WO2008053559A1 - GOLDEN Pd-In ALLOYS - Google Patents

GOLDEN Pd-In ALLOYS Download PDF

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Publication number
WO2008053559A1
WO2008053559A1 PCT/JP2006/321985 JP2006321985W WO2008053559A1 WO 2008053559 A1 WO2008053559 A1 WO 2008053559A1 JP 2006321985 W JP2006321985 W JP 2006321985W WO 2008053559 A1 WO2008053559 A1 WO 2008053559A1
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Prior art keywords
gold
alloy
indium
palladium
weight
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PCT/JP2006/321985
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French (fr)
Japanese (ja)
Inventor
Noriyoshi Ishi
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Lapis
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Priority to PCT/JP2006/321985 priority Critical patent/WO2008053559A1/en
Publication of WO2008053559A1 publication Critical patent/WO2008053559A1/en

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C5/00Alloys based on noble metals
    • C22C5/04Alloys based on a platinum group metal
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C28/00Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C5/00Alloys based on noble metals
    • C22C5/06Alloys based on silver

Definitions

  • Cu copper
  • Cs cesium
  • Copper has a high red reflectivity and low green and blue reflectivity, so even gold looks reddish.
  • silver (Ag) appears white because it exhibits a reflectivity of 90% or more over the entire visible light.
  • palladium (Pd) is a silver-white metal and has a face-centered cubic structure that is stable at room temperature.
  • Indium (In) is a silvery gray metal with a tetragonal crystal structure that is stable at room temperature. That is, both palladium and indium are silver and white metals.
  • the present invention is an elegant gold-colored gold alloy mainly composed of palladium (Pd) and indium (In), and is a decorative member (brooch, medal, button, tie pin, earring, pin Pd-In gold alloys that can be used as furniture, pendant heads, clock members (eg dial scales), furniture items such as western tableware, arts and crafts, or dental metal members It is.
  • gold-colored material used for decoration for example, various metals such as pure gold, a gold alloy, brass, or a metal surface plated with gold has been used.
  • pure gold or gold alloy is expensive, and gold plating may be peeled off.
  • Copper / zinc alloys and copper / aluminum alloys have low defects in strength and corrosion resistance!
  • titanium nitride films and sintered alloys have characteristics such as high hardness and excellent corrosion resistance, but they require special equipment and technology and are suitable for the production of individual gold alloys. Not done.
  • Patent Document 1 proposes a gold-colored sintered alloy having a golden color tone that improves the sinterability of a gold-colored sintered alloy in which titanium nitride or the like is bonded with a metal such as Ni or Co. Yes.
  • special equipment is required to produce a sintered alloy based on titanium nitride, which is suitable for the production of individual gold alloys.
  • Patent Document 1 JP-A-5-311311
  • the gold alloy according to the present invention does not contain gold (Au) and copper (Cu) exhibiting a gold color! However, it is a gold alloy exhibiting an excellent gold color. Therefore, it can be produced at a lower cost than conventional so-called gold alloys including pure gold and pure gold.
  • the price of each precious metal as of October 2006 is about 4400 yen for platinum (Au) is about 2300 yen Zg, palladium (Pd) is about 1300 yen Zg, and indium (In) is about 1 20 yen Zg and silver (Ag) are about 45 yen Zg. Therefore, the price of palladium is about half of the price of gold, and about 5% of indium.
  • the material price of a gold alloy with 50% palladium weight and 50% indium weight is 18K gold. It is converted to about 40% of the alloy.
  • the gold alloy according to the present invention is less likely to be scratched on the surface having higher hardness than the conventional gold alloy.
  • Vickers hardness of each precious metal is platinum 41, gold 22, silver 24
  • the Pd—In gold alloy according to the present invention has a Vickers hardness of about 160 to 360.
  • the gold alloy according to the present invention has the same corrosion resistance as the conventional 18K gold alloy and the like, as will be described later.
  • a first aspect of the present invention is an alloy containing at least palladium (Pd) and indium (In), wherein the ratio of the weight of palladium to the weight of indium is between 0.92 and 1.5, and a Pd -In based gold alloy, wherein the content of the indium content of Jiumu is both 10 weight 0/0 above.
  • a third aspect of the present invention is a binary alloy comprising palladium (Pd), indium (In), and inevitable impurities, wherein the ratio of the weight of palladium to the weight of indium is between 0.92 and 1.5.
  • This is a Pd-In gold alloy.
  • a fourth aspect of the present invention is an alloy containing palladium (Pd), indium (In), and silver (Ag), wherein both the palladium content and the indium content are 10% by weight or more, and A Pd-In-based golden alloy characterized by having a silver content of 80% by weight or less.
  • a sixth aspect of the present invention is an alloy containing palladium (Pd), indium (In), and copper (Cu), wherein both the palladium content and the indium content are 10% by weight or more, and
  • the Pd-In gold alloy is characterized by having a copper content of 40% by weight or less.
  • a seventh aspect of the present invention is an alloy containing palladium (Pd) and indium (In), and the color tone is any of red gold, pink gold, yellow gold, and yellow gold. It is a Pd-In gold alloy characterized by exhibiting such a color tone.
  • An eighth aspect of the present invention is an alloy containing palladium (Pd) and indium (In), and further in the atmosphere, 30% dilute hydrochloric acid, 99.7% acetic acid, 30% dilute sulfuric acid, or 10% excess. It is a Pd-In gold alloy characterized by having good corrosion resistance in any environment of either acid or hydrogen water. The invention's effect
  • the gold alloy according to the present invention does not contain gold (Au) and copper (Cu)! However, it is a gold alloy exhibiting an elegant gold color. Therefore, it is possible to produce a gold alloy product exhibiting a gold color at a lower price than a conventional gold alloy containing pure gold and pure gold.
  • the gold alloy according to the present invention is less expensive than conventional gold alloys. On the other hand, it has corrosion resistance equivalent to that of conventional gold alloys (for example, 12K alloys).
  • the gold alloy product according to the present invention can be easily produced with a metal melting apparatus or the like as in the case of conventional gold alloys.
  • 18K gold alloys such as red gold, yellow gold, and green gold are the same as above to compare the color tone with the above various prototype alloys. It was produced by the method. Table 6 shows the composition of these comparative gold alloys (gold alloy symbols: 18K gold alloy ⁇ red, 18K gold alloy 'yellow, 18K gold alloy' green, 12K gold alloy 'yellow, etc.).
  • 18K gold alloys are used for luxury items such as golden finger rings, necklaces, and earrings.
  • the composition of 18K gold alloy for decoration is usually 75% of gold (Au), and the other components are copper (Cu) and silver (Ag).
  • the standard composition of 18K gold alloy is Au (75%), Cu (10-15%), Ag (10-15%), and it has the power to show yellow or yellow, gold color. Re! / If the ratio of copper is further increased, the color of the gold alloy becomes reddish and is called red 'gold'. Conversely, if the ratio of silver is further increased, the color becomes green and the color is called green 'gold.
  • an alloy that is a candidate for a gold alloy is an “alloy (or various alloys)”, and among the alloys, an alloy that exhibits a gold color according to the present invention is a “gold alloy” and the above alloy
  • gold alloys and others The 18K gold alloy and others produced to compare the colors are called “gold alloys and others”.
  • Table 1 shows the composition, surface state, color tone, Picker's hardness, etc. of the binary alloy having two metal forces of palladium (Pd) and indium (In). All of these binary alloys are alloys in which the mixing ratio of palladium (Pd) and indium (In) is changed, but strictly including inevitable impurities.
  • the prototype symbol 8020 is 80% by weight of palladium
  • Indium is a 20% strength alloy.
