JP2008240057A - Fluid paste for preventing sulfurization of silver clay sintered compact - Google Patents
Fluid paste for preventing sulfurization of silver clay sintered compact Download PDFInfo
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この発明は、銀粘土焼結体の表面に銀色または銀色に近い色調の皮膜を形成して銀粘土焼結体表面の硫化を防止するための流動体ペーストに関するものである。 The present invention relates to a fluid paste for preventing a sulfidation of the surface of a silver clay sintered body by forming a film having a silver color or a color tone close to silver on the surface of the silver clay sintered body.
銀の宝飾品または美術工芸品は一般に鋳造または鍛造により製造されている。しかし、近年、銀粉末を含んだ銀粘土が市販されており、この銀粘土を所定の形状に成形して造形体を作製し、この造形体を乾燥したのち焼結して所定の形状を有する銀の宝飾品または美術工芸品を製造する方法が提案されている。この方法によると、銀粘土を通常の粘土細工と同じように自由に造形を行うことができ、造形して得られた造形体は、乾燥したのち、比較的小さな焼結炉を設置した場所に運び、そこで焼結することにより極めて簡単に銀の宝飾品または美術工芸品を製造することができる。 Silver jewelry or arts and crafts are generally manufactured by casting or forging. However, in recent years, silver clay containing silver powder has been commercially available. The silver clay is molded into a predetermined shape to produce a shaped body, and the shaped body is dried and then sintered to have a predetermined shape. Methods have been proposed for producing silver jewelry or arts and crafts. According to this method, silver clay can be freely modeled in the same way as ordinary clay work, and the molded body obtained by modeling is dried and then placed in a place where a relatively small sintering furnace is installed. Silver jewelry or arts and crafts can be produced very easily by carrying and sintering there.
前記従来の銀粘土は、質量％で(以下、％は質量％を示す)、平均粒径：３〜２０μｍの銀粉末：５０〜９５％、セルローズ系水溶性バインダー：０．８〜８％、油脂：０．１〜３％、界面活性剤：０．０３〜３％を含有し、残りが水からなるものであることは知られており、すでに市販されている。かかる銀粘土を焼結して得られた銀宝飾品または銀美術工芸品は、素材がＡｇであるために表面が硫化して黒色に変色しやすく、銀宝飾品または銀美術工芸品の銀光沢を長期間維持することは難しかった。これを解決するために、純Ａｇ粉末と、０．０５〜１質量％のＰｄ粉末とからなる混合粉末、もしくは０．０５〜１質量％のＰｄを含むＡｇ合金粉末を、有機バインダー水溶液に混合してなるスラリー状の組成物を、所望の形状に造形した物品に付着させ、乾燥固化させたのち焼結する銀粘土焼結体硫化防止のための方法が提案されている（特許文献１参照）。
しかし、この従来の純Ａｇ粉末とＰｄ粉末とからなる混合粉末を含む流動体ペーストを銀粘土造形体または銀粘土焼結体に塗布し乾燥したのち焼成して銀粘土焼結体表面に形成された皮膜はある程度の耐硫化性は得られるものの十分な耐硫化性が得られない。 However, it is formed on the surface of the silver clay sintered body by applying the fluid paste containing the mixed powder of the conventional pure Ag powder and Pd powder to the silver clay shaped body or the silver clay sintered body and drying it. Although the film has a certain degree of sulfidation resistance, sufficient sulfidation resistance cannot be obtained.
