JP2006118042A - Silver powder for silver clay and silver clay containing the silver powder - Google Patents
Silver powder for silver clay and silver clay containing the silver powder Download PDFInfo
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- JP2006118042A JP2006118042A JP2005272364A JP2005272364A JP2006118042A JP 2006118042 A JP2006118042 A JP 2006118042A JP 2005272364 A JP2005272364 A JP 2005272364A JP 2005272364 A JP2005272364 A JP 2005272364A JP 2006118042 A JP2006118042 A JP 2006118042A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 381
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 352
- 239000004332 silver Substances 0.000 title claims abstract description 352
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- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
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Abstract
Description
本発明は、低収縮性及び収縮率安定性に優れた銀粘土用銀粉末と、この銀粉末を含む銀粘土に関するものである。 The present invention relates to a silver clay silver powder excellent in low shrinkage and shrinkage rate stability, and a silver clay containing the silver powder.
従来、銀の宝飾品や美術工芸品は鋳造又は鍛造により製造されるの一般的であったが、近年、銀粉末を含んだ銀粘土が市販されるようになってきた。この銀粘土を成形・焼成することにより、所定の形状を有する銀の宝飾品や美術工芸品が製造される。上記銀粘土に含まれる銀粉末として、平均粒径が２μｍ以下、好ましくは０．５〜１．５μｍ、更に好ましくは０．６〜１．２μｍである小径の銀粒子を１５〜５０重量％と、平均粒径が２μｍを越え１００μｍ以下、好ましくは３〜２０μｍ、更に好ましくは３〜８μｍである大径の銀粒子とを混合することにより構成された銀粘土用銀粉末が開示されている（例えば、特許文献１参照。）。この銀粘土用銀粉末では、銀粉末５０〜９５重量％と、有機系バインダ０．５〜８重量％と、残部の水とを混合して銀粘土が作製される。
このように作製された銀粘土では、純銀の融点よりも２５０〜４１０℃低い温度、即ち５５０〜７１０℃未満の温度で焼成しても、十分に焼成でき、所望の引っ張り強度及び密度が得られるようになっている。
The silver clay thus produced can be sufficiently fired even at a temperature lower than the melting point of pure silver by 250 to 410 ° C., that is, a temperature of less than 550 to 710 ° C., and desired tensile strength and density can be obtained. It is like that.
上記従来の特許文献１に示された銀粘土では、６００℃程度と比較的低い温度で焼成すると、大径の銀粒子が焼結せずに、小径の銀粒子が焼結することにより、小径の銀粒子が大径の銀粒子を結合するため、かさ密度が殆ど変わることなく収縮率の小さい焼結体が得られる。
しかし、特許文献１に示された銀粘土では、大径の銀粒子の平均粒径の範囲が広すぎるため、焼成温度を８００〜９００℃まで高くすると、焼結体の収縮率が大きくなる場合があった。具体的には、大径の銀粒子の平均粒径が好ましい範囲の３〜２０μｍにおいて、焼結体の収縮率が大きくなる問題点があった。このため、収縮率の小さい焼結体を得るには、焼結温度を５５０〜７１０℃と低い温度に制御しなければならなかった。
本発明の目的は、焼結体の収縮率が小さく、かつ６００〜９００℃と広い温度範囲で焼成しても焼結体の収縮率が殆ど変化しない、銀粘土用銀粉末及びこの銀粉末を含む銀粘土を提供することにある。
本発明の別の目的は、従来と同等の有機バインダの混合割合、で従来より造形性を向上できる、銀粘土を提供することにある。
In the silver clay shown in the above-mentioned conventional Patent Document 1, when sintered at a relatively low temperature of about 600 ° C., the large diameter silver particles are not sintered, but the small diameter silver particles are sintered. Since the silver particles bind to the large-diameter silver particles, a sintered body having a small shrinkage can be obtained with almost no change in bulk density.
However, in the silver clay shown in Patent Document 1, since the range of the average particle diameter of the large-diameter silver particles is too wide, when the firing temperature is increased to 800 to 900 ° C., the shrinkage ratio of the sintered body increases. was there. Specifically, there is a problem that the shrinkage ratio of the sintered body increases when the average particle diameter of the large-diameter silver particles is 3 to 20 μm in the preferable range. For this reason, in order to obtain a sintered body having a small shrinkage rate, the sintering temperature had to be controlled to a low temperature of 550 to 710 ° C.
An object of the present invention is to provide a silver powder for silver clay and a silver powder, in which the shrinkage rate of the sintered body is small and the shrinkage rate of the sintered body hardly changes even when fired in a wide temperature range of 600 to 900 ° C. It is to provide silver clay containing.