  • Prototype 4060 is an alloy composed of 40% by weight palladium and 60% by weight indium.
  • the weight ratio of palladium to indium that is, the value obtained by dividing the weight percent of palladium by the weight percent of indium is shown in the "Pd / In" column of Table 1.
  • the weight ratio (Pd / In) of palladium and indium is 4.00, and in the prototype symbol 4060, it is 0.67.
  • the color tone of each alloy after polishing is shown in the "Alloy color tone” column. Color is 18K gold alloy In addition, it was judged by comparing with the color map of the existing ternary alloy of three kinds of metallic power of gold 'silver' and copper. The color tone of each alloy was whitish when palladium was 62% by weight or more (8020, 7030, 6238) and yellow gold when 6040 (Pd / In was 1.50). As the palladium decreased and the indium increased, the gold became darker, and from 5248 to 4753 became a very dark red gold.
  • Prototype symbols 8020, 7030, and 6238 were judged to be “non-golden” because the color tone of the alloy with a high percentage of palladium was whitish gold and cannot be considered a gold alloy.
  • the color tone of the alloy changed as described above depending on the blending ratio of palladium and indium, it was determined as “gold” as the color tone.
  • the Vickers hardness was measured with various alloys of 5 points using a micro Vickers hardness tester with a weight of 500 gf and a calorie holding time of 10 seconds, and the average value and standard deviation were displayed. (Table 1 and others).
  • the weight ratio of palladium to indium is 0.89 or 0.67, the surface state is unsatisfactory. Therefore, the weight ratio of palladium and indium suitable for the golden alloy is specified to be between 0.92 and 1.50.
  • Table 7 shows the discoloration resistance test results for investigating the corrosion resistance of prototype symbols 5545 and 5050 among the binary alloys of palladium (Pd) and indium (In).
  • the 18K gold alloy 'red used for comparison did not change color in the atmosphere or in various reagent immersion experiments (circles), and was found to have excellent corrosion resistance, that is, the corrosion resistance evaluation was judged to be “excellent”.
  • the 12K gold alloy red containing 40% by weight of copper was slightly discolored with acetic acid (99.7%) ( ⁇ mark), but under other conditions, it was judged that the corrosion resistance evaluation without discoloration was “good”.
  • the copper-zinc alloy (prototype symbol Cu65Zn35) and the copper-aluminum alloy (prototype symbol Cu90A110) do not change color in the atmosphere, but discolor under other conditions (marked X), and the corrosion resistance evaluation was judged to be “impossible”. .
  • the binary alloys composed of two metals, palladium and indium, prototype symbols 5545 and 5050 did not change color under all conditions, and the corrosion resistance evaluation was judged to be “excellent”. It was done.
  • the corrosion resistance was evaluated as “excellent” for all the discoloration resistance test items that were rated as “Good”. In the test in item 1, the test was evaluated as “good”; As for the corrosion resistance of the golden alloy, those with “OK” or higher were judged to have good corrosion resistance.
  • Table 2 shows the composition, surface state, color tone, and the like of the ternary alloy having palladium, indium, and silver (Ag) forces.
  • the surface conditions were all good ( ⁇ mark).
  • the color of the alloy is bright (pink, yellow or yellow) for all alloys, and the color becomes lighter with increasing silver.
  • Table 7 shows the results of the discoloration resistance test of the ternary alloy composed of rhodium, indium and silver. With 4040Ag20 with a silver content of 20%, there is no discoloration under all conditions, and the corrosion resistance evaluation is
  • Table 3 shows the composition, surface state, color tone and the like of the ternary alloy having palladium, indium and copper (Cu) force.
  • the surface condition was good (circle mark), and the color tone was also judged as “golden”.
  • Table 7 shows the discoloration resistance test results of ternary alloys (4040Cu20, etc.) made of palladium, indium and copper.
  • each content of palladium and indium is 10% by weight or more, and the content of copper is 40% by weight. In the case of% or less, it was found that a golden alloy having a gold color and good corrosion resistance was produced.
  • Palladium, color tone of the indium gold (Au) or platinum group metal added alloy include gold (A U) All If example mosquitoes ⁇ gold and a force palladium, red than 5050 indium binary alloy My thinness is thin.
  • 5045Sn5 with tin (Sn) and 5045Ga5 with gallium (Ga) were both yellow gold.
  • 5049Irl with 1% iridium (Ir) and 5049Sil with 1% silicon (Si) were both red gold.
  • Table 4 shows the Vickers hardness of each alloy.
  • the ternary alloy (4040Au20) made of palladium, indium and gold (Au) did not change color in all discoloration resistance test items, and the corrosion resistance evaluation was judged as “excellent”.
  • Corrosion resistance of the above-mentioned binary alloys of palladium and indium (5545 5050), ternary alloy with 40% gold (Au) 4040Au20 and ternary alloy with platinum added 5045Pt5 5045Rh5 5045Ru5 5045 Sn5 5045Ga5 5049IrU 5049Sil
  • the evaluation was “excellent”, and it was found that the gold alloy based on palladium and indium has excellent corrosion resistance.
  • the weight ratio of palladium to indium is between 0.92 and 1.5, and the palladium content and indium content alloy content are both 10 wt% or more, 60 wt% or less of gold (Au) 20% by weight or less of platinum (Pt) 10 wt% or less of rhodium (Rh) 5-fold bulk 0/0 following ruthenium ( Ru), tin (Sn) or gallium (Ga), or less than 1% by weight
  • iridium (Ir) or silicon (Si) was added, it was found that gold-colored alloys having good corrosion resistance were produced.
  • the palladium-indium alloy according to the present invention maintains its golden color tone and has good corrosion resistance even if a plurality of other metals X are added as required.
  • Table 5 shows the composition, surface state, color tone, and the like of the quaternary alloy containing the above-described ternary alloy composed of palladium, indium, and silver (Ag) and other metal Y.
  • the color of the alloy is all yellow gold, and the color does not change depending on the added metal, antimony (Sb), germanium (Ge), zinc (Zn), aluminum (A1) or platinum (Pt). I got it.
  • o Polished surface is uniformly alloyed, free from cracks and color spots
  • Table 8 shows the results of examining the corrosion resistance of these alloys.
  • 10 10Ag80 with a total content of palladium and indium of 20% is a 1010Ag75Pt5 that has a corrosion resistance evaluation of “possible” and has a good corrosion resistance Pt.
  • the evaluation of corrosion resistance is “good”. While maintaining the gold color in this way, It is possible to produce an alloy having a good composition.
  • Palladium forms a total solid solution with silver, copper, gold, platinum, and rhodium, and also dissolves ruthenium to about 16% by weight.
  • silver forms a complete solid solution with gold
  • copper is a eutectic alloy with a solid solution range.
  • Platinum forms a solid solution with a rapid cooling from a liquid state.
  • Copper forms a solid solution with gold, platinum and rhodium in addition to palladium.
  • Gold forms a solid solution with platinum in addition to palladium, silver and copper.
  • palladium, silver, copper, gold, and platinum are easy to be alloyed except rhodium, ruthenium, and iridium.
  • Indium has a solid solubility limit, but dissolves in these metals.
  • rhodium, ruthenium and iridium are effective to be added in a small amount depending on the purpose of use because they refine the alloy crystal and improve its characteristics.
  • Tin, zinc, silicon, antimony, aluminum and gallium improve the forgeability, so it is effective to add a small amount.
  • the gold alloy according to the present invention does not contain gold (Au) and copper (Cu)! However, it is a gold alloy exhibiting an elegant gold color. Therefore, it is possible to produce a gold alloy product exhibiting a gold color at a lower price than a conventional gold alloy containing pure gold and pure gold.
  • the gold alloy according to the present invention is less expensive than conventional gold alloys. On the other hand, it has corrosion resistance equivalent to that of conventional gold alloys (for example, 12K alloys).
  • the gold alloy product according to the present invention can be easily produced with a metal melting apparatus or the like as in the case of conventional gold alloys.

