Example” column described later, and is a quaternary alloy (Ag—Ge—Sn—Ti) additionally containing titanium (Ti). Then, it is clear from the result of Comparative Example 10 in the [Example] column described later, and no effective blending effect is obtained.
本発明のＡｇ−Ｇｅ−Ｓｎ−Ａｌ合金、又はＡｇ−Ｇｅ−Ｓｎ−Ｌａ合金において、Ａｇの割合が５０ｗｔ％以上の範囲で前述の美麗な色調と優れた加工特性とを保持しつつ、優れた耐塩化特性や耐硫化特性を有する銀合金が得られる。しかし、銀装飾品としては銀品位が高いことが望まれるため、Ａｇの割合については９０ｗｔ％以上に設定し、それ以外の三元素の割合を特定する実験を行ったところ、特にその配合割合については、Ａｇ９０〜９５ｗｔ％と、ＧｅとＳｎとを併せて３．３〜９．９ｗｔ％と、残部をＡｌ又はＬａとした銀合金の場合には、当該範囲にて銀装飾品に適した色調のバリエーションを有する高品位の銀合金製品とすることができる。
さらに、特に望ましくは、銀９２〜９３ｗｔ％と、ゲルマニウム３．５〜５．５ｗｔ％と、錫１．４〜２．４ｗｔ％と、残部をアルミニウム又はランタンとした銀合金の場合には、当該範囲にて銀装飾品に適した色調のバリエーションを有する高品位の銀合金製品とすることができる。
In the Ag-Ge-Sn-Al alloy or the Ag-Ge-Sn-La alloy of the present invention, the above-mentioned beautiful color tone and excellent processing characteristics are maintained while the proportion of Ag is in the range of 50 wt% or more. In addition, a silver alloy having chlorination resistance and sulfidation resistance is obtained. However, since silver quality is desired to be high for silver ornamental products, the proportion of Ag was set to 90 wt% or more, and an experiment was conducted to identify the proportion of the other three elements. In the case of a silver alloy in which Ag is 90 to 95 wt%, Ge and Sn are combined in a range of 3.3 to 9.9 wt%, and the balance is Al or La, the color tone suitable for silver ornaments in this range It can be set as the high quality silver alloy product which has a variation.
More preferably, in the case of a silver alloy having 92 to 93 wt% silver, 3.5 to 5.5 wt% germanium, 1.4 to 2.4 wt% tin, and aluminum or lanthanum as the balance, High-quality silver alloy products having variations in color tone suitable for silver ornaments in a range can be obtained.
本発明では、後述する［実施例］の欄に記載するように耐塩化特性の判断として、ＪＩＳＺ２３７１に準拠してＣＡＳＳ試験を実施し、変色の有無を判定した。
但し、本発明のＪＩＳＺ２３７１に準拠したＣＡＳＳ試験は、前述の先行技術文献よりも試験条件がより過酷なため、より耐塩化特性の良悪の判断が明確になった。
例えば前記特許文献１では、Ａｇ−Ｇｅ−Ｚｎ合金に関し、耐塩化特性に優れている結果を記載しているが、後述する［実施例］の欄の比較例６の結果として示したように前記Ａｇ−Ｇｅ−Ｚｎ合金は決して充分な耐塩化特性を有していないことが確認された。
In the present invention, as described in the “Example” section described later, as a determination of the chlorination resistance, a CASS test was performed in accordance with JISZ2371, and the presence or absence of discoloration was determined.
However, since the CASS test based on JISZ2371 of the present invention has more severe test conditions than the above-mentioned prior art documents, the determination of the quality of the chlorination resistance has become clearer.
For example, in the above-mentioned Patent Document 1, a result of excellent chlorination resistance is described regarding an Ag—Ge—Zn alloy, but as shown as a result of Comparative Example 6 in the “Example” column described later, It was confirmed that the Ag—Ge—Zn alloy never has sufficient chlorination resistance.
本発明では、後述する［実施例］の欄に記載するように耐硫化特性の判断として、３％硫化ナトリウム水溶液に試験片を３０秒間浸漬した後の表面状態を評価し、変色の有無を判定した。
これに対し、前記特許文献１では、硫化アンモニア曝気試験を２５℃の温度で１０分間行い、試験前後の色差を測定している。
また、前記特許文献２では、硫化ナトリウム濃度が０．０８％の人工汗に３０秒間浸漬した後の変色度合いを判定している。
この前記特許文献２における硫化ナトリウム濃度の相違からも明らかなように、本発明の硫化試験は、前述の先行技術文献よりも試験条件がより明らかに過酷なため、より耐硫化特性の良悪の判断が明確になった。
In the present invention, as described in the [Example] section described later, as a determination of the anti-sulfur property, the surface condition after immersing the test piece in a 3% aqueous sodium sulfide solution for 30 seconds is evaluated to determine the presence or absence of discoloration. did.