そこで、本発明者らは、一層耐硫化性に優れた銀粘土焼結体を得るべく研究を行った。その結果、
（イ）平均粒径：０．５〜２．０μｍのＡｕ粉末：３０〜６０質量％を含有し、残部が平均粒径：０．５〜１．５μｍのＡｇ粉末からなるＡｇ−Ａｕ混合粉末を作製し、このＡｇ−Ａｕ混合粉末：７０〜９５％、有機系バインダー：３〜２１％、一価アルコール：０．３〜３％、多価アルコール：０．０４〜２％、流動パラフィン：０．２〜１％を含有し、残部が水からなる組成を有する銀粘土焼結体硫化防止用流動体ペーストを銀粘土造形体または銀粘土焼結体に塗布して乾燥し焼成して得られた銀粘土焼結体の表面に形成した皮膜は、従来の純Ａｇ粉末とＰｄ粉末とからなる混合粉末を含む流動体ペーストを銀粘土造形体または銀粘土焼結体に塗布し乾燥したのち焼成して得られた銀粘土焼結体の表面に形成された皮膜に比べて一層優れた耐硫化性を示す、という研究結果が得られたのである。
Therefore, the present inventors have studied to obtain a silver clay sintered body having further excellent sulfidation resistance. as a result,
(A) Au powder having an average particle diameter of 0.5 to 2.0 [mu] m: Ag-Au mixed powder containing 30 to 60% by mass and the balance being made of Ag powder having an average particle diameter of 0.5 to 1.5 [mu] m This Ag—Au mixed powder: 70 to 95%, organic binder: 3 to 21%, monohydric alcohol: 0.3 to 3%, polyhydric alcohol: 0.04 to 2%, liquid paraffin: A silver clay sintered body having a composition containing 0.2 to 1%, the balance being water, applied to a silver clay shaped body or silver clay sintered body and dried and fired. The film formed on the surface of the obtained silver clay sintered body is coated with a fluid paste containing a conventional mixed powder composed of pure Ag powder and Pd powder on the silver clay shaped body or silver clay sintered body and dried. Compared to the film formed on the surface of the sintered silver clay obtained by firing The result of research showing that it is resistant to sulfidation was obtained.
この発明は、かかる研究結果にもとづいてなされたものであって、
質量％で(以下、％は質量％を示す)、平均粒径：０．５〜２．０μｍのＡｕ粉末：３０〜６０質量％を含有し、残部が平均粒径：０．５〜１．５μｍのＡｇ粉末からなるＡｇ−Ａｕ混合粉末を７０〜９５％含有し、さらに有機系バインダー：３〜２１％、一価アルコール：０．３〜３％、多価アルコール：０．０４〜２％、流動パラフィン：０．２〜１％を含有し、残部が水からなる組成を有する銀粘土焼結体硫化防止用流動体ペースト、に特徴を有するものである。
This invention was made based on the results of such research,
In mass% (hereinafter,% represents mass%), average particle size: 0.5 to 2.0 μm Au powder: 30 to 60% by mass, the balance being average particle size: 0.5 to 1%. Contains 70 to 95% of Ag-Au mixed powder made of 5 μm Ag powder, further organic binder: 3 to 21%, monohydric alcohol: 0.3 to 3%, polyhydric alcohol: 0.04 to 2% Liquid paraffin: a silver clay sintered body fluid prevention paste for preventing sulfidation having a composition containing 0.2 to 1% and the balance being water.
この発明の銀粘土焼結体硫化防止用ペーストに含まれる有機バインダーとしてはポリビニルアルコール、ポリビニルピロリドン、ポリエチレングリコール、デキストラン、プルラン、キサンタンガムなどの水溶性高分子が好ましく、水溶性高分子の中でもポリビニルアルコールが最も好ましい。 The organic binder contained in the silver clay sintered body anti-sulfurization paste of the present invention is preferably a water-soluble polymer such as polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, dextran, pullulan, xanthan gum, and among the water-soluble polymers, polyvinyl alcohol Is most preferred.
この発明の銀粘土焼結体硫化防止用ペーストに含まれる一価アルコールは、ＯＨ基が１個あり、Ｃの数が１〜５の鎖式アルコールであって、メタノール、エタノール、プロピルアルコール、ブチルアルコール、ペンチルアルコールが含まれるが、この中でも人体に最も害の少ないエタノールが最も好ましい。 The monohydric alcohol contained in the silver clay sintered body anti-sulfurization paste of the present invention is a chain alcohol having one OH group and 1 to 5 carbon atoms, which is methanol, ethanol, propyl alcohol, butyl. Alcohol and pentyl alcohol are included, and among these, ethanol which is least harmful to the human body is most preferable.