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  • Chemical & Material Sciences (AREA)
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Abstract

Conventional gold and gold alloys are expensive, while copper-zinc alloys are poor in corrosion resistance though they are inexpensive. Further, sintered titanium nitride alloy has the disadvantage of necessitating special equipment and technique and so on. The invention has been accomplished on the basis of a finding that alloys consisting of palladium (Pd) and indium (In) sparkle with gold though both palladium and indium are white metals. Golden Pd-In alloys according to the invention are golden and have advantages in that they are more inexpensive than gold and gold alloys and excellent in corrosion resistance and that no special equipment is necessary in producing the Pd-In alloys.

Description

明 細 書  Specification
Pd-In系金色合金  Pd-In gold alloy
技術分野  Technical field
[0001] 一般に、人間の視細胞には赤、緑、青に感じる 3種類の細胞があり、その刺激の割 合によって色を感じていると言われている。金 (Au)が金色に輝くのは、赤と緑の反射 率が 90%以上と高ぐ青の反射率が 50%以下と低くなつているために金色に見えると 言われている。  [0001] In general, human visual cells have three types of cells that feel red, green, and blue, and it is said that the color is sensed by the percentage of stimulation. It is said that gold (Au) shines in gold because red and green reflectivity is 90% or higher and blue reflectivity is 50% or less.
同様の性質を持つ金属には、他に銅 (Cu)とセシウム (Cs)があり、銅は赤の反射率 が高ぐ緑と青の反射率が低いため、金色でも赤っぽく見える。また、銀 (Ag)は可視 光全域にわたって 90%以上の反射率を示すので白く見える。  Other metals with similar properties include copper (Cu) and cesium (Cs). Copper has a high red reflectivity and low green and blue reflectivity, so even gold looks reddish. In addition, silver (Ag) appears white because it exhibits a reflectivity of 90% or more over the entire visible light.
[0002] 一方、パラジウム (Pd)は銀白色の金属で、常温で安定な面心立方構造を有する。  On the other hand, palladium (Pd) is a silver-white metal and has a face-centered cubic structure that is stable at room temperature.
インジウム (In)は銀色系灰色の金属で、常温で安定な正方晶の結晶構造を有する。 すなわち、パラジウムとインジウムは、いずれも、銀色、白色系の金属である。  Indium (In) is a silvery gray metal with a tetragonal crystal structure that is stable at room temperature. That is, both palladium and indium are silver and white metals.
[0003] 本発明は、パラジウム (Pd)とインジウム (In)を主な母体とする、優美な金色を呈する 金色合金であり、装飾用部材 (ブローチ、メダル、ボタン、ネクタイピン、イアリング、ピ ァス、ペンダントヘッド、時計部材 (例えば文字盤の目盛り)など)、洋食器類などの調 度品部材、美術工芸品あるいは歯科用金属部材としても利用可能な、 Pd-In系金色 合金に係るものである。  [0003] The present invention is an elegant gold-colored gold alloy mainly composed of palladium (Pd) and indium (In), and is a decorative member (brooch, medal, button, tie pin, earring, pin Pd-In gold alloys that can be used as furniture, pendant heads, clock members (eg dial scales), furniture items such as western tableware, arts and crafts, or dental metal members It is.
背景技術  Background art
[0004] 従来、例えば装飾用に使用される金色を呈する材料としては、純金や金合金、黄 銅等の各種金属、または、金属表面に金メッキを施したものが使用されてきた。 しかし、純金あるいは金合金は高価であり、金メッキは剥がれることがあるという欠点 かあつた。  [0004] Conventionally, as a gold-colored material used for decoration, for example, various metals such as pure gold, a gold alloy, brass, or a metal surface plated with gold has been used. However, pure gold or gold alloy is expensive, and gold plating may be peeled off.
銅 ·亜鉛合金及び銅 ·アルミニウム合金は安価ではある力 耐食性が良くな 、と!/、う 欠点があった。  Copper / zinc alloys and copper / aluminum alloys have low defects in strength and corrosion resistance!
一方、窒化チタンの皮膜及び焼結合金は、硬度が高ぐ耐食性に優れるなどの特 性を有しているが、特殊な装置と技術が必要であり、個別の金色合金の作製には適 していない。 On the other hand, titanium nitride films and sintered alloys have characteristics such as high hardness and excellent corrosion resistance, but they require special equipment and technology and are suitable for the production of individual gold alloys. Not done.
[0005] 例えば、特許文献 1には、窒化チタン等を Ni、 Co等の金属で結合させた金色焼結 合金の焼結性を改善した、金色の色調を有する金色焼結合金が提案されている。し かし、窒化チタンを母体とする焼結合金の作製には、特殊な装置が必要となり、個別 の金色合金の作製には適して ヽな 、。  [0005] For example, Patent Document 1 proposes a gold-colored sintered alloy having a golden color tone that improves the sinterability of a gold-colored sintered alloy in which titanium nitride or the like is bonded with a metal such as Ni or Co. Yes. However, special equipment is required to produce a sintered alloy based on titanium nitride, which is suitable for the production of individual gold alloys.
特許文献 1 :特開平 5— 311311号公報  Patent Document 1: JP-A-5-311311
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0006] 上述したように、従来の金合金は高価である。銅 ·亜鉛合金及び銅 ·アルミニウム合 金は安価であるが、耐食性が劣る。窒化チタンの焼結合金は、硬度及び耐食性に優 れるが、特殊な装置と技術が必要であり、個別の金色合金の作製には適していない 等の欠点があった。 [0006] As described above, conventional gold alloys are expensive. Copper-zinc alloys and copper-aluminum alloys are inexpensive but have poor corrosion resistance. Titanium nitride sintered alloys are superior in hardness and corrosion resistance, but they require special equipment and techniques, and are not suitable for the production of individual gold alloys.
[0007] 発明者は、各種の合金の研究中に、いずれも銀色、白色系の金属であるパラジゥ ム(Pd)とインジウム (In)との合金が金色に輝くことを発見した。  [0007] During the study of various alloys, the inventor discovered that an alloy of palladium (Pd) and indium (In), which are silver and white metals, all shines in gold.
そこで、各種の組成で実験を重ねた結果、適度な硬度があり、純金製品あるいは従 来の金合金に比べて価格が安ぐ耐食性もあり、さらに当該合金を作製するのに特 殊な装置を必要としな!ヽ等の優れた特性を有する新 Uヽ金色合金を発明した。  Therefore, as a result of repeated experiments with various compositions, it has moderate hardness, is cheaper and more corrosion-resistant than pure gold products or conventional gold alloys, and has a special device for producing such alloys. We have invented a new U-gold alloy with excellent properties such as no need!
[0008] 本発明に係る金色合金は、金色を呈する金 (Au)及び銅 (Cu)を含有しな!、でも、優 美な金色を呈する金色合金である。従って、純金及び純金を含む従来のいわゆる金 合金より安価に作製することができる。  [0008] The gold alloy according to the present invention does not contain gold (Au) and copper (Cu) exhibiting a gold color! However, it is a gold alloy exhibiting an excellent gold color. Therefore, it can be produced at a lower cost than conventional so-called gold alloys including pure gold and pure gold.
ちなみに、平成 18年 10月時点での各貴金属の価格は、プラチナよ は約 4400円 ん金(Au)は約 2300円 Zg、パラジウム(Pd)は約 1300円 Zg、インジウム(In)は約 1 20円 Zg、銀 (Ag)は約 45円 Zgである。従って、パラジウムの価格は金の価格の約半 分、インジウムは約 5%であり、例えば、パラジウム重量 50%、インジウム重量 50%の 金色合金 (後述する試作記号 5050)の素材価格は、 18K金合金の約 40%程度と換算 される。  By the way, the price of each precious metal as of October 2006 is about 4400 yen for platinum (Au) is about 2300 yen Zg, palladium (Pd) is about 1300 yen Zg, and indium (In) is about 1 20 yen Zg and silver (Ag) are about 45 yen Zg. Therefore, the price of palladium is about half of the price of gold, and about 5% of indium. For example, the material price of a gold alloy with 50% palladium weight and 50% indium weight (prototype symbol 5050 described later) is 18K gold. It is converted to about 40% of the alloy.
[0009] し力も、本発明に係る金色合金は、従来の金合金に比べて硬度が高ぐ表面に傷 が生じにくい。ちなみに、各貴金属のビッカース硬さは、プラチナ 41、金 22、銀 24であ るのに対して、本発明による Pd-In系金色合金は、ビッカース硬さは 160から 360程度 である。 [0009] In addition, the gold alloy according to the present invention is less likely to be scratched on the surface having higher hardness than the conventional gold alloy. By the way, Vickers hardness of each precious metal is platinum 41, gold 22, silver 24 In contrast, the Pd—In gold alloy according to the present invention has a Vickers hardness of about 160 to 360.
その一方で、本発明に係る金色合金は、後述するように従来の 18K金合金等と同 等の耐食性を有する。  On the other hand, the gold alloy according to the present invention has the same corrosion resistance as the conventional 18K gold alloy and the like, as will be described later.
さらに、本発明に係る金色合金力もなる製品を作製するには、従来の金合金と同様 に、金属溶解装置で簡単に作製することができるので、特殊な装置や技術が不要で 、金色合金による製品の個別作製が可能となる。  Furthermore, in order to produce a product having a gold alloy strength according to the present invention, it can be easily produced with a metal melting apparatus, as in the case of a conventional gold alloy. Individual product production is possible.
課題を解決するための手段  Means for solving the problem