On the other hand, in the said patent document 1, the ammonia sulfide aeration test is performed for 10 minutes at the temperature of 25 degreeC, and the color difference before and behind a test is measured.
Moreover, in the said patent document 2, the discoloration degree after being immersed in the artificial sweat whose sodium sulfide density | concentration is 0.08% for 30 second is determined.
As apparent from the difference in the sodium sulfide concentration in Patent Document 2, the sulfurization test of the present invention is more severe in the test conditions than the above-mentioned prior art document, so that the resistance to sulfuration is better and worse. Judgment became clear.
〔実施例１（Lot.No１１）〕
銀９２．５％−ゲルマニウム５．２９％−錫２．１１％−アルミニウム０．１％の組成の銀合金（ＡｇＧｅ5.29Ｓｎ2.11Ａｌ0.1）を用いて測定試料を作製した
[Example 1 (Lot. No. 11)]
A measurement sample was prepared using a silver alloy (AgGe 5.29 Sn 2.11 Al 0.1 ) having a composition of silver 92.5% -germanium 5.29 % -tin 2.11% -aluminum 0.1%.
〔実施例２（Lot.No１２）〕
銀９２．５％−ゲルマニウム５％−錫２％−アルミニウム０．５％の組成の銀合金（ＡｇＧｅ5Ｓｎ2Ａｌ0.5）を用いて測定試料を作製した
[Example 2 (Lot. No. 12)]
A measurement sample was prepared using a silver alloy (AgGe 5 Sn 2 Al 0.5 ) having a composition of silver 92.5% -germanium 5 % -tin 2% -aluminum 0.5%.
〔実施例３（Lot.No１３）〕
銀９２．５％−ゲルマニウム４．６４％−錫１．８６％−アルミニウム１．０％の組成の銀合金（ＡｇＧｅ4.64Ｓｎ1.86Ａｌ1.0）を用いて測定試料を作製した
[Example 3 (Lot. No. 13)]
A measurement sample was prepared using a silver alloy (AgGe 4.64 Sn 1.86 Al 1.0 ) having a composition of silver 92.5% -germanium 4.64 % -tin 1.86% -aluminum 1.0%.
〔実施例４（Lot.No１４）〕
銀９２．５％−ゲルマニウム３．５７％−錫１．４３％−アルミニウム２．５％の組成の銀合金（ＡｇＧｅ3.57Ｓｎ1.43Ａｌ2.5）を用いて測定試料を作製した
[Example 4 (Lot. No. 14)]
A measurement sample was prepared using a silver alloy (AgGe 3.57 Sn 1.43 Al 2.5 ) having a composition of 92.5% silver, 3.57% germanium, 1.43% tin, and 2.5% aluminum.
〔実施例５（Lot.No１５）〕
銀９２．５％−ゲルマニウム５．０７％−錫２．３３％−ランタン０．１％の組成の銀合金（ＡｇＧｅ5.07Ｓｎ2.33Ｌａ0.1）を用いて測定試料を作製した
[Example 5 (Lot. No. 15)]
A measurement sample was prepared using a silver alloy (AgGe 5.07 Sn 2.33 La 0.1 ) having a composition of 92.5% silver, 5.07% germanium, 2.33% tin, and 0.1% lanthanum.
〔実施例６（Lot.No１６）〕
銀９２．５％−ゲルマニウム５％−錫２．３％−ランタン０．２％の組成の銀合金（ＡｇＧｅ5Ｓｎ2.3Ｌａ0.2）を用いて測定試料を作製した
[Example 6 (Lot. No. 16)]
A measurement sample was prepared using a silver alloy (AgGe 5 Sn 2.3 La 0.2 ) having a composition of silver 92.5% -germanium 5 % -tin 2.3% -lanthanum 0.2%.