Another object of the present invention is to provide a silver clay that can improve the formability as compared with a conventional organic binder having a mixing ratio of an organic binder.
請求項１に係る発明は、平均粒径が０．１〜０．５μｍである第１銀粒子２０〜５０重量％と、平均粒径が３０〜６０μｍである第２銀粒子８０〜５０重量％とを混合してなる銀粘土用銀粉末である。
この請求項１に記載された銀粘土用銀粉末では、この銀粉末を用いて作製した銀粘土を６００℃程度と比較的低い温度で焼成すると、第２銀粒子が焼結せずに第１銀粒子が焼結して、第１銀粒子が第２銀粒子を結合するため、収縮率の小さい焼結体が得られる。一方、この銀粉末を用いて作製した銀粘土を９００℃程度と比較的高い温度で焼成すると、第１銀粒子が焼結するとともに、第２銀粒子が僅かに焼結し始めるけれども、第２銀粒子の平均粒径が大径であるため焼結し難く、収縮率の小さい焼結体を得ることができる。
In the invention according to claim 1, the first silver particles having an average particle diameter of 0.1 to 0.5 μm are 20 to 50% by weight, and the second silver particles having an average particle diameter of 30 to 60 μm are 80 to 50% by weight. Is a silver powder for silver clay.
In the silver powder for silver clay described in claim 1, when silver clay produced using this silver powder is fired at a relatively low temperature of about 600 ° C., the second silver particles are not sintered and the first Since the silver particles are sintered and the first silver particles are bonded to the second silver particles, a sintered body having a small shrinkage is obtained. On the other hand, when the silver clay produced using this silver powder is fired at a relatively high temperature of about 900 ° C., the first silver particles are sintered and the second silver particles begin to be slightly sintered. Since the average particle diameter of the silver particles is large, it is difficult to sinter and a sintered body having a small shrinkage rate can be obtained.
請求項２に係る発明は、請求項１に係る発明であって、更に第２銀粒子の真球度が１０％以下であり、第２銀粒子の比表面積が０．１ｍ2／ｇ以下であることを特徴とする。
この請求項２に記載された銀粘土用銀粉末では、第２銀粒子を真球に近い形状にするとともにその比表面積を小さくし、この第２銀粒子と第１銀粒子を混合してなる銀粉末を含む銀粘土の有機バインダの混合割合を少なくすることにより、第２銀粒子同士が互いに密に接触するとともに、これらの第２銀粒子の僅かな隙間に第１銀粒子が侵入した状態で焼成することができる。なお、上記銀粉末に混合される有機バインダの混合割合を従来と同等にすると、上記銀粉末を含む銀粘土は従来の銀粘土より造形性を向上できる。
The invention according to claim 2 is the invention according to claim 1, wherein the sphericity of the second silver particles is 10% or less, and the specific surface area of the second silver particles is 0.1 m 2 / g or less. It is characterized by being.
In the silver powder for silver clay described in claim 2, the second silver particles are formed in a shape close to a true sphere, the specific surface area is reduced, and the second silver particles and the first silver particles are mixed. By reducing the mixing ratio of the organic binder of silver clay containing silver powder, the second silver particles are in intimate contact with each other, and the first silver particles have entered the slight gap between these second silver particles. Can be fired. In addition, if the mixing ratio of the organic binder mixed with the said silver powder is made equivalent to the past, the silver clay containing the said silver powder can improve a moldability rather than the conventional silver clay.
請求項３に係る発明は、請求項１に係る発明であって、更に第１銀粒子の粒度分布の半値幅Ｈ1が０．２〜０．８μｍであり、第２銀粒子の粒度分布の半値幅Ｈ2が２０〜８０μｍであることを特徴とする。
この請求項３に記載された銀粘土用銀粉末では、第２銀粒子の粒度分布の半値幅Ｈ2が２０〜８０μｍと狭いため、大径の第２銀粒子の粒径が揃うため、銀粉末を含む銀粘土を９００℃程度と高い温度で焼成しても、第２銀粒子が更に焼結し難くなる。
The invention according to claim 3 is the invention according to claim 1, wherein the half-value width H 1 of the particle size distribution of the first silver particles is 0.2 to 0.8 μm, and the particle size distribution of the second silver particles is The half width H 2 is 20 to 80 μm.
In the silver powder for silver clay described in claim 3, since the half-value width H 2 of the particle size distribution of the second silver particles is as narrow as 20 to 80 μm, the particle diameters of the large second silver particles are uniform. Even if the silver clay containing the powder is fired at a high temperature of about 900 ° C., the second silver particles are more difficult to sinter.