[0010] 上述したように、発明者は各種の合金を研究していて、銀色、白色系の金属である ノ ラジウムとインジウムの合金が金色に輝くことを発見した。そこで、各種の組成でど のような特性を有する金色合金が作製できるか、実験を重ねた結果、以下の態様か らなる新し ヽ金色合金を発明した。 [0010] As described above, the inventor has studied various alloys, and has discovered that an alloy of silver and white, which is a silver and white metal, shines in gold. Therefore, as a result of repeated experiments as to what kind of properties can be produced with various compositions, a new gold-colored alloy having the following aspects has been invented.
[0011] この発明の第 1の態様は、少なくともパラジウム (Pd)とインジウム (In)を含む合金で あって、パラジウムの重量とインジウムの重量の比が 0.92〜1.5の間であり、かつ、パラ ジゥムの含有率とインジウムの含有率が共に 10重量0 /0以上であることを特徴とする Pd -In系金色合金である。 [0011] A first aspect of the present invention is an alloy containing at least palladium (Pd) and indium (In), wherein the ratio of the weight of palladium to the weight of indium is between 0.92 and 1.5, and a Pd -In based gold alloy, wherein the content of the indium content of Jiumu is both 10 weight 0/0 above.
[0012] この発明の第 2の態様は、パラジウム (Pd)、インジウム(In)にカ卩えて、他の金属とし て 60重量%以下の金 (Au)、 20重量%以下の白金(Pt)、 10重量%以下のロジウム(R h)、 5重量%以下のルテニウム(Ru)、錫(Sn)、ガリウム(Ga)、 1重量%以下のイリジゥ ム(Ir)又は珪素(Si)の 、ずれか一以上の金属を含むことを特徴とする Pd-In系金色 合金である。  [0012] In the second aspect of the present invention, in addition to palladium (Pd) and indium (In), 60% by weight or less of gold (Au) and 20% by weight or less of platinum (Pt) as other metals. 10% by weight rhodium (Rh), 5% by weight ruthenium (Ru), tin (Sn), gallium (Ga), 1% by weight iridium (Ir) or silicon (Si) It is a Pd-In gold alloy characterized by containing one or more metals.
[0013] この発明の第 3の態様は、パラジウム(Pd)とインジウム(In)及び不可避不純物から なる二元合金であって、パラジウムの重量とインジウムの重量の比が 0.92〜1.5の間で あることを特徴とする Pd-In系金色合金である。  [0013] A third aspect of the present invention is a binary alloy comprising palladium (Pd), indium (In), and inevitable impurities, wherein the ratio of the weight of palladium to the weight of indium is between 0.92 and 1.5. This is a Pd-In gold alloy.
[0014] この発明の第 4の態様は、パラジウム (Pd)、インジウム(In)及び銀 (Ag)を含む合金 であって、パラジウムの含有率とインジウムの含有率が共に 10重量%以上、かつ、銀 の含有率が 80重量%以下であることを特徴とする Pd-In系金色合金である。  [0014] A fourth aspect of the present invention is an alloy containing palladium (Pd), indium (In), and silver (Ag), wherein both the palladium content and the indium content are 10% by weight or more, and A Pd-In-based golden alloy characterized by having a silver content of 80% by weight or less.
[0015] この発明の第 5の態様は、ノ《ラジウム (Pd)、インジウム(In)及び銀 (Ag)に加えて、 他の金属として 5重量0 /0以下のアンチモン(Sb)、ゲルマニウム(Ge)、亜鉛 (Zn)、白 金(Pt)、又は 0.5重量%以下のアルミニウム (A1)の!、ずれか一以上の金属を含むこと を特徴とする Pd-In系金色合金である。 [0015] In the fifth aspect of the present invention, in addition to nano << radium (Pd), indium (In) and silver (Ag), 5 weight 0/0 following antimony other metals (Sb), germanium (Ge), zinc (Zn), platinum (Pt), or 0.5 wt% or less of aluminum (A1)!, Shift one or more It is a Pd-In gold alloy characterized by containing metal.
[0016] この発明の第 6の態様は、パラジウム (Pd)、インジウム(In)及び銅 (Cu)を含む合金 であって、パラジウムの含有率とインジウムの含有率が共に 10重量%以上、かつ、銅 の含有率が 40重量%以下であることを特徴とする Pd-In系金色合金である。  [0016] A sixth aspect of the present invention is an alloy containing palladium (Pd), indium (In), and copper (Cu), wherein both the palladium content and the indium content are 10% by weight or more, and The Pd-In gold alloy is characterized by having a copper content of 40% by weight or less.
[0017] この発明の第 7の態様は、パラジウム (Pd)とインジウム (In)を含む合金であって、そ の色調がレッドの金色、ピンクの金色、イェローの金色、イェローぼい金色のいずれ かの色調を呈することを特徴とする Pd-In系金色合金である。  [0017] A seventh aspect of the present invention is an alloy containing palladium (Pd) and indium (In), and the color tone is any of red gold, pink gold, yellow gold, and yellow gold. It is a Pd-In gold alloy characterized by exhibiting such a color tone.
[0018] この発明の第 8の態様は、パラジウム(Pd)とインジウム(In)を含む合金であって、更 に大気中、 30%希塩酸、 99.7%酢酸、 30%希硫酸、又は 10%過酸ィ匕水素水のいず れの環境下でも良好な耐食性を有することを特徴とする Pd-In系金色合金である。 発明の効果  [0018] An eighth aspect of the present invention is an alloy containing palladium (Pd) and indium (In), and further in the atmosphere, 30% dilute hydrochloric acid, 99.7% acetic acid, 30% dilute sulfuric acid, or 10% excess. It is a Pd-In gold alloy characterized by having good corrosion resistance in any environment of either acid or hydrogen water. The invention's effect
[0019] 本発明に係る金色合金は、金 (Au)及び銅 (Cu)を含有しな!、でも、優美な金色を 呈する金色合金である。従って、純金及び純金を含む従来のいわゆる金合金より安 価に、金色を呈する金色合金製品を作製することができる。  [0019] The gold alloy according to the present invention does not contain gold (Au) and copper (Cu)! However, it is a gold alloy exhibiting an elegant gold color. Therefore, it is possible to produce a gold alloy product exhibiting a gold color at a lower price than a conventional gold alloy containing pure gold and pure gold.
本発明に係る金色合金は、従来の金合金に比べて安価である。一方で、従来の金 合金 (例えば 12K合金等)と同等の耐食性を有する。  The gold alloy according to the present invention is less expensive than conventional gold alloys. On the other hand, it has corrosion resistance equivalent to that of conventional gold alloys (for example, 12K alloys).
さらに本発明に係る金色合金製品は、従来の金合金と同様に金属溶解装置等で 簡便に作製することができる。  Furthermore, the gold alloy product according to the present invention can be easily produced with a metal melting apparatus or the like as in the case of conventional gold alloys.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0020] 本発明の実施の形態を以下説明する。 [0020] Embodiments of the present invention will be described below.
(実施例 1)  (Example 1)
パラジウム (Pd)とインジウム (In)の高純度地金を秤量し、高周波溶解装置を使用し て、アルゴンガス雰囲気下で溶解して各種試作合金を作製した (試作記号 : 8020、 40 60他)。その試作合金の組成を表 1に示す。  Various prototype alloys were prepared by weighing high purity ingots of palladium (Pd) and indium (In) and melting them in an argon gas atmosphere using a high frequency melting device (prototype symbols: 8020, 40 60, etc.) . Table 1 shows the composition of the prototype alloy.
[0021] [表 1] ¾ 1 試作 Pd-In合金の とその特性 [0021] [Table 1] ¾ 1 Prototype Pd-In alloy and its properties
Figure imgf000006_0001
Figure imgf000006_0001
* 1 : その他には,不可避不純物を含む  * 1: Others include inevitable impurities
* 2 : O 研磨面が均一に合金化され、亀裂および色斑が無い  * 2: O Polished surface is uniformly alloyed and there are no cracks and color spots
X それ以外のもの  X Other
* 3 : 平均値 (棵準偏差)、 n=5 上記各種試作合金と色調を比較するために、レッド.ゴールド、イェロー.ゴールド、 グリーン.ゴールドの 3種類の 18K金合金等を、上記と同じ方法で作製した。表 6にこ れらの比較金合金の組成を示す (金合金記号: 18K金合金 ·レッド、 18K金合金'イエ ロー、 18K金合金'グリーン、 12K金合金'イェロー他)。 * 3: Average value (standard deviation), n = 5 Three types of 18K gold alloys such as red gold, yellow gold, and green gold are the same as above to compare the color tone with the above various prototype alloys. It was produced by the method. Table 6 shows the composition of these comparative gold alloys (gold alloy symbols: 18K gold alloy · red, 18K gold alloy 'yellow, 18K gold alloy' green, 12K gold alloy 'yellow, etc.).
[表 6] 表 6 比較金合金等の組成 [Table 6] Table 6 Composition of comparative gold alloys, etc.
Figure imgf000006_0002
現在、金色の指環、ネックレス、ピアスなどの高級品には、 18K金合金が用いられて いる。通常、装飾品用 18K金合金の組成は金 (Au)が 75%であり、ほかの成分は銅( Cu)と銀 (Ag)である。 18K金合金の標準的組成は、 Au (75%)、 Cu (10〜15%)、 Ag(10〜15%)であり、イエ ローあるいはイェローぽ 、金色を呈すること力 イエロ一.ゴールドと呼ばれて!/、る。 銅の比率を更に多くすると、金合金の色調は赤っぽくなり、レッド'ゴールドと呼ばれ 、逆に銀の比率を更に多くすると緑がかり、グリーン 'ゴールドと呼ばれている。
Figure imgf000006_0002
Currently, 18K gold alloys are used for luxury items such as golden finger rings, necklaces, and earrings. The composition of 18K gold alloy for decoration is usually 75% of gold (Au), and the other components are copper (Cu) and silver (Ag). The standard composition of 18K gold alloy is Au (75%), Cu (10-15%), Ag (10-15%), and it has the power to show yellow or yellow, gold color. Re! / If the ratio of copper is further increased, the color of the gold alloy becomes reddish and is called red 'gold'. Conversely, if the ratio of silver is further increased, the color becomes green and the color is called green 'gold.
そこで、この実験の色調検査には、上記 3種類の色調の 18K金合金を作製して比 較材として用いた。  Therefore, in the color tone inspection of this experiment, the 18K gold alloys with the above three types of color tone were prepared and used as comparison materials.
耐変色試験には、レッド'ゴールドと呼ばれている 18K金合金'レッドのほ力 12K金 合金 ·レッド、銅 ·亜鉛合金(Cu65Zn35)、銅 ·アルミニウム合金(Cu90A110)等を作製 して、比較材として用いた。  For the discoloration resistance test, 18K gold alloy called red 'Gold' red force 12K gold alloy · Red, copper · zinc alloy (Cu65Zn35), copper · aluminum alloy (Cu90A110), etc. were prepared and compared. Used as material.