〔実施例７（Lot.No１７）〕
銀９２．５％−ゲルマニウム４．９３％−錫２．２７％−ランタン０．３％の組成の銀合金（ＡｇＧｅ4.93Ｓｎ2.27Ｌａ0.3）を用いて測定試料を作製した
[Example 7 (Lot. No. 17)]
Silver 92.5% - germanium 4.93% - 2.27% tin - to prepare a measurement sample using a lanthanum 0.3% silver alloy composition (AgGe 4.93 Sn 2.27 La 0.3)
〔実施例８（Lot.No１８）〕
銀９２．５％−ゲルマニウム４．７９％−錫２．２１％−ランタン０．５％の組成の銀合金（ＡｇＧｅ4.79Ｓｎ2.21Ｌａ0.5）を用いて測定試料を作製した
[Example 8 (Lot. No. 18)]
A measurement sample was prepared using a silver alloy (AgGe 4.79 Sn 2.21 La 0.5 ) having a composition of silver 92.5% -germanium 4.79 % -tin 2.21% -lanthanum 0.5%.
〔比較例１（Lot.No１）〕
銀１００％の組成の純銀を用いて測定試料を作製した
[Comparative Example 1 (Lot. No. 1)]
A measurement sample was prepared using pure silver having a composition of 100% silver.
〔比較例２（Lot.No２）〕
銀９２．５％−銅７．５％の組成の銀合金（ＡｇＣｕ7.5）を用いて測定試料を作製した
[Comparative Example 2 (Lot. No. 2)]
A measurement sample was prepared using a silver alloy (AgCu 7.5 ) having a composition of silver 92.5% -copper 7.5%.
〔比較例３（Lot.No３）〕
銀９２．５％−ゲルマニウム５％−錫２．５％の組成の銀合金（ＡｇＧｅ5Ｓｎ2.5）を用いて測定試料を作製した
[Comparative Example 3 (Lot. No. 3)]
A measurement sample was prepared using a silver alloy (AgGe 5 Sn 2.5 ) having a composition of silver 92.5% -germanium 5 % -tin 2.5%.
〔比較例４（Lot.No４）〕
銀９２．５％−銅５％−錫２％−ケイ素０．５％の組成の銀合金（ＡｇＣｕ5Ｓｎ2Ｓｉ0.5）を用いて測定試料を作製した
[Comparative Example 4 (Lot. No. 4)]
A measurement sample was prepared using a silver alloy (AgCu 5 Sn 2 Si 0.5 ) having a composition of silver 92.5% -copper 5% -tin 2% -silicon 0.5%.
〔比較例５（Lot.No５）〕
銀９２．５％−ゲルマニウム２．５％−銅２．５％−錫２．５％の組成の銀合金（ＡｇＧｅ2.5Ｃｕ2.5Ｓｎ2.5）を用いて測定試料を作製した
[Comparative Example 5 (Lot. No. 5)]
A measurement sample was prepared using a silver alloy (AgGe 2.5 Cu 2.5 Sn 2.5 ) having a composition of silver 92.5% -germanium 2.5 % -copper 2.5 % -tin 2.5 %.
〔比較例６（Lot.No６）〕
銀９２．５％−ゲルマニウム５％−錫２．５％の組成の銀合金（ＡｇＧｅ5Ｚｎ2.5）を用いて測定試料を作製した
[Comparative Example 6 (Lot. No. 6)]
A measurement sample was prepared using a silver alloy (AgGe 5 Zn 2.5 ) having a composition of silver 92.5% -germanium 5 % -tin 2.5%.
〔比較例７（Lot.No７）〕
銀９２．５％−亜鉛５％−錫２％−チタン０．５％の組成の銀合金（ＡｇＺｎ5Ｓｎ2Ｔｉ0.5）を用いて測定試料を作製した
[Comparative Example 7 (Lot. No. 7)]
A measurement sample was prepared using a silver alloy (AgZn 5 Sn 2 Ti 0.5 ) having a composition of silver 92.5% -zinc 5 % -tin 2% -titanium 0.5%.
〔比較例８（Lot.No８）〕
銀９２．５％−亜鉛５％−錫２％−ケイ素０．５％の組成の銀合金（ＡｇＺｎ5Ｓｎ2Ｓｉ0.5）を用いて測定試料を作製した
[Comparative Example 8 (Lot. No. 8)]
A measurement sample was prepared using a silver alloy (AgZn 5 Sn 2 Si 0.5 ) having a composition of silver 92.5% -zinc 5 % -tin 2% -silicon 0.5%.
〔比較例９（Lot.No９）〕
銀９２．５％−亜鉛５％−ゲルマニウム２％−アルミニウム０．５％の組成の銀合金（ＡｇＺｎ5Ｇｅ2Ａｌ0.5）を用いて測定試料を作製した
[Comparative Example 9 (Lot. No. 9)]
A measurement sample was prepared using a silver alloy (AgZn 5 Ge 2 Al 0.5 ) having a composition of silver 92.5% -zinc 5 % -germanium 2% -aluminum 0.5%.
