JP4110356B2 - Method of forming a gold film on the surface of a silver clay sintered body - Google Patents

Method of forming a gold film on the surface of a silver clay sintered body Download PDF

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Publication number
JP4110356B2
JP4110356B2 JP2001089148A JP2001089148A JP4110356B2 JP 4110356 B2 JP4110356 B2 JP 4110356B2 JP 2001089148 A JP2001089148 A JP 2001089148A JP 2001089148 A JP2001089148 A JP 2001089148A JP 4110356 B2 JP4110356 B2 JP 4110356B2
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Prior art keywords
gold
silver
silver clay
powder
sintered body
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JP2002285206A (en
Inventor
寿一 平沢
康夫 井戸
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Mitsubishi Materials Corp
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Mitsubishi Materials Corp
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Description

【0001】
【発明の属する技術分野】
この発明は、銀粘土焼結体の表面に金被膜を形成する方法に関するものである。
【0002】
【従来の技術】
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。
【0003】
前記従来の銀粘土は、平均粒径:3〜20μmの銀粉末:50〜95重量%、セルローズ系水溶性バインダー:0.8〜8重量%、油脂:0.1〜3重量%、界面活性剤:0.03〜3重量%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(特開平4−26707号公報参照)、すでに市販されている。
かかる銀粘土から得られた銀宝飾品または美術工芸品は、さらにその表面に金被膜からなる模様などをつけることにより一層豪華な銀宝飾品または美術工芸品を造ることがある。この模様などを形成するための金被膜は、金箔を銀粘土焼結体に貼り付けたのち焼き付けることにより形成されていた。
【0004】
【発明が解決しようとする課題】
しかし、金箔を銀粘土焼結体に貼り付け焼き付ける方法で金被膜を形成した銀宝飾品または美術工芸品は、焼付け時に銀粘土焼結体がさらに収縮するために、銀粘土焼結体の表面に貼り付けた金箔に皺が発生し、さらに金箔が銀粘土焼結体に十分接合しないために剥離しやすいなどの欠点があった。そのため、金粉末を有機系バインダーおよび水と共に混合し、この混合して得られた流動体ペーストを銀粘土造形体に塗布し、乾燥したのち銀粘土造形体を燒結すると同時に流動体ペーストに含まれる金粉末をも焼結し、それによって表面に金被膜を有する銀宝飾品または美術工芸品を得ようという試みもなされている。しかし、この方法で得られた銀宝飾品または美術工芸品の表面に形成された金被膜は、密度が低く、さらに剥離しやすかった。
【0005】
【課題を解決するための手段】
そこで、本発明者らは、流動体ペーストを銀粘土造形体に塗布し燒結ことにより銀宝飾品または美術工芸品の表面に形成された金被膜の特性を改善すべくさらなる研究を行った。その結果、
(イ)流動体ペーストに含まれる金の融点は1063℃であり、一方、銀粘土造形体に含まれる銀の融点は960.5℃であって、銀粉末の焼結温度は800〜900℃であるが、金粉末の焼結温度は1000〜1050℃であるところから、銀粘土造形体を通常の800〜900℃で焼結しても流動体ペーストに含まれる金粉末は十分に焼結されず、得られた金被膜の密度が低く、さらに剥離しやすくなること、
(ロ)これを改善するには、流動体ペーストに含まれる金粉末の粒子を銀粘土に含まれる銀粉末よりも一層微細化して平均粒径:3μm未満以下(好ましくは2μm以下)の金微粉末にすると、銀粘土造形体を焼結する温度で焼結しても流動体ペーストに含まれる金粉末の粒径が十分に微細であるところから焼結温度が低下し、銀粘土の焼結温度で焼結しても十分に高密度で密着性の優れた金被膜を得ることができる、などの研究結果が得られたのである。
【0006】
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、
(1)銀粘土造形体の表面に、金粉末、有機系バインダーおよび水からなる流動体ペーストを塗布したのち焼成することにより銀粘土焼結体の表面に金被膜を形成する方法において、前記流動体ペーストに含まれる金粉末は、平均粒径:3μm未満(好ましくは2μm以下)の金微細粉末である銀粘土焼結体の表面に金被膜を形成する方法、に特徴を有するものである。
【0007】
前記3μm未満(好ましくは2μm以下)の金微細粉末は、化学還元法により得られた球状金粉末であることが一層好ましい。したがって、この発明は、
(2)銀粘土造形体の表面に、金粉末、有機系バインダーおよび水からなる流動体ペーストを塗布したのち焼成する銀粘土焼結体の表面に金被膜を形成する方法において、前記流動体ペーストに含まれる金粉末は、3μm未満(好ましくは2μm以下)の化学還元法により得られた球状金微粉末である銀粘土焼結体の表面に金被膜を形成する方法、に特徴を有するものである。
前記流動体ペーストに含まれる化学還元法により得られた球状金粉末は60〜92質量%の範囲内にあることが好ましい。
【0008】
【発明の実施の形態】
この発明を、実施例に基づいて詳細に説明する。
実施例1
化学還元法により製造した平均粒径:2μmのAu微粉末を用意し、有機系バインダーとして水溶性セルローズを用意し、さらに水を用意した。前記Au微粉末:80質量%、水溶性セルローズ:1.3質量%、残部:水となるように配合し、混合して流動性のあるスラリー状のペーストを作製した。
【0009】
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質量%、メチルセルローズ:4.5質量%、界面活性剤:1.0質量%、オリーブ油:0.3質量%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。
【0010】
この銀粘土を造形して得られた造形体を乾燥させたのち、前記金微粉末を含有するペーストを塗布して乾燥させ、これを大気中、温度:900℃で30分間燒結することにより表面に金被膜を有する燒結体を作製し、得られた燒結体を磁気研磨機を用いて30分間研磨したが、金−銀の接合界面での剥離は起こらず、また密度の高い金被膜が形成されていることが分かった。
【0011】
実施例2
化学還元法により製造した平均粒径:1.5μmのAu微粉末を用意し、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、さらにエタノールおよび水を用意した。前記Au微粉末、ポリビニルアルコール、エタノールおよび水をAu微粉末:80質量%、ポリビニルアルコール:4質量%、エタノール:8質量%、残部:水となるように配合し、混合して流動性のあるスラリー状のペーストを作製した。
【0012】
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質量%、メチルセルローズ:4.5質量%、界面活性剤:1.0質量%、オリーブ油:0.3質量%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。
【0013】
この銀粘土を造形して得られた造形体を乾燥させたのち、前記金微粉末を含有するペーストをさらに塗布して乾燥させ、これを大気中、温度:900℃で30分間燒結することにより表面に金被膜を有する燒結体を作製し、得られた燒結体を磁気研磨機を用いて30分間研磨したが、金−銀の接合界面での剥離は起こらず、また密度の十分に高い金被膜が形成されていることが分かった。
【0014】
【発明の効果】
実施例1〜2から明らかなように、平均粒径:3μm未満を有するAu粉末に有機系バインダーを添加したスラリー状の流動性ペーストは、銀粘土造形体に塗布したのち通常の銀粘土焼結温度で焼結しても、十分な密着性を有しかつ十分な密度を有する金被膜が得られ、一層優れた豪華な美術工芸品や宝飾品を提供することができる。
[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for forming a gold film on the surface of a silver clay sintered body.
[0002]
[Prior art]
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 for producing silver jewelry or arts and crafts have been proposed. 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.
[0003]
The conventional silver clay has an average particle size of 3 to 20 μm, silver powder: 50 to 95% by weight, cellulose water-soluble binder: 0.8 to 8% by weight, fat and oil: 0.1 to 3% by weight, and surface activity. Agent: It is known that it contains 0.03 to 3% by weight, and the remainder consists of water (see JP-A-4-26707), and is already commercially available.
Silver jewelery or arts and crafts obtained from such silver clay may further make a gorgeous silver jewelery or arts and crafts by adding a pattern made of a gold film on the surface thereof. A gold film for forming this pattern or the like was formed by attaching a gold foil to a silver clay sintered body and then baking it.
[0004]
[Problems to be solved by the invention]
However, silver jewelry or arts and crafts with a gold film formed by sticking and baking gold foil on a silver clay sintered body shrinks the silver clay sintered body further during baking, so the surface of the silver clay sintered body There were defects such as wrinkles on the gold foil affixed to the metal foil, and the gold foil was not sufficiently bonded to the silver clay sintered body and thus easily peeled off. Therefore, the gold powder is mixed with the organic binder and water, and the fluid paste obtained by mixing the mixture is applied to the silver clay shaped body, dried and then sintered, and simultaneously contained in the fluid paste. Attempts have also been made to sinter gold powder, thereby obtaining silver jewelry or arts and crafts with a gold coating on the surface. However, the gold film formed on the surface of silver jewelry or arts and crafts obtained by this method has a low density and is easy to peel off.