この発明の銀粘土焼結体硫化防止用ペーストに含まれる多価アルコールは、ＯＨ基が２個以上あり、Ｃの数が１〜５の鎖式アルコールであって、グリセリン、ジグリセリン、イソプレングリコール、１−３ブチレングリコールなどが含まれるが、この中でもグリセリンが最も好ましい。 The polyhydric alcohol contained in the silver clay sintered body anti-sulfurization paste of the present invention is a chain alcohol having 2 or more OH groups and 1 to 5 C, and is glycerin, diglycerin, isoprene glycol Although 1-3 butylene glycol etc. are contained, glycerol is the most preferable among these.
この発明の銀粘土焼結体硫化防止用ペーストに含まれるＡｇ−Ａｕ混合粉末を構成するＡｕ粉末の平均粒径を０．５〜２μｍとしたのは、Ａｕ粉末の平均粒径を０．５μｍ未満となるように微細化しても格別な効果はなく、かえって粉末を製造するコストが高くなるので好ましくないからであり、一方、平均粒径が２μｍを越えると焼結性が悪く、均一な皮膜が得られないので好ましくないからである。
また、この発明の銀粘土焼結体硫化防止用ペーストに含まれるＡｇ−Ａｕ混合粉末を構成するＡｇ粉末の平均粒径を０．５〜１．５μｍとしたのは、Ａｇ粉末の平均粒径を０．５μｍ未満となるように微細化しても格別な効果はなく、かえって粉末を製造するコストが高くなるので好ましくないからであり、一方、平均粒径が１．５μｍを越えると焼結性が悪く、均一な皮膜が得られないので好ましくないからである。
さらに、この発明の銀粘土焼結体硫化防止用ペーストに含まれるＡｇ−Ａｕ混合粉末に含まれる平均粒径：０．５〜２μｍを有するＡｕ粉末の配合量を３０〜６０％にした理由は、Ａｕ粉末が３０％未満ではペースト塗布層に含まれるＡｕ粉末の含有量が少なすぎて所望の耐硫化性に優れた皮膜が得られないので好ましくなく、一方、６０％を越えて含有すると、黄金色を呈するようになり、銀特有の色調を保つことができなくなるので好ましくないからである。
さらに、この発明の銀粘土焼結体硫化防止用ペーストに含まれる前記Ａｇ−Ａｕ混合粉末の含有量を７０〜９５％にしたのは、Ａｇ−Ａｕ混合粉末の含有量が７０％未満ではペースト塗布層に含まれる金または金合金粉末の含有量が少なすぎて所望の耐硫化性が得られず、所望の耐硫化性を得ようとすると塗布回数が極端に多くなるので塗布に時間がかかるので好ましくなく、一方、９５％を越えて含有すると、ペーストの流動性が無くなって、均一に塗布することができなくなるので好ましくないからである。
The reason why the average particle size of the Au powder constituting the Ag-Au mixed powder contained in the paste for preventing sulfidation of the silver clay sintered body of the present invention is 0.5-2 μm is that the average particle size of the Au powder is 0.5 μm. If the average particle size exceeds 2 μm, the sinterability is poor, and a uniform film is not preferable because there is no particular effect even if the size is reduced to less than 1. This is because it is not preferable.
In addition, the average particle diameter of the Ag powder constituting the Ag-Au mixed powder contained in the silver clay sintered body sulfidation preventing paste of the present invention is 0.5 to 1.5 μm. This is because there is no particular effect even if the particle size is reduced to less than 0.5 μm, and it is not preferable because the cost of producing the powder becomes high. On the other hand, if the average particle size exceeds 1.5 μm, the sinterability This is because it is not preferable because a uniform film cannot be obtained.