〔比較例１０（Lot.No１０）〕
銀９２．５％−ゲルマニウム５％−錫２％−チタン０．５％の組成の銀合金（ＡｇＧｅ5Ｓｎ2Ｔｉ0.5）を用いて測定試料を作製した
[Comparative Example 10 (Lot. No. 10)]
A measurement sample was prepared using a silver alloy (AgGe 5 Sn 2 Ti 0.5 ) having a composition of silver 92.5% -germanium 5 % -tin 2% -titanium 0.5%.
〈評価方法〉
１．Ｌ＊〈明度〉
試料研磨後の表面を色差計にて測定し、その測定値を表１に示した。
２．硬さ試験
圧延研磨後の試料表面をビッカース硬さ試験機を用いて測定し、その測定値を表１に示した。
<Evaluation method>
1. L * <Brightness>
The surface after sample polishing was measured with a color difference meter, and the measured values are shown in Table 1.
2. Hardness test The sample surface after rolling and polishing was measured using a Vickers hardness tester, and the measured values are shown in Table 1.
３．加工性
溶解後４ｍｍのインゴットを圧延機で１ｍｍまで圧延時の状態を評価し、評価結果を表１に示した。
評価基準は以下の通りである。
◎ 圧延良好
○ バリはでるが圧延可
△ 割れが発生
3. Workability After melting, an ingot of 4 mm was evaluated with a rolling mill to 1 mm during rolling, and the evaluation results are shown in Table 1.
The evaluation criteria are as follows.
◎ Good rolling ○ Burr comes out but rolling is possible △ Cracking occurs
４．ＣＡＳＳ試験（＝耐塩化特性評価）
ＪＩＳＺ２３７１に準拠してＣＡＳＳ試験を実施し、評価結果を表１に示した。
試験条件は以下の通りである。
試験液：塩化ナトリウム ５０±５ｇ／Ｌ
塩化銅（II）０．２０５±０．０１５ｇ／Ｌ
噴霧室内温度：５０±２℃
噴霧時間：４８時間
評価基準は以下の通りである。
◎ 変色なし
○ 変色わずか（一部のみ）
△ 半面が変色
× 全面が変色
4). CASS test (= chloride resistance evaluation)
A CASS test was conducted according to JISZ2371, and the evaluation results are shown in Table 1.
The test conditions are as follows.
Test solution: Sodium chloride 50 ± 5 g / L
Copper (II) chloride 0.205 ± 0.015g / L
Spray room temperature: 50 ± 2 ° C
Spraying time: 48 hours Evaluation criteria are as follows.
◎ No discoloration ○ Slight discoloration (only part)
△ One side is discolored × The whole surface is discolored
５．硫化試験（＝耐硫化特性評価）
３％硫化ナトリウム水溶液に３０秒間浸漬した後の表面状態を評価し、評価結果を表１に示した。
評価基準は以下の通りである。
〇 変色わずか（一部のみ）
× 全面が変色
5. Sulfurization test (= sulfidation resistance evaluation)
The surface state after being immersed in a 3% aqueous sodium sulfide solution for 30 seconds was evaluated, and the evaluation results are shown in Table 1.
The evaluation criteria are as follows.
〇 Slight discoloration (only part)
× The entire surface is discolored
〈結果〉
〔考察〕
表１より明らかなように単に銀−ゲルマニウム合金に錫を添加して合金化させるだけ（＝比較例３）では、充分な耐塩化特性を発揮することができなかった。あるいは、銀−ゲルマニウム−錫合金にＣｕを添加して合金化させても（＝比較例５）、Ｔｉを添加して合金化させても（＝比較例１０）、充分な耐塩化特性を発揮することができなかった。
これに対し、本発明の実施例１〜８では、銀−ゲルマニウム−錫合金にＡｌまたはＬａを添加させて合金化することで、充分な耐塩化特性及び耐硫化特性が得られた。これは、単なる銀−ゲルマニウムや銀−ゲルマニウム−錫合金とは異なるＡｌやＬａに起因した耐食性の表面皮膜を銀合金表面に形成するため、耐塩化特性や耐硫化特性の向上がはかられたと推測する。
また、Ａｌを０．１〜１．０ｗｔ％含有する実施例１〜３では極めて良好な加工性を有することが確認された。なお、Ａｌを２．５ｗｔ％含有する実施例４やＬａを含有する実施例５〜８では、当該加工性試験にて圧延で割れが発生したが、これらの実施例４〜８の銀合金組成の場合でも、熱間圧延を行ったり、圧延前に適切な焼きなましを行うことで、圧延時のバリや割れを抑えられることは別途確認している。即ち一般的な熱処理技術で加工性は対応可能であった。
これらの結果より、実施例１〜３では、加工性について問題がないが、少なくとも実施例４〜８に関しては、圧延工程を必要としない型を用いた鋳込みで最終製品形状を作製する製造形態がより好ましいことが確認された。
なお、耐塩化特性並びに耐硫化特性の確認試験として、指輪（リング）に加工した製品を用い、ふた月からみ月程度の連続装着の後にその変色を確認した。
この場合にも、表１とほぼ同様の結果が得られた。即ち、Ａｇ−Ｇｅ−Ｚｎ合金製の指輪や、その他の比較例１〜１０でも明らかな変色が確認されており、本発明の実施例では変色が認められなかった。
[Discussion]
As can be seen from Table 1, if the silver-germanium alloy was simply alloyed by adding tin (= Comparative Example 3), sufficient chlorination resistance could not be exhibited. Alternatively, even if Cu is added to a silver-germanium-tin alloy for alloying (= Comparative Example 5) or Ti is added for alloying (= Comparative Example 10), sufficient chlorination resistance is exhibited. I couldn't.