[0005]
[Means for Solving the Problems]
Therefore, the present inventors conducted further research to improve the properties of the gold coating formed on the surface of silver jewelry or arts and crafts by applying a fluid paste to a silver clay shaped body and sintering. as a result,
(A) The melting point of gold contained in the fluid paste is 1063 ° C., while the melting point of silver contained in the silver clay shaped body is 960.5 ° C., and the sintering temperature of the silver powder is 800 to 900 ° C. However, since the sintering temperature of the gold powder is 1000 to 1050 ° C., the gold powder contained in the fluid paste is sufficiently sintered even if the silver clay shaped body is sintered at a normal 800 to 900 ° C. The density of the obtained gold film is low, and it becomes easier to peel off,
(B) To improve this, the gold powder particles contained in the fluid paste are made finer than the silver powder contained in the silver clay, and the average particle size is less than 3 μm (preferably 2 μm or less). When powdered, the sintering temperature is lowered because the particle size of the gold powder contained in the fluid paste is sufficiently fine even when sintering at a temperature at which the silver clay shaped body is sintered. Research results have been obtained such that a gold film having a sufficiently high density and excellent adhesion can be obtained even when sintered at a temperature.
[0006]
This invention was made based on the results of such research,
(1) In the method of forming a gold film on the surface of a silver clay sintered body by applying a fluid paste made of gold powder, an organic binder and water to the surface of the silver clay shaped body and then firing, The gold powder contained in the body paste is characterized by a method of forming a gold film on the surface of a silver clay sintered body which is a fine gold powder having an average particle size of less than 3 μm (preferably 2 μm or less).
[0007]
The gold fine powder of less than 3 μm (preferably 2 μm or less) is more preferably a spherical gold powder obtained by a chemical reduction method. Therefore, the present invention
(2) In the method of forming a gold film on the surface of a silver clay sintered body to be fired after applying a fluid paste made of gold powder, an organic binder and water to the surface of the silver clay shaped body, the fluid paste The gold powder contained in is characterized by a method of forming a gold film on the surface of a silver clay sintered body which is a spherical gold fine powder obtained by a chemical reduction method of less than 3 μm (preferably 2 μm or less). is there.
The spherical gold powder obtained by the chemical reduction method contained in the fluid paste is preferably in the range of 60 to 92% by mass.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail based on examples.
Example 1
Au fine powder having an average particle diameter of 2 μm produced by a chemical reduction method was prepared, water-soluble cellulose was prepared as an organic binder, and water was further prepared. The Au fine powder: 80% by mass, the water-soluble cellulose: 1.3% by mass, and the balance: water, were mixed and mixed to prepare a fluid slurry paste.
[0009]
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% by mass, methyl cellulose: 4.5% by mass, A commercially available silver clay having a composition of surfactant: 1.0% by mass, olive oil: 0.3% by mass, and water: balance was prepared.
[0010]
After the shaped body obtained by shaping this silver clay is dried, the paste containing the gold fine powder is applied and dried, and this is sintered in the atmosphere at a temperature of 900 ° C. for 30 minutes for surface treatment. A sintered body having a gold film was prepared, and the obtained sintered body was polished for 30 minutes using a magnetic polishing machine, but peeling at the gold-silver bonding interface did not occur, and a high-density gold film was formed. I found out that
[0011]
Example 2
Au fine powder having an average particle diameter of 1.5 μm produced by a chemical reduction method was prepared, polyvinyl alcohol was prepared as an organic binder, and ethanol and water were further prepared. The Au fine powder, polyvinyl alcohol, ethanol and water are blended so that the fine Au powder is 80% by mass, the polyvinyl alcohol is 4% by mass, the ethanol is 8% by mass, and the balance is water. A slurry-like paste was prepared.
[0012]
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% by mass, methyl cellulose: 4.5% by mass, A commercially available silver clay having a composition of surfactant: 1.0% by mass, olive oil: 0.3% by mass, and water: balance was prepared.
[0013]
After drying the shaped body obtained by shaping this silver clay, the paste containing the fine gold powder is further applied and dried, and this is sintered in the atmosphere at a temperature of 900 ° C. for 30 minutes. A sintered body having a gold film on the surface was prepared, and the obtained sintered body was polished for 30 minutes using a magnetic polishing machine, but peeling at the gold-silver bonding interface did not occur, and gold having a sufficiently high density It was found that a film was formed.
[0014]
【The invention's effect】
As is clear from Examples 1 and 2, a slurry-like fluid paste in which an organic binder is added to Au powder having an average particle size of less than 3 μm is applied to a silver clay shaped body, followed by normal silver clay sintering. Even if it sinters at temperature, the gold film which has sufficient adhesiveness and sufficient density can be obtained, and more excellent luxurious arts and crafts and jewelry can be provided.