請求項４に係る発明は、請求項１ないし３いずれか１項に記載の銀粘土用銀粉末５０〜９５重量％と、有機系バインダ０．５〜８重量％と、残部の水とを混合してなる銀粘土である。
この請求項４に記載された銀粘土では、この銀粘土を６００℃程度と比較的低い温度で焼成すると、第２銀粒子が焼結せずに第１銀粒子が焼結して、第１銀粒子が第２銀粒子を結合するため、収縮率の小さい焼結体が得られる。一方、この銀粘土を９００℃程度と比較的高い温度で焼成すると、第１銀粒子が焼結するとともに、第２銀粒子が僅かに焼結し始めるけれども、第２銀粒子の平均粒径が大径であるため焼結し難く、収縮率の小さい焼結体を得ることができる。
また水の一部を０．０３〜３重量％の界面活性剤又は０．１〜３重量％の油脂のいずれか一方又は双方に置き換えることが好ましい。
The invention according to claim 4 is a mixture of 50 to 95% by weight of silver powder for silver clay according to any one of claims 1 to 3, 0.5 to 8% by weight of an organic binder, and the remaining water. It is made of silver clay.
In the silver clay described in claim 4, when the silver clay is fired at a relatively low temperature of about 600 ° C., the first silver particles are sintered without the second silver particles being sintered. Since the silver particles bind the second silver particles, a sintered body having a small shrinkage rate is obtained. On the other hand, when this silver clay is fired at a relatively high temperature of about 900 ° C., the first silver particles are sintered and the second silver particles begin to sinter slightly. Since it has a large diameter, it is difficult to sinter and a sintered body having a small shrinkage rate can be obtained.
Moreover, it is preferable to replace a part of water with either one or both of 0.03 to 3% by weight of surfactant or 0.1 to 3% by weight of fats and oils.
以上述べたように、本発明によれば、平均粒径０．１〜０．５μｍの第１銀粒子２０〜５０重量％と、平均粒径３０〜６０μｍの第２銀粒子８０〜５０重量％との混合物により銀粉末を構成したので、この銀粉末を用いて作製した銀粘土を、６００℃程度と比較的低い温度で焼成すると、焼結しない第２銀粒子を第１銀粒子の焼結により結合した状態で焼結体が作製され、９００℃程度と比較的高い温度で焼成しても、殆ど焼結しない第２銀粉末を第１銀粉末の焼結により結合した状態で焼結体が作製される。この結果、焼結体の収縮率が小さく、かつ６００〜９００℃と広い温度範囲で焼成しても焼結体の収縮率が殆ど変化せず、収縮率の小さい焼結体を得ることができる。 As described above, according to the present invention, the first silver particles having an average particle diameter of 0.1 to 0.5 μm are 20 to 50% by weight and the second silver particles having an average particle diameter of 30 to 60 μm are 80 to 50% by weight. Since the silver powder was composed of a mixture of the silver powder, when the silver clay produced using the silver powder was fired at a relatively low temperature of about 600 ° C., the second silver particles that were not sintered were sintered to the first silver particles. The sintered body is produced in a state where the second silver powder, which is hardly sintered even when fired at a relatively high temperature of about 900 ° C., is joined by sintering the first silver powder. Is produced. As a result, the shrinkage rate of the sintered body is small, and even when sintered in a wide temperature range of 600 to 900 ° C., the shrinkage rate of the sintered body hardly changes and a sintered body having a small shrinkage rate can be obtained. .
また第２銀粒子の真球度を１０％以下にし、第２銀粒子の比表面積を０．１ｍ2／ｇ以下にすれば、第２銀粒子が真球に近い形状になるとともにその比表面積が小さくなる。この結果、銀粉末を含む銀粘土の有機バインダの混合割合を少なくすることにより、第２銀粒子同士が互いに密に接触するとともに、これらの第２銀粒子の僅かな隙間に第１銀粒子が侵入した状態で焼成することができるので、焼結体の収縮率を更に小さくすることができる。なお、上記銀粉末に混合される有機バインダの混合割合を従来と同等にすれば、上記銀粉末を含む銀粘土は従来の銀粘土より造形性を向上できる。
また第１銀粒子の粒度分布の半値幅Ｈ1を０．２〜０．８μｍとし、第２銀粒子の粒度分布の半値幅Ｈ2を２０〜８０μｍとすれば、大径の第２銀粒子の粒径が揃うため、銀粉末を含む銀粘土を９００℃程度と高い温度で焼成しても、第２銀粒子が更に焼結し難くなる。この結果、焼結体の収縮率を更に小さくすることができる。
Further, if the sphericity of the second silver particles is 10% or less and the specific surface area of the second silver particles is 0.1 m 2 / g or less, the second silver particles have a shape close to a true sphere and its specific surface area. Becomes smaller. As a result, by reducing the mixing ratio of the organic binder of silver clay containing silver powder, the second silver particles are in intimate contact with each other, and the first silver particles are in a slight gap between these second silver particles. Since it can be fired in the invading state, the shrinkage rate of the sintered body can be further reduced. In addition, if the mixing ratio of the organic binder mixed with the said silver powder is made equivalent to the past, the silver clay containing the said silver powder can improve a moldability rather than the conventional silver clay.