[0024] 以下、本明細書において、金色合金の候補となる合金を「合金 (あるいは各種合金 )」と、当該合金の内、本発明に係る金色を呈する合金を「金色合金」と、上記合金と 色調を比較するために作製した 18K金合金他を「金合金他」と呼ぶ。  Hereinafter, in the present specification, an alloy that is a candidate for a gold alloy is an “alloy (or various alloys)”, and among the alloys, an alloy that exhibits a gold color according to the present invention is a “gold alloy” and the above alloy The 18K gold alloy and others produced to compare the colors are called “gold alloys and others”.
[0025] 表 1に、パラジウム(Pd)とインジウム(In)の 2種類の金属力もなる二元合金の組成、 表面状態、色調及びピッカース硬さ等を示す。本二元合金はいずれもパラジウム (Pd )とインジウム (In)の配合比率を変えた合金であるが、厳密には不可避不純物を含む 表 1中、例えば、試作記号 8020は、パラジウム 80重量%、インジウム 20重量%力 な る合金である。また試作記号 4060は、パラジウム 40重量%、インジウム 60重量%から なる合金である。  [0025] Table 1 shows the composition, surface state, color tone, Picker's hardness, etc. of the binary alloy having two metal forces of palladium (Pd) and indium (In). All of these binary alloys are alloys in which the mixing ratio of palladium (Pd) and indium (In) is changed, but strictly including inevitable impurities. In Table 1, for example, the prototype symbol 8020 is 80% by weight of palladium, Indium is a 20% strength alloy. Prototype 4060 is an alloy composed of 40% by weight palladium and 60% by weight indium.
[0026] パラジウムとインジウムの重量比、すなわち、パラジウムの重量%をインジウムの重 量%で割った値を表 1の「Pd/In」欄に示す。例えば、試作記号 8020では、パラジウム とインジウムの重量比(Pd/In)は 4.00となり、試作記号 4060では、 0.67となる。  [0026] The weight ratio of palladium to indium, that is, the value obtained by dividing the weight percent of palladium by the weight percent of indium is shown in the "Pd / In" column of Table 1. For example, in the prototype symbol 8020, the weight ratio (Pd / In) of palladium and indium is 4.00, and in the prototype symbol 4060, it is 0.67.
[0027] 上記方法にて作製した各種合金、金合金他の表面を研磨したあとで、肉眼及び顕 微鏡を用いて、その表面状態及び色調を観察した。その結果、各種合金の研磨面が 均一に合金化されていて、亀裂及び色斑が無いものには〇印を、それ以外のものに は X印を表示した (表 1他)。なお、試作記号 4753、 4060には微細な亀裂がみられ表 面状態が不良と判定された( X印)。  [0027] After polishing the surfaces of various alloys, gold alloys and the like prepared by the above method, the surface state and color tone were observed using the naked eye and a microscope. As a result, the polished surfaces of various alloys were evenly alloyed, and those with no cracks and color spots were marked with a circle, and the others were marked with an X (Table 1 and others). Prototype symbols 4753 and 4060 showed a fine crack and the surface condition was judged to be poor (marked X).
[0028] 研磨した後の各種合金の色調を、「合金の色調」の欄に示す。色調は、 18K金合金 及び既存の金 '銀'銅の 3種の金属力 なる三元合金の色調図と比較して判定した。 各合金の色調は、パラジウムが 62重量%以上(8020、 7030、 6238)では白っぽくなり 、 6040 (Pd/Inが 1.50)ではイェローぼい金色であった。パラジウムの減少、インジウム の増加とともに金色が濃くなり、 5248から 4753では非常に濃いレッドの金色になった。 試作記号 8020、 7030、 6238は、パラジウムの割合が多ぐ合金の色調は白っぽい金 色であり、金色の合金とは見なせないので「非金色」と判定された。それに対して、試 作記号 6040〜4060については、パラジウム、インジウムの配合比率によって上述した ように合金の色調は変化するものの、色調として「金色」と判定された。 [0028] The color tone of each alloy after polishing is shown in the "Alloy color tone" column. Color is 18K gold alloy In addition, it was judged by comparing with the color map of the existing ternary alloy of three kinds of metallic power of gold 'silver' and copper. The color tone of each alloy was whitish when palladium was 62% by weight or more (8020, 7030, 6238) and yellow gold when 6040 (Pd / In was 1.50). As the palladium decreased and the indium increased, the gold became darker, and from 5248 to 4753 became a very dark red gold. Prototype symbols 8020, 7030, and 6238 were judged to be “non-golden” because the color tone of the alloy with a high percentage of palladium was whitish gold and cannot be considered a gold alloy. On the other hand, for trial symbols 6040 to 4060, although the color tone of the alloy changed as described above depending on the blending ratio of palladium and indium, it was determined as “gold” as the color tone.
[0029] また、ビッカース硬さは、マイクロビッカース硬さ試験機を使用して、加重 500gf、カロ 重保持時間を 10秒間として 5点の各種合金で測定し、その平均値及び標準偏差を表 示した (表 1他)。 [0029] The Vickers hardness was measured with various alloys of 5 points using a micro Vickers hardness tester with a weight of 500 gf and a calorie holding time of 10 seconds, and the average value and standard deviation were displayed. (Table 1 and others).
[0030] 以上から、パラジウムとインジウムの重量比が 0.89、 0.67の場合には表面状態が不 良となり、逆に 1.63以上では、非金色となる。従って、金色合金に適したパラジウムと インジウムの重量比を 0.92〜 1.50の間と規定する。  [0030] From the above, when the weight ratio of palladium to indium is 0.89 or 0.67, the surface state is unsatisfactory. Therefore, the weight ratio of palladium and indium suitable for the golden alloy is specified to be between 0.92 and 1.50.
[0031] (耐食性についての実験)  [0031] (Experiment on corrosion resistance)
パラジウム(Pd)とインジウム(In)の二元合金のうち、試作記号 5545、 5050の耐食性 を調査するための耐変色試験結果を表 7に示す。  Table 7 shows the discoloration resistance test results for investigating the corrosion resistance of prototype symbols 5545 and 5050 among the binary alloys of palladium (Pd) and indium (In).
耐食性を比較するために、パラジウムとインジウムの二元合金(5545、 5050)と、 18K 金合金 ·レッド、 12K金合金 ·レッド、銅 ·亜鉛合金(Cu65Zn35)、銅 ·アルミニウム合金 (Cu90A110)を、大気中(30日間)及び、希塩酸 (30%)、酢酸 (99.7%)、希硫酸 (30% )及び過酸化水素水(10%)の各種試薬に 48時間浸漬した耐変色試験を行った。  To compare the corrosion resistance, binary alloys of palladium and indium (5545, 5050), 18K gold alloy · red, 12K gold alloy · red, copper · zinc alloy (Cu65Zn35), copper · aluminum alloy (Cu90A110), A discoloration resistance test was conducted in the air (30 days) and by immersion in various reagents of dilute hydrochloric acid (30%), acetic acid (99.7%), dilute sulfuric acid (30%) and hydrogen peroxide (10%) for 48 hours.
[0032] [表 7] 表 7 »栾 ft 餘結奥(* 1 ) [0032] [Table 7] Table 7 »栾 ft 餘 back (* 1)
Figure imgf000009_0001
Figure imgf000009_0001
*ι ο:変色なし、△:僅かに変色、 X:変色あ y  * ι ο: No discoloration, △: Slight discoloration, X: Discoloration y
[0033] 比較に用いた 18K金合金'レッドは、大気中も各種試薬の浸漬実験でも変色せず( 〇印)、耐食性が優れている、すなわち耐食性評価が「優」と判断された。 [0033] The 18K gold alloy 'red used for comparison did not change color in the atmosphere or in various reagent immersion experiments (circles), and was found to have excellent corrosion resistance, that is, the corrosion resistance evaluation was judged to be “excellent”.
銅を 40重量%含む 12K金合金'レッドは、酢酸 (99.7%)で僅かに変色したが(△印 )、ほかの条件では変色はなぐ耐食性評価は「良」と判断された。  The 12K gold alloy red containing 40% by weight of copper was slightly discolored with acetic acid (99.7%) (△ mark), but under other conditions, it was judged that the corrosion resistance evaluation without discoloration was “good”.
銅 ·亜鉛合金 (試作記号 Cu65Zn35)及び銅 ·アルミニウム合金 (試作記号 Cu90A110 )は、大気中では変色しないが、その他の条件では変色し(X印)、耐食性評価は「不 可」と判断された。  The copper-zinc alloy (prototype symbol Cu65Zn35) and the copper-aluminum alloy (prototype symbol Cu90A110) do not change color in the atmosphere, but discolor under other conditions (marked X), and the corrosion resistance evaluation was judged to be “impossible”. .
上記比較材の耐食性評価結果に対して、パラジウム、インジウムの 2種の金属から 構成される二元合金、試作記号 5545及び 5050は、全ての条件で変色せず、耐食性 評価は「優」と判断された。  Compared to the corrosion resistance evaluation results of the above comparative materials, the binary alloys composed of two metals, palladium and indium, prototype symbols 5545 and 5050, did not change color under all conditions, and the corrosion resistance evaluation was judged to be “excellent”. It was done.
[0034] ここで耐食性の評価は、すべての耐変色試験項目で〇となったものを「優」、レヽず れカ 1項の試験で△となったものは「良」、 2項の試験で△となったものは「可」、それ 以外のものは「不可」と評価した。金色合金の耐食性として、「可」以上のものは耐食 性が良好と判断した。 [0034] Here, the corrosion resistance was evaluated as "excellent" for all the discoloration resistance test items that were rated as "Good". In the test in item 1, the test was evaluated as “good”; As for the corrosion resistance of the golden alloy, those with “OK” or higher were judged to have good corrosion resistance.
[0035] (実施例 2) [0035] (Example 2)
次に、パラジウム、インジウムの他に銀 (Ag)あるいは銅 (Cu)を加えた各種合金の特 性を調査した。  Next, the characteristics of various alloys in which silver (Ag) or copper (Cu) was added in addition to palladium and indium were investigated.
パラジウム (Pd)、インジウム (In)、銀 (Ag)、銅 (Cu)の高純度地金を秤量し、高周波 溶解装置を使用してアルゴンガス雰囲気下で溶解して各種合金を試作した (試作記 号: 4040Ag20 4040Cu20他)。これらの合金組成を表 2〜3に示す。  High-purity ingots of palladium (Pd), indium (In), silver (Ag), and copper (Cu) are weighed and melted in an argon gas atmosphere using a high-frequency melting device to prototype various alloys (prototype Symbol: 4040Ag20 4040Cu20 etc.). These alloy compositions are shown in Tables 2-3.