Claims (2)

銀粘土造形体の表面に、金粉末、有機系バインダーおよび水からなる流動体ペーストを塗布したのち焼成することにより銀粘土焼結体の表面に金被膜を形成する方法において、
前記流動体ペーストに含まれる金粉末は、平均粒径:3μm未満の金微細粉末であることを特徴とする銀粘土焼結体の表面に金被膜を形成する方法。
In the method of forming a gold film on the surface of a silver clay sintered body by applying a fluid paste composed of gold powder, an organic binder and water to the surface of the silver clay shaped body, followed by firing,
The gold powder contained in the fluid paste is a fine gold powder having an average particle diameter of less than 3 μm. A method for forming a gold coating on the surface of a silver clay sintered body.
前記平均粒径:3μm未満の金微細粉末は、化学還元法により得られた球状金微粉末であることを特徴とする請求項1記載の銀粘土焼結体の表面に金被膜を形成する方法。2. The method for forming a gold film on the surface of a silver clay sintered body according to claim 1, wherein the gold fine powder having an average particle size of less than 3 μm is a spherical gold fine powder obtained by a chemical reduction method. .
JP2001089148A 2001-03-27 2001-03-27 Method of forming a gold film on the surface of a silver clay sintered body Expired - Lifetime JP4110356B2 (en)

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