If the half-value width H 1 of the particle size distribution of the first silver particles is 0.2 to 0.8 μm and the half-value width H 2 of the particle size distribution of the second silver particles is 20 to 80 μm, the second silver particles having a large diameter Therefore, even if silver clay containing silver powder is fired at a high temperature of about 900 ° C., the second silver particles are more difficult to sinter. As a result, the shrinkage rate of the sintered body can be further reduced.
更に上記銀粘土用銀粉末５〜９５重量％と、有機系バインダ０．５〜８重量％と、残部の水とを混合物により銀粘土を構成すれば、この銀粘土を、６００℃程度と比較的低い温度で焼成すると、焼結しない第２銀粒子を第１銀粒子の焼結により結合した状態で焼結体が作製され、９００℃程度と比較的高い温度で焼成しても、殆ど焼結しない第２銀粉末を第１銀粉末の焼結により結合した状態で焼結体が作製される。この結果、上記と同様に焼結体の収縮率が小さく、かつ６００〜９００℃と広い温度範囲で焼成しても焼結体の収縮率が殆ど変化せず、収縮率の小さい焼結体を得ることができる。 Furthermore, if the silver clay is composed of a mixture of 5 to 95% by weight of the silver powder for silver clay, 0.5 to 8% by weight of the organic binder, and the remaining water, the silver clay is compared with about 600 ° C. When sintered at a relatively low temperature, a sintered body is produced in a state where the second silver particles that are not sintered are combined by sintering the first silver particles. A sintered body is produced in a state in which the second silver powder not to be bonded is bonded by sintering the first silver powder. As a result, similarly to the above, the sintered body has a small shrinkage rate, and even when sintered in a wide temperature range of 600 to 900 ° C., the sintered body shrinkage rate hardly changes, and a sintered body having a small shrinkage rate is obtained. Obtainable.
次に本発明を実施するための最良の形態を図面に基づいて説明する。
本発明の銀粘土用銀粉末は、平均粒径が０．１〜０．５μｍ、好ましくは０．２〜０．４μｍである第１銀粒子と、平均粒径が３０〜６０μｍ、好ましくは３５〜５０μｍである第２銀粒子とを混合することにより構成される。また第１銀粒子及び第２銀粒子の混合割合は、第１銀粒子が２０〜５０重量％、好ましくは２５〜４０重量％であり、第２銀粒子が８０〜５０重量％、好ましくは６０〜７５重量％である。ここで、小径の第１銀粒子の平均粒径を０．１〜０．５μｍの範囲に限定したのは、０．１μｍ未満では銀粒子同士が凝集してしまい、０．５μｍを越えると焼成温度の下限値が高くなってしまうからである。また大径の第２銀粒子の平均粒径を３０〜６０μｍの範囲に限定したのは、３０μｍ未満では９００℃での焼成時に第２銀粒子が焼結して焼結体の収縮率が大きくなり、６０μｍを越えると粘土としての造形性が悪くなるからである。上記小径の第１銀粒子の混合割合を２０〜５０重量％の範囲に限定し、大径の第２銀粒子の混合割合を８０〜５０重量％の範囲に限定したのは、第１銀粒子が２０重量％未満であって第２銀粒子が８０重量％を越えると、焼結体の機械的強度が弱くなり、第１銀粒子が５０重量％を越え第２銀粒子が５０％未満では、粘土状にするために添加する有機系バインダの量が増加するとともに焼結体の収縮率が大きくなるからである。なお、小径の第１銀粒子は化学還元法、電解還元法、ビーズミル法などにより作製され、大径の第２銀粒子は水アトマイズ法、ガスアトマイズ法、回転ディスク法などにより作製される。
Next, the best mode for carrying out the present invention will be described with reference to the drawings.