[0036] [表 2] 表 2 試作 PcHn-Ag合金の組成とその特性 [0036] [Table 2] Table 2 Composition and properties of prototype PcHn-Ag alloy
Figure imgf000010_0001
Figure imgf000010_0001
* 1 : その他には、不可避不純物を含む  * 1: Others include inevitable impurities
* 2 O 研磨面が均一に合金化され. *裂および色斑が無い  * 2 O Polished surface is uniformly alloyed. * No cracks and color spots
それ以外のもの  Other than that
* 3 : 平均値 (探準偏差)、 =5  * 3: Average value (searching deviation), = 5
[0037] [表 3] [0037] [Table 3]
¾ 3 試作 Pd-ίη - Cu合金の 成とその特性 ¾ 3 Preparation of Pd-ίη-Cu alloy and its properties
Figure imgf000011_0001
Figure imgf000011_0001
* 1 : その他には、不可避不純物を含む  * 1: Others include inevitable impurities
* 2 O 研癢面が均一に合金化され、 ¾裂および色斑が無い  * 2 O Polished surface is uniformly alloyed, and there is no ¾ crack or color spot
それ以外のもの  Other than that
* 3 : 平均値 (棵準塥差)、 π=5  * 3: Average value (standard difference), π = 5
[0038] 同様に、各種合金の表面を研磨したあとで、肉眼及び顕微鏡を用いて、その表面 状態及び色調を観察した結果を表 2〜3の「表面状態」の欄に示す。ここで〇印で示 されている合金はその研磨面が均一に合金化されていて、亀裂及び色斑が無いと判 断されるものを示し、それ以外のものは X印で示しているのは上述した二元合金の 場合と同様である。 [0038] Similarly, after polishing the surfaces of various alloys, the results of observing the surface state and color tone with the naked eye and a microscope are shown in the "Surface state" column of Tables 2-3. Here, the alloy indicated by ◯ indicates that the polished surface is uniformly alloyed and is judged to be free of cracks and color spots, and the other is indicated by X. Is the same as in the case of the binary alloy described above.
[0039] 表 2に、パラジウム、インジウム及び銀 (Ag)力もなる三元合金について、その組成と 表面状態、色調等を示す。  [0039] Table 2 shows the composition, surface state, color tone, and the like of the ternary alloy having palladium, indium, and silver (Ag) forces.
表面状態は全て良好(〇印)であった。合金の色調は、全ての合金とも明るい(ピン ク、イェローあるいはイェローぼい)金色であり、銀の増加とともにその色調は薄くなつ た力 銀が 80%含有される 1010Ag80でもイェローぽぃ金色であった。従って、いずれ の合金の色調も「金色」と判定された。  The surface conditions were all good (◯ mark). The color of the alloy is bright (pink, yellow or yellow) for all alloys, and the color becomes lighter with increasing silver. Even 1010Ag80, which contains 80% silver, is yellow gold. It was. Therefore, the color tone of any alloy was determined to be “golden”.
[0040] 前記表 7に、ノ ジウム、インジウム及び銀力 なる三元合金の耐変色試験結果を 示す。銀の含有量が 20%の 4040Ag20では、全ての条件で変色せず、耐食性評価は[0040] Table 7 shows the results of the discoloration resistance test of the ternary alloy composed of rhodium, indium and silver. With 4040Ag20 with a silver content of 20%, there is no discoloration under all conditions, and the corrosion resistance evaluation is
「優」と判断された。 It was judged as “excellent”.
銀の含有量の増加とともに耐食性は悪くなり、 3030Ag40、 2020Ag60では、過酸ィ匕 水素水では僅かに変色、 1010Ag80では酢酸及び過酸化水素水で僅かに変色した 力 それ以外の試験項目では変色しなかった。すなわち 3030Ag40、 2020Ag60の耐 食性評価は「良」、 1010Ag80の耐食性評価は「可」と判断された。  Corrosion resistance worsens with increasing silver content, with 3030Ag40 and 2020Ag60 slightly discolored with peroxyhydrogen water, with 1010Ag80 slightly discolored with acetic acid and hydrogen peroxide solution. There wasn't. In other words, the corrosion resistance evaluation of 3030Ag40 and 2020Ag60 was judged as “good”, and the corrosion resistance evaluation of 1010Ag80 was judged as “good”.
表 2、表 7の結果から、パラジウムとインジウムの含有率が共に 10重量0 /0以上、かつ 、銀の含有率が 80重量%以下の場合に、金色を呈し、かつ、良好な耐食性を有する 金色合金が作製されることが分力ゝつた。 Table 2, from the results in Table 7, both the palladium and indium content 10 weight 0/0 or more, and It was found that when the silver content was 80% by weight or less, a golden alloy having a golden color and having good corrosion resistance was produced.
[0041] 前記表 3に、パラジウム、インジウム及び銅(Cu)力 なる三元合金について、その 組成と表面状態、色調等を示す。いずれの合金でも表面状態は良好であった(〇印 )、また色調も「金色」と判定された。 [0041] Table 3 shows the composition, surface state, color tone and the like of the ternary alloy having palladium, indium and copper (Cu) force. In any alloy, the surface condition was good (circle mark), and the color tone was also judged as “golden”.
表 7に、パラジウム、インジウム及び銅からなる三元合金 (4040Cu20他)の耐変色試 験結果を示す。  Table 7 shows the discoloration resistance test results of ternary alloys (4040Cu20, etc.) made of palladium, indium and copper.
[0042] 表 7から分かるとおり、銅の含有率の増加とともに(4040Cu20→1010Cu80)耐食性 は悪くなる力 銅が最も多い 1010Cu80 (銅の含有率 80%)でも、希塩酸の耐変色試 験結果にぉ 、て、銅 ·亜鉛合金 (Cu65Zn35)及び銅 ·アルミニウム合金 (Cu90A110)よ り良いことが分力つた。ノ ラジウムとインジウムが各 10%含まれることにより銅の耐食性 (耐希塩酸)が向上していることが想定される。  [0042] As can be seen from Table 7, the corrosion resistance decreases with increasing copper content (4040Cu20 → 1010Cu80) Even with 1010Cu80 (copper content 80%), which has the largest amount of copper, Thus, it was found that it was better than copper-zinc alloy (Cu65Zn35) and copper-aluminum alloy (Cu90A110). It is assumed that the corrosion resistance (dilute hydrochloric acid resistance) of copper is improved by containing 10% each of radium and indium.
[0043] 表 3、表 7の結果から、パラジウム、インジウム及び銅力 なる三元合金のうち、パラ ジゥムとインジウムの各含有率が共に 10重量%以上で、かつ、銅の含有率が 40重量 %以下の場合に、金色を呈し、かつ、良好な耐食性を有する金色合金が作製される ことが分力つた。  [0043] From the results in Tables 3 and 7, among the ternary alloys consisting of palladium, indium and copper, each content of palladium and indium is 10% by weight or more, and the content of copper is 40% by weight. In the case of% or less, it was found that a golden alloy having a gold color and good corrosion resistance was produced.
[0044] (実施例 3)  [0044] (Example 3)
次に、パラジウム、インジウムの他に他の金属 Xを加えた各種合金の特性を調査し た。  Next, the characteristics of various alloys with other metals X in addition to palladium and indium were investigated.
パラジウム(Pd)、インジウム(In)の他に、金 (Au)、白金 (Pt)、ロジウム (Rh)、ルテ-ゥ ム (Ru)、錫 (Sn)、ガリウム、 (Ga)、イリジウム (Ir)及び珪素(Si)の高純度地金を秤量し、 高周波溶解装置を使用してアルゴンガス雰囲気下で溶解して各種合金を試作した( 試作記号: 4040Au20、 5045Pt5、 5045Rh5他)。これらの合金組成を表 4に示す。  In addition to palladium (Pd) and indium (In), gold (Au), platinum (Pt), rhodium (Rh), ruthenium (Ru), tin (Sn), gallium, (Ga), iridium (Ir ) And high-purity ingots of silicon (Si) were weighed and melted in an argon gas atmosphere using a high-frequency melting apparatus to make various alloys (prototype symbols: 4040Au20, 5045Pt5, 5045Rh5, etc.). Table 4 shows these alloy compositions.
[0045] [表 4] 表 4 試作 Pd- Ιη-Χ 合金の組成とその特性 [0045] [Table 4] Table 4 Composition and properties of prototype Pd-Χη-Χ alloy
Figure imgf000013_0001
Figure imgf000013_0001
* 1 : その他には、不可避不純物を含む  * 1: Others include inevitable impurities
* 2 O 研磨面が均一に合金化され、 S裂および色斑が無い  * 2 O Polished surface is uniformly alloyed, and there are no S cracks and color spots
X それ以外のもの  X Other
* 3 : 平均値 (檫準偏差),n=5  * 3: Average value (standard deviation), n = 5
[0046] パラジウム、インジウムに金 (Au)又は白金族金属を加えた合金の色調は、金 (AU) をカ卩えた場合は全て金色であった力 パラジウム、インジウム二元合金の 5050より赤 みが薄くなつた。 [0046] Palladium, color tone of the indium gold (Au) or platinum group metal added alloy include gold (A U) All If example mosquitoes卩gold and a force palladium, red than 5050 indium binary alloy My thinness is thin.
白金を加えた場合、 5045P1:5及び 4545PU0はイェローの金色であった力 4040Pt20 はイェローぽぃ金色になった。 ロジウム(Rh)を加えた場合、 5045Rh5及び 4545RM0はイェローの金色であった。ル テニゥム(Ru)を加えた 5045Ru5の色調はイェローの金色であった。  When platinum was added, the force 4040Pt20 became yellow gold when 5045P1: 5 and 4545PU0 were yellow gold. When rhodium (Rh) was added, 5045Rh5 and 4545RM0 were yellow gold. The color of 5045Ru5 with the addition of Rutenum (Ru) was yellow.
さらに錫(Sn)をカ卩えた 5045Sn5、ガリウム(Ga)をくわえた 5045Ga5は、共にイェロー の金色であった。イリジウム (Ir)を 1%加えた 5049Irl、珪素(Si)を 1%加えた 5049Sil は共にレッドの金色であった。  Furthermore, 5045Sn5 with tin (Sn) and 5045Ga5 with gallium (Ga) were both yellow gold. 5049Irl with 1% iridium (Ir) and 5049Sil with 1% silicon (Si) were both red gold.
各合金のビッカース硬さを表 4に示す。  Table 4 shows the Vickers hardness of each alloy.
[0047] 上記金 (Au)及び白金族金属である白金 (Pt)、ロジウム (Rh)、ルテニウム (Ru)、イリ ジゥム(Ir)他を加えた三元合金(4040Au20、 5045Pt5、 5045Rh5、 5045Ru5、 5049Irl 他)の耐食性を調べた結果を表 8に示す。 [0047] The ternary alloys (4040Au20, 5045Pt5, 5045Rh5, 5045Ru5, etc.) with the addition of gold (Au) and platinum group metals platinum (Pt), rhodium (Rh), ruthenium (Ru), iridium (Ir), etc. Table 8 shows the results of examining the corrosion resistance of 5049Irl et al.