Furthermore, the reason why the blending amount of the Au powder having an average particle diameter of 0.5 to 2 μm contained in the Ag—Au mixed powder contained in the silver sulfide sintered body sulfidation preventing paste of the present invention is 30 to 60% is as follows. If the Au powder content is less than 30%, the content of the Au powder contained in the paste coating layer is too small to obtain a film excellent in desired sulfidation resistance. On the other hand, if the content exceeds 60%, This is because a golden color is exhibited, and the color tone peculiar to silver cannot be maintained, which is not preferable.
Furthermore, the content of the Ag-Au mixed powder contained in the paste for preventing sulfidation of the silver clay sintered body of the present invention is 70 to 95% because the content of the Ag-Au mixed powder is less than 70%. The content of the gold or gold alloy powder contained in the coating layer is too small to obtain the desired sulfidation resistance, and when trying to obtain the desired sulfidation resistance, the number of times of coating becomes extremely large, so the coating takes time. On the other hand, if the content exceeds 95%, the fluidity of the paste is lost, and it becomes impossible to apply uniformly, which is not preferable.
有機バインダーは銀粘土造形体に対するペーストの粘着性を付与するために添加するが、その含有量は３％未満では十分な粘性が得られないために塗布直後のペーストの垂れを防止することができないので好ましくなく、一方、２１％を越えて含有すると粘性が高くなりすぎて柔らかい筆などで塗布することができないようになるので好ましくない。したがって、有機系バインダー（特に好ましくはポリビニルアルコール）の含有量は３〜２１％（一層好ましくは、６〜１５％）に定めた。 The organic binder is added in order to give the adhesiveness of the paste to the silver clay shaped body, but if its content is less than 3%, sufficient viscosity cannot be obtained, so that dripping of the paste immediately after application cannot be prevented. On the other hand, if it exceeds 21%, the viscosity becomes so high that it cannot be applied with a soft brush or the like. Therefore, the content of the organic binder (particularly preferably polyvinyl alcohol) is set to 3 to 21% (more preferably 6 to 15%).
一価アルコールはエタノールが最も好ましく、銀粘土焼結体硫化防止用流動体ペーストに含有させて銀粘土造形体に塗布した後の乾燥スピードを向上させ、それによって、塗布直後のペーストの垂れを防止する作用を有するが、その含有量が０．３％未満では乾燥に時間がかかるために塗布直後のペーストの垂れおよび広がりを防止することができないので好ましくなく、一方、３％を越えて含有しても格別な効果がなく、かえってアルコール性臭気が感じられるようになるので好ましくない。したがって、一価アルコールの含有量は０．３〜３％（一層好ましくは、０．６〜１．５％）に定めた。 The monohydric alcohol is most preferably ethanol, and it is included in the fluid paste for sulfidation prevention of silver clay sintered body to improve the drying speed after applying to the silver clay shaped body, thereby preventing dripping of the paste immediately after application. However, if the content is less than 0.3%, it takes time to dry, and thus it is not preferable because it cannot prevent dripping and spreading of the paste immediately after coating. On the other hand, the content exceeds 3%. However, it is not preferable because there is no special effect and an alcoholic odor can be felt. Therefore, the content of monohydric alcohol is set to 0.3 to 3% (more preferably, 0.6 to 1.5%).