The silver powder for silver clay of the present invention has first silver particles having an average particle diameter of 0.1 to 0.5 μm, preferably 0.2 to 0.4 μm, and an average particle diameter of 30 to 60 μm, preferably 35. It is comprised by mixing with the 2nd silver particle which is -50 micrometers. The mixing ratio of the first silver particles and the second silver particles is such that the first silver particles are 20 to 50% by weight, preferably 25 to 40% by weight, and the second silver particles are 80 to 50% by weight, preferably 60%. ~ 75 wt%. Here, the average particle size of the first silver particles having a small diameter is limited to the range of 0.1 to 0.5 μm because the silver particles are aggregated when the particle diameter is less than 0.1 μm, and the firing is performed when the particle diameter exceeds 0.5 μm. This is because the lower limit value of the temperature becomes high. Moreover, the reason why the average particle diameter of the large-diameter second silver particles is limited to the range of 30 to 60 μm is that if it is less than 30 μm, the second silver particles are sintered during firing at 900 ° C. and the shrinkage ratio of the sintered body is large. When the thickness exceeds 60 μm, the formability as clay becomes worse. The reason why the mixing ratio of the first silver particles having a small diameter is limited to a range of 20 to 50% by weight and the mixing ratio of the second silver particles having a large diameter is limited to a range of 80 to 50% by weight is the first silver particles. Is less than 20% by weight and the second silver particles exceed 80% by weight, the mechanical strength of the sintered body becomes weak, and the first silver particles exceeds 50% by weight and the second silver particles are less than 50%. This is because the shrinkage rate of the sintered body increases as the amount of the organic binder added to make the clay increases. The first silver particles having a small diameter are produced by a chemical reduction method, an electrolytic reduction method, a bead mill method or the like, and the second silver particles having a large diameter are produced by a water atomizing method, a gas atomizing method, a rotating disk method or the like.
なお、上記第１銀粒子や第２銀粒子の粒度分布の測定には、MICROTRAC FRA型粒度分析計（LEED & NORTHRUP社製）が通常用いられる。このMICROTRAC FRA型粒度分析計では、ヘキサメタリン酸ナトリウムを分散剤として用い、銀粉末を水中に分散させた状態で粒子の粒度分布を測定するようになっている。なお、MICROTRAC FRA型粒度分析計による粒度分析中に、粒子の凝集により粒度分布の極大ピークが複数個観測され、本来の平均粒径より大きな値が観測される場合がある。しかし、このような凝集状態を含めた粒子の平均粒径のデータに基づいて本発明の粒子の平均粒径と相違すると主張することはできない。なぜなら、粒度分布を測定する粒子が何も混合しない粉末状態であるときに凝集していても、この粒子をバインダと十分に混練して粘土状態としたものでは、混練による剪断力により凝集が解けるため、粒子の平均粒径は凝集のない平均粒径、即ち本発明の粒子の平均粒径の範囲内に入るからである。上記凝集状態を含む粒子では、必要に応じて超音波洗浄機により凝集した粒子の分散を促進するなどした後に粒子の粒度分布を測定することが好ましい。また上記処理を施しても凝集が解けない場合には、走査型電子顕微鏡にて無作為にサンプリングした粉末を５点以上観察し、粒子同士が焼結の初期段階である凝結の状態でないことを確認した上で、得られた画像を解析することにより粒度分布を決定してもよい。即ち、本発明において平均粒径と記述しているものは、凝集がないと仮定したときの平均粒子径若しくは１次粒子径と言い換えることができる。 A MICROTRAC FRA particle size analyzer (manufactured by LEED & NORTHRUP) is usually used to measure the particle size distribution of the first silver particles and the second silver particles. In this MICROTRAC FRA type particle size analyzer, the particle size distribution of particles is measured with silver powder dispersed in water using sodium hexametaphosphate as a dispersant. During particle size analysis using a MICROTRAC FRA type particle size analyzer, a plurality of maximum peaks in the particle size distribution are observed due to particle aggregation, and a value larger than the original average particle size may be observed. However, it cannot be argued that it is different from the average particle size of the particles of the present invention based on the data on the average particle size of the particles including such agglomerated state. This is because even if the particles whose particle size distribution is measured are in a powder state where nothing is mixed, if the particles are sufficiently kneaded with a binder to form a clay state, the agglomeration can be dissolved by the shearing force due to kneading. Therefore, the average particle size of the particles falls within the range of the average particle size without aggregation, that is, the average particle size of the particles of the present invention. In the case of the particles containing the aggregated state, it is preferable to measure the particle size distribution of the particles after promoting the dispersion of the aggregated particles with an ultrasonic cleaner as necessary. In addition, if the aggregation cannot be solved even after the above treatment, observe 5 or more powders randomly sampled with a scanning electron microscope, and confirm that the particles are not in a coagulation state, which is the initial stage of sintering. After confirmation, the particle size distribution may be determined by analyzing the obtained image. That is, what is described as an average particle diameter in the present invention can be paraphrased as an average particle diameter or a primary particle diameter when it is assumed that there is no aggregation.