パラジウム、インジウム及び金 (Au)からなる三元合金 (4040Au20)については、全て の耐変色試験項目で変色せず、耐食性評価は「優」と判断された。 上述したパラジウム、インジウムの二元合金(5545 5050)、金 (Au)を 20%加えた三 元合金 4040Au20及び白金等を加えた三元合金(5045Pt5 5045Rh5 5045Ru5 5045 Sn5 5045Ga5 5049IrU 5049Sil)のいずれも耐食性評価は「優」であり、パラジウム 及びインジウムを母体とする金色合金が優れた耐食性を有することが分かった。 The ternary alloy (4040Au20) made of palladium, indium and gold (Au) did not change color in all discoloration resistance test items, and the corrosion resistance evaluation was judged as “excellent”. Corrosion resistance of the above-mentioned binary alloys of palladium and indium (5545 5050), ternary alloy with 40% gold (Au) 4040Au20 and ternary alloy with platinum added (5045Pt5 5045Rh5 5045Ru5 5045 Sn5 5045Ga5 5049IrU 5049Sil) The evaluation was “excellent”, and it was found that the gold alloy based on palladium and indium has excellent corrosion resistance.
[¾8] [¾8]
¾ 8 結晏(* 1 ) ¾ 8 ligation (* 1)
Figure imgf000014_0001
Figure imgf000014_0001
*1 O :変色なし、厶:僅かに変色、 :変色あり 表 4、表 8の結果から、パラジウムとインジウムの重量の比が 0.92〜1.5の間であり、 かつ、パラジウムの含有率とインジウムの含有率が共に 10重量%以上である合金に、 60重量%以下の金 (Au) 20%重量以下の白金 (Pt) 10重量%以下のロジウム (Rh) 5重暈0 /0以下のルテニウム (Ru)、錫 (Sn)若しくはガリウム (Ga)、又は 1重量%以下 のイリジウム(Ir)若しくは珪素(Si)を加えた場合に、金色を呈し、かつ、良好な耐食性 を有する金色合金が作製されることが分力ゝつた。 * 1 O: No discoloration, 厶: Slight discoloration,: Discoloration Based on the results in Tables 4 and 8, the weight ratio of palladium to indium is between 0.92 and 1.5, and the palladium content and indium content alloy content are both 10 wt% or more, 60 wt% or less of gold (Au) 20% by weight or less of platinum (Pt) 10 wt% or less of rhodium (Rh) 5-fold bulk 0/0 following ruthenium ( Ru), tin (Sn) or gallium (Ga), or less than 1% by weight When iridium (Ir) or silicon (Si) was added, it was found that gold-colored alloys having good corrosion resistance were produced.
従って、本発明に係るパラジウムとインジウムの合金は、必要に応じて上記その他 の金属 Xを複数種類添加してもその金色の色調を保ち、良好な耐食性をもつことが 想定される。  Therefore, it is assumed that the palladium-indium alloy according to the present invention maintains its golden color tone and has good corrosion resistance even if a plurality of other metals X are added as required.
[0050] (実施例 4) [0050] (Example 4)
上述したパラジウム、インジウム及び銀 (Ag)からなる三元合金に、更に他の金属 Y を含む四元合金について、表 5にその組成と表面状態、色調等を示す。  Table 5 shows the composition, surface state, color tone, and the like of the quaternary alloy containing the above-described ternary alloy composed of palladium, indium, and silver (Ag) and other metal Y.
表面状態は全て良好(〇印)であった。合金の色調は、全てイェローぼい金色であ り、添加する金属、アンチモン (Sb)、ゲルマニウム(Ge)、亜鉛 (Zn)、アルミニウム (A1) 又は白金 (Pt)によって、色調は変化しな力つた。いずれの合金の色調も「金色」と判 定された。各合金のビッカース硬さを表 5に示す。  The surface conditions were all good (◯ mark). The color of the alloy is all yellow gold, and the color does not change depending on the added metal, antimony (Sb), germanium (Ge), zinc (Zn), aluminum (A1) or platinum (Pt). I got it. The color tone of all the alloys was determined to be “golden”. Table 5 shows the Vickers hardness of each alloy.
[0051] [表 5] 恙 5 ¾作 Pd - In - Ae~Y 合金の組成とその特性 [0051] [Table 5] IV 5 ¾ Composition and properties of Pd-In-Ae ~ Y alloys
Figure imgf000015_0001
Figure imgf000015_0001
その他には,不可避不 tt物を含む  Others include inevitable tt objects
o 研磨面が均一に合金化され,亀裂および色斑が無い  o Polished surface is uniformly alloyed, free from cracks and color spots
それ以外のもの  Other than that
平均値 (標準偏差). n=5 Average value (standard deviation). N = 5
[0052] また、これらの合金の耐食性を調べた結果を前記表 8に示す。 [0052] Table 8 shows the results of examining the corrosion resistance of these alloys.
いずれの合金も、過酸化水素水の試験結果では僅かに変色が見られたが、他の検 查項目はいずれも〇であり、これらの合金の耐食性評価は「良」であることが分力 た  All the alloys showed slight discoloration in the hydrogen peroxide test results, but all other test items were ◯, and the corrosion resistance evaluation of these alloys was “good”. The
[0053] なお、表 7及び表 8の結果より、パラジウムとインジウムの含有率の合計が 20%の 10 10Ag80は、耐食性の評価が「可」である力 耐食性の良い Ptをカ卩えた 1010Ag75Pt5で は、耐食性の評価が「良」となっている。このように金色を保ちながら、適宜耐食性の 良 、組成の合金を作製することが可能である。 [0053] From the results of Tables 7 and 8, 10 10Ag80 with a total content of palladium and indium of 20% is a 1010Ag75Pt5 that has a corrosion resistance evaluation of “possible” and has a good corrosion resistance Pt. The evaluation of corrosion resistance is “good”. While maintaining the gold color in this way, It is possible to produce an alloy having a good composition.
[0054] 以上表 5、 8の結果から、パラジウム、インジウム及び銀を含む合金であって、パラジ ゥムの含有率とインジウムの含有率が共に 10重量%以上で、かつ、銀の含有率が 80 重量%以下であり、その他の金属として 5重量%以下のアンチモン(Sb)、ゲルマニウ ム(Ge)、亜鉛 (Zn)、白金(Pt)、又は 0.5重量0 /0以下のアルミニウム (A1)をカ卩えても、 金色の色調を保ち、かつ良好な耐食性をもつ合金が作製できることが確認できた。 従って、本発明に係るパラジウム、インジウム及び銀を含む合金は、必要に応じて、 その他の上記金属 Yを複数種類添加してもその金色の色調を保ち、良好な耐食性を ちっことが想定される。 [0054] From the results in Tables 5 and 8 above, it is an alloy containing palladium, indium and silver, both the palladium content and the indium content are 10% by weight or more, and the silver content is and 80 wt% or less, as other metal than 5% by weight of antimony (Sb), germanium beam (Ge), zinc (Zn), platinum (Pt), or 0.5 0/0 following aluminum (A1) It was confirmed that an alloy having a golden color tone and good corrosion resistance could be produced even if it was made. Therefore, it is assumed that the alloy containing palladium, indium and silver according to the present invention maintains its golden color tone and has good corrosion resistance even if a plurality of other types of the above metals Y are added as required. .
[0055] なお、パラジウムとインジウム他には以下の特性がある。 [0055] In addition to palladium and indium, there are the following characteristics.
パラジウムは銀、銅、金、白金、ロジウムと全率固溶体をつくり、またルテニウムを約 16 重量%まで固溶する。  Palladium forms a total solid solution with silver, copper, gold, platinum, and rhodium, and also dissolves ruthenium to about 16% by weight.
銀はパラジウム以外にも金と全率固溶体をつくり、銅とは固溶体範囲の有る共晶合 金となる。また、白金とは液体状態からの急冷処理により全率固溶体をつくる。  In addition to palladium, silver forms a complete solid solution with gold, and copper is a eutectic alloy with a solid solution range. Platinum forms a solid solution with a rapid cooling from a liquid state.
銅はパラジウム以外にも金、白金、ロジウムと全率固溶体をつくる。  Copper forms a solid solution with gold, platinum and rhodium in addition to palladium.
金はパラジウム、銀、銅以外にも白金と全率固溶体をつくる。  Gold forms a solid solution with platinum in addition to palladium, silver and copper.
[0056] 従って、パラジウム、銀、銅、金、白金は、ロジウム、ルテニウムおよびイリジウムを除 き合金化し易い。インジウムは固溶限があるが、それらの金属に固溶する。 Therefore, palladium, silver, copper, gold, and platinum are easy to be alloyed except rhodium, ruthenium, and iridium. Indium has a solid solubility limit, but dissolves in these metals.
従って、パラジウム 'インジウム二元合金とそれらの金属を組合せた四元以上の合 金で、金色を呈し、耐食性の良好な合金を作製することが可能である。  Therefore, it is possible to produce a gold-colored alloy with good corrosion resistance by using a quaternary or higher alloy obtained by combining palladium'indium binary alloys and these metals.
[0057] なお、ロジウム、ルテニウムおよびイリジウムは合金結晶を微細化して、その特性を 向上させるので、使用目的により少量添加するのが効果的である。 [0057] It should be noted that rhodium, ruthenium and iridium are effective to be added in a small amount depending on the purpose of use because they refine the alloy crystal and improve its characteristics.
錫、亜鉛、珪素、アンチモン、アルミニウムおよびガリウムは铸造性を向上させるの で、少量添加するのが効果的である。  Tin, zinc, silicon, antimony, aluminum and gallium improve the forgeability, so it is effective to add a small amount.
産業上の利用可能性  Industrial applicability
[0058] 本発明に係る金色合金は、金 (Au)及び銅 (Cu)を含有しな!、でも、優美な金色を 呈する金色合金である。従って、純金及び純金を含む従来のいわゆる金合金より安 価に、金色を呈する金色合金製品を作製することができる。 本発明に係る金色合金は、従来の金合金に比べて安価である。一方で、従来の金 合金 (例えば 12K合金等)と同等の耐食性を有する。 [0058] The gold alloy according to the present invention does not contain gold (Au) and copper (Cu)! However, it is a gold alloy exhibiting an elegant gold color. Therefore, it is possible to produce a gold alloy product exhibiting a gold color at a lower price than a conventional gold alloy containing pure gold and pure gold. The gold alloy according to the present invention is less expensive than conventional gold alloys. On the other hand, it has corrosion resistance equivalent to that of conventional gold alloys (for example, 12K alloys).
さらに本発明に係る金色合金製品は、従来の金合金と同様に金属溶解装置等で 簡便に作製することができる。  Furthermore, the gold alloy product according to the present invention can be easily produced with a metal melting apparatus or the like as in the case of conventional gold alloys.