多価アルコールはグリセリンが最も好ましく、銀粘土焼結体硫化防止用流動体ペーストに含有させてペースト表面の乾燥を遅らせることにより得られた銀粘土焼結体硫化防止用流動体ペースト乾燥膜の内部に微細な気孔が生成することを防止し、さらに密着性に優れたＰｔまたはＰｄ流動体ペースト乾燥膜を得る作用を有するが、その含有量が０．０４％未満では所望の効果が得られないので好ましくなく、一方、２％を越えて含有すると、銀粘土焼結体硫化防止用流動体ペーストの塗布膜の乾燥が極端に遅れるようになるので好ましくない。したがって、グリセリンの含有量は０．０４〜２％（一層好ましくは、０．１〜１．０％）に定めた。 The polyhydric alcohol is most preferably glycerin, and is contained in the silver clay sintered body sulfidation-preventing fluid paste, and the inside of the silver clay sintered body sulfidation-preventing fluid paste drying film obtained by delaying drying of the paste surface. It prevents the formation of fine pores and provides a dry Pt or Pd fluid paste dry film with excellent adhesion, but if the content is less than 0.04%, the desired effect cannot be obtained. On the other hand, if the content exceeds 2%, the drying of the coating film of the silver clay sintered body anti-sulfurization fluid paste is extremely delayed, which is not preferable. Therefore, the glycerin content is set to 0.04 to 2% (more preferably, 0.1 to 1.0%).
流動パラフィンは、銀粘土焼結体硫化防止用流動体ペーストに含有させてペースト容器からの離型性を高める作用を有するが、その含有量が０．２％未満では容器へのＰｔまたはＰｄ流動体ペーストの付着量が多くなるので好ましくなく、一方、１．０％を越えて含有すると、油分が多いために乾燥後のペースト膜が軟化するので好ましくない。したがって、流動パラフィンの含有量は０．２〜１％（一層好ましくは０．３〜０．８％）に定めた。 Liquid paraffin has the effect of increasing the releasability from the paste container by being contained in the silver clay sintered body fluid prevention paste to prevent sulfidation, but if its content is less than 0.2%, Pt or Pd flows into the container. On the other hand, when the content exceeds 1.0%, it is not preferable because the paste film after drying is softened due to a large amount of oil. Therefore, the content of liquid paraffin is set to 0.2 to 1% (more preferably 0.3 to 0.8%).
この発明の銀粘土焼結体硫化防止用流動体ペーストは銀粘土焼結体表面に耐硫化性に優れた皮膜を形成することができ、銀製の美術工芸品や宝飾品の銀光沢を一層長期間保持することができる。 The silver clay sintered body fluid prevention paste according to the present invention can form a film having excellent resistance to sulfidation on the surface of the silver clay sintered body, further enhancing the silver luster of silver arts and crafts and jewelry. Can be held for a period.
平均粒径：０．８μｍを有するＡｕ粉末および平均粒径：１．２μｍを有するＡｇ粉末を用意し、有機系バインダーとしてポリビニルアルコールを用意し、一価アルコールとしてエタノールを用意し、さらに多価アルコールとしてグリセリン、流動パラフィンおよび水を用意した。前記Ａｕ粉末およびＡｇ粉末を表１に示される割合で混合してＡｇ−Ａｕ混合粉末を作製し、これらＡｇ−Ａｕ混合粉末、ポリビニルアルコール、エタノール、グリセリン、流動パラフィンおよび水を表１に示される割合で配合し、混合して流動性のあるスラリー状の本発明ペースト１〜４および比較ペースト１〜２を作製した。
さらに、Ａｇ粉末およびＰｄ粉末を含む流動性のある市販のスラリー状ペーストを用意し、従来ペーストとした。
An Au powder having an average particle diameter of 0.8 μm and an Ag powder having an average particle diameter of 1.2 μm are prepared, polyvinyl alcohol is prepared as an organic binder, ethanol is prepared as a monohydric alcohol, and a polyhydric alcohol is prepared. Glycerin, liquid paraffin and water were prepared. The Au powder and Ag powder are mixed in the ratio shown in Table 1 to produce an Ag-Au mixed powder. These Ag-Au mixed powder, polyvinyl alcohol, ethanol, glycerin, liquid paraffin and water are shown in Table 1. It mix | blended in a ratio and mixed and produced this slurry-like paste 1-4 of this invention and comparative paste 1-2.