また大径の第２銀粒子の真球度は１０％以下、好ましくは８％以下であり、第２銀粒子の比表面積は０．１ｍ2／ｇ以下、好ましくは０．０２〜０．０９ｍ2／ｇである。本明細書及び特許請求の範囲において、第２銀粒子の真球度とは、１つの第２銀粒子の最大直径と最小直径との差を、その第２銀粒子の平均直径で除した値をいう。具体的には、先ず第２銀粒子を電子顕微鏡により撮影し、その写真に写った第２銀粒子の直径を角度を変えて複数箇所で測定する。次いで第２銀粒子の最大直径、最小直径及び平均直径を求める。次に第２銀粒子の最大直径と最小直径との差を平均直径で除してその第２銀粒子の真球度を算出する。上記操作を複数の第２銀粒子について行って複数の第２銀粒子の真球度を算出し、その最大値を真球度の下限値とする。ここで、第２銀粒子の真球度を１０％以下に限定し、第２銀粒子の比表面積を０．１ｍ2／ｇ以下に限定したのは、真球度が１０％を越え比表面積が０．１ｍ2／ｇを越えると第２銀粒子同士が密に接触できないからである。なお、上記真球度が１０％以下の大径の第２銀粒子は水アトマイズ法で作製される。 The sphericity of the large-diameter second silver particles is 10% or less, preferably 8% or less, and the specific surface area of the second silver particles is 0.1 m 2 / g or less, preferably 0.02 to 0.09 m. 2 / g. In the present specification and claims, the sphericity of the second silver particle is a value obtained by dividing the difference between the maximum diameter and the minimum diameter of one second silver particle by the average diameter of the second silver particle. Say. Specifically, first, the second silver particles are photographed with an electron microscope, and the diameters of the second silver particles appearing in the photograph are measured at a plurality of locations at different angles. Next, the maximum diameter, minimum diameter, and average diameter of the second silver particles are determined. Next, the sphericity of the second silver particle is calculated by dividing the difference between the maximum diameter and the minimum diameter of the second silver particle by the average diameter. The above operation is performed on the plurality of second silver particles to calculate the sphericity of the plurality of second silver particles, and the maximum value is set as the lower limit of the sphericity. Here, the sphericity of the second silver particles is limited to 10% or less, and the specific surface area of the second silver particles is limited to 0.1 m 2 / g or less. This is because the second silver particles cannot be in intimate contact with each other when the particle size exceeds 0.1 m 2 / g. The large-diameter second silver particles having a sphericity of 10% or less are produced by a water atomization method.
更に第１銀粒子の粒度分布の半値幅Ｈ1（図１）は０．２〜０．８μｍ、好ましくは０．３〜０．６μｍであり、第２銀粒子の粒度分布の半値幅Ｈ2（図１）は２０〜８０μｍ、好ましくは３０〜５０μｍである。本明細書及び特許請求の範囲において、半値幅とは、第１及び第２銀粒子の山形の粒度分布曲線において、銀粒子の個数が最大値の１／２の値における銀粒子の平均粒径の幅をいう。ここで、第１銀粒子の粒度分布の半値幅Ｈ1を０．２〜０．８μｍの範囲に限定したのは、０．２μｍ未満では分級が難しく、０．８μｍを越えると焼結体の収縮率を大きくする粒径の銀粒子を含んでしまうからである。また第２銀粒子の粒度分布の半値幅Ｈ2を２０〜８０μｍの範囲に限定したのは、２０μｍ未満では分級が難しく、８０μｍを越えると焼結体の収縮率を大きくする粒径の銀粒子を含んでしまうからである。なお、上記粒度分布の半値幅Ｈ1が０．２〜０．８μｍである第１銀粒子は化学還元法で作製され、粒度分布の半値幅Ｈ2が２０〜８０μｍの第２銀粒子は水アトマイズ法で作製される。 Further, the half width H 1 (FIG. 1) of the particle size distribution of the first silver particles is 0.2 to 0.8 μm, preferably 0.3 to 0.6 μm, and the half width H 2 of the particle size distribution of the second silver particles. (FIG. 1) is 20-80 micrometers, Preferably it is 30-50 micrometers. In the present specification and claims, the half width is the average particle diameter of silver particles when the number of silver particles is ½ of the maximum value in the mountain-shaped particle size distribution curve of the first and second silver particles. The width of Here, the reason why the half width H 1 of the particle size distribution of the first silver particles is limited to the range of 0.2 to 0.8 μm is that classification is difficult if it is less than 0.2 μm, and if it exceeds 0.8 μm, This is because silver particles having a particle size that increases the shrinkage rate are included. Further, the half-value width H 2 of the particle size distribution of the second silver particles is limited to the range of 20 to 80 μm. If the particle size is less than 20 μm, classification is difficult. It is because it will be included. Note that the first silver particles half width H 1 of the particle size distribution is 0.2~0.8μm is produced by a chemical reduction method, a second silver particles of the half-value width H 2 is 20~80μm water of the particle size distribution It is produced by the atomizing method.