On the other hand, in Examples 1 to 8 of the present invention, sufficient chlorination resistance and sulfation resistance were obtained by adding Al or La to the silver-germanium-tin alloy for alloying. This is because a corrosion-resistant surface film caused by Al or La, which is different from simple silver-germanium or silver-germanium-tin alloy, is formed on the surface of the silver alloy. Infer.
Moreover, it was confirmed that Examples 1 to 3 containing 0.1 to 1.0 wt% Al have extremely good workability. In Example 4 containing 2.5 wt% of Al and Examples 5 to 8 containing La, cracks occurred during rolling in the workability test. The silver alloy compositions of Examples 4 to 8 were used. Even in this case, it has been separately confirmed that burrs and cracks during rolling can be suppressed by performing hot rolling or performing appropriate annealing before rolling. That is, workability could be handled by a general heat treatment technique.
From these results, in Examples 1 to 3, there is no problem in workability, but at least for Examples 4 to 8, there is a manufacturing form for producing a final product shape by casting using a mold that does not require a rolling process. It was confirmed that it was more preferable.
In addition, as a confirmation test of chlorination resistance and sulfidation resistance, a product processed into a ring (ring) was used, and the discoloration was confirmed after continuous wearing for about two months.
In this case, the same result as in Table 1 was obtained. That is, clear discoloration was confirmed in the ring made of Ag-Ge-Zn alloy and other Comparative Examples 1 to 10, and no discoloration was observed in the examples of the present invention.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60162741A (en) * | 1984-01-31 | 1985-08-24 | Sumitomo Metal Mining Co Ltd | Bonding wire |
| JPS6210231A (en) * | 1985-07-08 | 1987-01-19 | Seiko Epson Corp | Sulfurization resistant silver alloy |
| JPS6220850A (en) * | 1985-07-19 | 1987-01-29 | Citizen Watch Co Ltd | Tarnish resistant silver alloy |
| CN1644725A (en) * | 2004-01-20 | 2005-07-27 | 香港生产力促进局 | Tarnish-resistant hard silver alloy |
| JP2006037169A (en) * | 2004-07-27 | 2006-02-09 | Furuya Kinzoku:Kk | Silver alloy, sputtering target thereof and thin film thereby |
| JP2008179890A (en) * | 2006-12-27 | 2008-08-07 | Supreme:Kk | Noble metal alloy for accessory, and accessory made of the noble metal alloy for accessory |
-
2013
- 2013-07-23 JP JP2013152551A patent/JP5467445B1/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60162741A (en) * | 1984-01-31 | 1985-08-24 | Sumitomo Metal Mining Co Ltd | Bonding wire |
| JPS6210231A (en) * | 1985-07-08 | 1987-01-19 | Seiko Epson Corp | Sulfurization resistant silver alloy |
| JPS6220850A (en) * | 1985-07-19 | 1987-01-29 | Citizen Watch Co Ltd | Tarnish resistant silver alloy |
| CN1644725A (en) * | 2004-01-20 | 2005-07-27 | 香港生产力促进局 | Tarnish-resistant hard silver alloy |
| JP2006037169A (en) * | 2004-07-27 | 2006-02-09 | Furuya Kinzoku:Kk | Silver alloy, sputtering target thereof and thin film thereby |
| JP2008179890A (en) * | 2006-12-27 | 2008-08-07 | Supreme:Kk | Noble metal alloy for accessory, and accessory made of the noble metal alloy for accessory |
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