Furthermore, a commercially available slurry-like paste containing Ag powder and Pd powder was prepared and used as a conventional paste.
一方、平均粒径：５．０μｍを有するアトマイズＡｇ粉末に対し、メチルセルローズ、界面活性剤、オリーブ油および水を添加し、銀粘土用銀粉末：８５％、メチルセルローズ：４．５％、界面活性剤：１．０％、オリーブ油：０．３％および水：残部となる配合組成を有する市販の銀粘土を用意した。 On the other hand, methyl cellulose, surfactant, olive oil and water were added to atomized Ag powder having an average particle size of 5.0 μm, silver powder for silver clay: 85%, methyl cellulose: 4.5%, surface activity A commercially available silver clay having a blending composition of 1.0%, olive oil: 0.3% and water: the balance was prepared.
この銀粘土を造形し乾燥したのち焼結することにより縦：２０ｍｍ、横：２０ｍｍ、厚さ：３ｍｍの寸法を有する銀粘土焼結体を作製し、この銀粘土焼結体の半面にスクリーン印刷により前記本発明ペースト１〜４、比較ペースト１〜２および従来ペーストを厚み：２００μｍとなるように塗布し３分間乾燥させたのち、温度：８５０℃、２０分間保持の条件で焼成し、表面に耐硫化性皮膜を有する銀粘土焼結体を作製した。 A silver clay sintered body having dimensions of 20 mm in length, 20 mm in width, and 3 mm in thickness is produced by shaping, drying and sintering this silver clay, and screen printing is performed on one side of the silver clay sintered body. After applying the pastes 1 to 4 of the present invention, the comparative pastes 1 to 2 and the conventional paste to a thickness of 200 μm and drying for 3 minutes, firing was carried out at a temperature of 850 ° C. for 20 minutes, and applied to the surface. A silver clay sintered body having a sulfide-resistant film was prepared.
このようにして得られた表面に耐硫化性皮膜を有する耐硫化性銀粘土焼結体を０．１％硫化アンモニウム水溶液に５分間浸漬したのち取り出してその表面を目視にて観察し、その結果を表１に示した。 The resulting sulfide-resistant silver clay sintered body having a sulfide-resistant film on the surface was immersed in a 0.1% aqueous solution of ammonium sulfide for 5 minutes and then taken out and the surface was visually observed. Is shown in Table 1.
表１から明らかなように、本発明ペースト１〜４を用いて作製した耐硫化性銀粘土焼結体は黒色化していないのに対し、従来ペーストを用いて作製した耐硫化性銀粘土焼結体は黒色化していることから、本発明ペースト１〜４は従来ペーストに比べて優れた耐硫化性皮膜を形成できることが分かる。しかし、Ａｕ粉末の含有量が３０％よりも少ないＡｇ−Ａｕ混合粉末を含む比較ペースト１は若干黒色化し、さらにＡｕ粉末の含有量が６０％よりも多いＡｇ−Ａｕ混合粉末を含む比較ペースト２は黒色化することはないが黄金色を呈するようになるのでこの発明の目的に沿うものではないことが分かる。 As is apparent from Table 1, the sulfide-resistant silver clay sintered body produced using the pastes 1 to 4 of the present invention is not blackened, whereas the sulfide-resistant silver clay sintered body produced using the conventional paste is not blackened. Since the body is blackened, it can be seen that the pastes 1 to 4 of the present invention can form an excellent sulfide-resistant film as compared with the conventional paste. However, the comparative paste 1 containing the Ag-Au mixed powder with the Au powder content less than 30% is slightly blackened, and the comparative paste 2 containing the Ag-Au mixed powder with the Au powder content more than 60%. Although it does not blacken, it becomes golden, so it can be seen that it does not meet the object of the present invention.
Claims (3)
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| JP2011179081A (en) * | 2010-03-02 | 2011-09-15 | Mitsubishi Materials Corp | Method for producing noble metal article |
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