このように構成された銀粘土用銀粉末では、この銀粉末を用いて作製した銀粘土を６００℃程度と比較的低い温度で焼成すると、第２銀粒子が焼結せずに第１銀粒子が焼結して、第１銀粒子が第２銀粒子を結合するため、収縮率の小さい焼結体が得られる。一方、この銀粉末を用いて作製した銀粘土を９００℃程度と比較的高い温度で焼成すると、第１銀粒子が焼結するとともに、第２銀粒子が僅かに焼結し始めるけれども、第２銀粒子の平均粒径が大径であるため焼結し難く、収縮率の小さい焼結体を得ることができる。この結果、焼結体の収縮率が小さく、かつ６００〜９００℃と広い温度範囲で焼成しても焼結体の収縮率が殆ど変化せず、収縮率の小さい焼結体を得ることができる。 In the silver powder for silver clay constructed as described above, when the silver clay produced using this silver powder is fired at a relatively low temperature of about 600 ° C., the second silver particles are not sintered and the first silver particles Since the first silver particles are bonded to the second silver particles, a sintered body having a small shrinkage rate is obtained. On the other hand, when the silver clay produced using this silver powder is fired at a relatively high temperature of about 900 ° C., the first silver particles are sintered and the second silver particles begin to be slightly sintered. Since the average particle diameter of the silver particles is large, it is difficult to sinter and a sintered body having a small shrinkage rate can be obtained. As a result, the shrinkage rate of the sintered body is small, and even when sintered in a wide temperature range of 600 to 900 ° C., the shrinkage rate of the sintered body hardly changes and a sintered body having a small shrinkage rate can be obtained. .
また第２銀粒子を真球に近い形状にするとともにその比表面積を小さくしたので、この第２銀粒子と第１銀粒子を混合してなる銀粉末を含む銀粘土の有機バインダの混合割合を少なくすれば、第２銀粒子同士が互いに密に接触するとともに、これらの第２銀粒子の僅かな隙間に第１銀粒子が侵入した状態で焼成することができる。この結果、焼結体の収縮率を更に小さくすることができる。なお、上記銀粉末に混合される有機バインダの混合割合を従来と同等にすれば、上記銀粉末を含む銀粘土は従来の銀粘土より造形性を向上できる。
更に第２銀粒子の粒度分布の半値幅Ｈ2が２０〜８０μｍと狭いため、大径の第２銀粒子の粒径が揃うため、銀粉末を含む銀粘土を９００℃程度と高い温度で焼成しても、第２銀粒子が更に焼結し難くなる。この結果、焼結体の収縮率を更に小さくすることができる。
In addition, since the second silver particles have a shape close to a true sphere and the specific surface area is reduced, the mixing ratio of the organic binder of silver clay containing silver powder obtained by mixing the second silver particles and the first silver particles is If the number is reduced, the second silver particles can be in close contact with each other, and firing can be performed in a state where the first silver particles have entered into the slight gap between the second silver particles. As a result, the shrinkage rate of the sintered body can be further reduced. In addition, if the mixing ratio of the organic binder mixed with the said silver powder is made equivalent to the past, the silver clay containing the said silver powder can improve a moldability rather than the conventional silver clay.
Furthermore, since the half-value width H 2 of the particle size distribution of the second silver particles is as narrow as 20 to 80 μm, the particle size of the second silver particles having large diameters is uniform, so that silver clay containing silver powder is fired at a high temperature of about 900 ° C. Even so, the second silver particles are more difficult to sinter. As a result, the shrinkage rate of the sintered body can be further reduced.