Claims

請求の範囲 The scope of the claims
[1] 少なくともパラジウム (Pd)とインジウム (In)を含む合金であって、当該パラジウムの 重量と当該インジウムの重量の比が 0.92〜1.5の間であり、かつ、前記パラジウムの含 有率と前記インジウムの含有率が共に 10重量%以上であることを特徴とする Pd-In系 金色合金。  [1] An alloy containing at least palladium (Pd) and indium (In), the ratio of the weight of the palladium to the weight of the indium being between 0.92 and 1.5, and the content of the palladium and the above A Pd-In-based golden alloy characterized in that both indium contents are 10% by weight or more.
[2] 前記パラジウム(Pd)、インジウム(In)に加えて、他の金属として 60重量%以下の金( Au)、 20重量%以下の白金(Pt)、 10重量%以下のロジウム(Rh)、 5重量%以下のル テニゥム(Ru)、錫(Sn)、ガリウム(Ga)、 1重量%以下のイリジウム(Ir)又は珪素(Si)の Vヽずれか一以上の金属を含むことを特徴とする請求項 1に記載の Pd-In系金色合金  [2] In addition to palladium (Pd) and indium (In), other metals include 60 wt% or less gold (Au), 20 wt% or less platinum (Pt), 10 wt% or less rhodium (Rh) 5% by weight or less of ruthenium (Ru), tin (Sn), gallium (Ga), 1% by weight or less of iridium (Ir) or silicon (Si) V or one or more metals The Pd-In gold alloy according to claim 1
[3] パラジウム(Pd)とインジウム(In)及び不可避不純物力もなる二元合金であって、当 該パラジウムの重量と当該インジウムの重量の比が 0.92〜1.5の間であることを特徴と する Pd-In系金色合金。 [3] Pd characterized in that it is a binary alloy that also has palladium (Pd), indium (In), and inevitable impurity power, and the ratio of the weight of the palladium to the weight of the indium is between 0.92 and 1.5. -In series gold alloy.
[4] パラジウム (Pd)、インジウム (In)及び銀 (Ag)を含む合金であって、前記パラジウム の含有率と前記インジウムの含有率が共に 10重量%以上、かつ、前記銀の含有率が[4] An alloy containing palladium (Pd), indium (In), and silver (Ag), wherein both the palladium content and the indium content are 10% by weight or more, and the silver content is
80重量%以下であることを特徴とする Pd-In系金色合金。 Pd-In gold alloy characterized by being 80 wt% or less.
[5] 前記パラジウム (Pd)、インジウム (In)及び銀 (Ag)にカ卩えて、他の金属として 5重量[5] 5 weight as other metal in addition to palladium (Pd), indium (In) and silver (Ag)
%以下のアンチモン(Sb)、ゲルマニウム(Ge)、亜鉛 (Zn)、白金(Pt)、又は 0.5重量% Antimony (Sb), germanium (Ge), zinc (Zn), platinum (Pt), or 0.5 weight
%以下のアルミニウム (A1)の 、ずれか一以上の金属を含むことを特徴とする請求項% Aluminum (A1) or less, including any one or more metals.
4に記載の Pd-In系金色合金。 4. Pd-In-based golden alloy as described in 4.
[6] パラジウム (Pd)、インジウム (In)及び銅 (Cu)を含む合金であって、前記パラジウム の含有率と前記インジウムの含有率が共に 10重量%以上、かつ、前記銅の含有率が[6] An alloy containing palladium (Pd), indium (In), and copper (Cu), wherein both the palladium content and the indium content are 10% by weight or more, and the copper content is
40重量%以下であることを特徴とする Pd-In系金色合金。 Pd-In gold alloy characterized by being 40 wt% or less.
[7] 前記パラジウム(Pd)とインジウム(In)を含む合金であって、その色調がレッドの金色[7] An alloy containing palladium (Pd) and indium (In), the color of which is red gold
、ピンクの金色、イェローの金色、イェローぼい金色のいずれかの色調を呈すること を特徴とする、請求項 1乃至 6のいずれ力 1項に記載の Pd-In系金色合金。 The Pd-In gold alloy according to any one of claims 1 to 6, wherein the Pd-In gold alloy exhibits any one of the following colors: pink gold, yellow gold, yellow gold.
[8] 前記パラジウム (Pd)とインジウム (In)を含む合金であって、更に大気中、 30%希塩 酸、 99.7%酢酸、 30%希硫酸、又は 10%過酸化水素水のいずれの環境下でも良好 な耐食性を有することを特徴とする、請求項 7に記載の Pd-In系金色合金。 [8] An alloy containing palladium (Pd) and indium (In), and in the atmosphere, any environment of 30% dilute hydrochloric acid, 99.7% acetic acid, 30% dilute sulfuric acid, or 10% hydrogen peroxide water Good even under 8. The Pd—In-based golden alloy according to claim 7, characterized by having excellent corrosion resistance.
PCT/JP2006/321985 2006-11-02 2006-11-02 GOLDEN Pd-In ALLOYS WO2008053559A1 (en)

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JP2012527529A (en) * 2009-05-18 2012-11-08 ヘイマール ウント ミュール ゲゼルシャフト ミット ベシュレンクテル ハフツング Palladium gem alloy

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JPS50150629A (en) * 1974-05-27 1975-12-03
JPS5651544A (en) * 1979-10-01 1981-05-09 Tokuriki Honten Co Ltd Silver alloy for casting
JPS57108233A (en) * 1980-11-06 1982-07-06 Heraeus Gmbh W C Alloy for silver base dental cast
JPS58204141A (en) * 1982-05-21 1983-11-28 Sankin Kogyo Kk Low karat gold alloy for casting assuming gold color
JPS5916943A (en) * 1982-07-16 1984-01-28 G C Dental Ind Corp Gold alloy for dental use
JPS59162240A (en) * 1983-03-04 1984-09-13 インステイテユ−ト・メタルルギ−・イメニ・エ−・エ−・バイコバ・アカデミ−・ナウク・エスエスエスア−ル Palladium base alloy having broad range color
JPS60187638A (en) * 1984-12-24 1985-09-25 Tokuriki Honten Co Ltd Silver alloy for casting
JPS6415339A (en) * 1987-04-28 1989-01-19 Erefuanto Ederumetaale Bv Castable palladium alloy and production of tooth restoring substance, ornament and analogue
JPH01129939A (en) * 1987-11-16 1989-05-23 Toyo Kagaku Kenkyusho:Kk Golden alloy for dental casting

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Publication number Priority date Publication date Assignee Title
JPS50150629A (en) * 1974-05-27 1975-12-03
JPS5651544A (en) * 1979-10-01 1981-05-09 Tokuriki Honten Co Ltd Silver alloy for casting
JPS57108233A (en) * 1980-11-06 1982-07-06 Heraeus Gmbh W C Alloy for silver base dental cast
JPS58204141A (en) * 1982-05-21 1983-11-28 Sankin Kogyo Kk Low karat gold alloy for casting assuming gold color
JPS5916943A (en) * 1982-07-16 1984-01-28 G C Dental Ind Corp Gold alloy for dental use
JPS59162240A (en) * 1983-03-04 1984-09-13 インステイテユ−ト・メタルルギ−・イメニ・エ−・エ−・バイコバ・アカデミ−・ナウク・エスエスエスア−ル Palladium base alloy having broad range color
JPS60187638A (en) * 1984-12-24 1985-09-25 Tokuriki Honten Co Ltd Silver alloy for casting
JPS6415339A (en) * 1987-04-28 1989-01-19 Erefuanto Ederumetaale Bv Castable palladium alloy and production of tooth restoring substance, ornament and analogue
JPH01129939A (en) * 1987-11-16 1989-05-23 Toyo Kagaku Kenkyusho:Kk Golden alloy for dental casting

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012527529A (en) * 2009-05-18 2012-11-08 ヘイマール ウント ミュール ゲゼルシャフト ミット ベシュレンクテル ハフツング Palladium gem alloy

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