上記銀粉末を用いた銀粘土は、上記銀粉末５０〜９５重量％、好ましくは９０〜９４重量％と、有機系バインダ０．５〜８重量％、好ましくは０．８〜４重量％と、残部の水とを混合することにより構成される。ここで、銀粉末の混合割合を５０〜９５重量％の範囲に限定したのは、５０重量％未満では銀粘土を焼成して得られた焼結体が十分に金属光沢を示さず、９５重量％を越えると粘土としての伸びおよび強度が低下するからである。有機系バインダとしては、セルロース系バインダ、ポリビニール系バインダ、アクリル系バインダ、ワックス系バインダ、樹脂系バインダ、澱粉、ゼラチン、小麦粉などのバインダを使用できるけれども、セルロース系バインダ、特に水溶性セルロースを用いることが最も好ましい。上記バインダは、加熱すると速やかにゲル化して造形体の形状保持を容易にするために添加される。また有機系バインダの混合割合を０．５〜８重量％の範囲に限定したのは、０．５重量％未満では銀粉末を結合できず、８重量％を越えると銀粘土の成形時に微細なひび割れが発生し、光沢も減少するからである。 The silver clay using the silver powder is 50 to 95% by weight, preferably 90 to 94% by weight, 0.5 to 8% by weight of an organic binder, preferably 0.8 to 4% by weight, It is constituted by mixing the remaining water. Here, the mixing ratio of the silver powder was limited to the range of 50 to 95% by weight. When the amount was less than 50% by weight, the sintered body obtained by firing silver clay did not exhibit a sufficient metallic luster, and 95% by weight. This is because if the content exceeds 50%, the elongation and strength of the clay decrease. As the organic binder, a binder such as a cellulose binder, a polyvinyl binder, an acrylic binder, a wax binder, a resin binder, starch, gelatin, and wheat flour can be used, but a cellulose binder, particularly a water-soluble cellulose is used. Most preferred. The binder is added in order to quickly gel when heated to facilitate the shape maintenance of the shaped body. Further, the mixing ratio of the organic binder is limited to the range of 0.5 to 8% by weight. If the amount is less than 0.5% by weight, the silver powder cannot be bonded. This is because cracks occur and gloss decreases.
なお、水の一部を０．０３〜３重量％、好ましくは０．０４〜１重量％の界面活性剤又は０．１〜３重量％、好ましくは０．２〜２重量％の油脂のいずれか一方又は双方に置き換えてもよい。ここで、界面活性剤の添加量を０．０３〜３重量％の範囲に限定したのは、０．０３重量％未満では銀粒子の分散が得られず、３重量％を越えると粘土乾燥時の強度が得られないからである。また油脂の添加量を１〜３重量％の範囲に限定したのは、１重量％未満では手などへの付着防止効果が得られず、３重量％を越えると粘土乾燥に時間を要し、乾燥後に脆くなるからである。なお、界面活性剤の種類は特に限定されるものではなく、アニオン系、カチオン系、ノニオン系等の界面活性剤を使用することができる。また油脂としては、有機酸（オレイン酸、ステアリン酸、フタル酸、パルミチン酸、セパシン酸、アセチルクエン酸、ヒドロキシ安息香酸、ラウリン酸、ミリスチン酸、カプロン酸、エナント酸、酪酸、カプリン酸）、有機酸エステル（メチル基、エチル基、プロピル基、ブチル基、オクチル基、ヘキシル基、ジメチル基、ジエチル基、イソプロピル基、イソブチル基を有する有機酸エステル）、高級アルコール（オクタノール、ノナノール、デカノール）、多価アルコール（グリセリン、アラビット、ソルビタン、）、エーテル（ジオクチルエーテル、ジデシルエーテル）、或いは上記有機酸、有機酸エステル、高級アルコール、多価アルコール及びエーテルからなる群より選ばれた１種又は２種以上の混合物（例えば、オレイン酸を多く含むオリーブ油）などが挙げられる。 A part of water is either 0.03 to 3% by weight, preferably 0.04 to 1% by weight of surfactant or 0.1 to 3% by weight, preferably 0.2 to 2% by weight of fat or oil. Either or both may be replaced. Here, the addition amount of the surfactant is limited to the range of 0.03 to 3% by weight. If the amount is less than 0.03% by weight, the dispersion of silver particles cannot be obtained. This is because the above strength cannot be obtained. Moreover, the addition amount of fats and oils was limited to the range of 1 to 3% by weight. If the amount is less than 1% by weight, an effect of preventing adhesion to hands and the like cannot be obtained, and if it exceeds 3% by weight, it takes time to dry the clay. This is because it becomes brittle after drying. In addition, the kind of surfactant is not specifically limited, Surfactants, such as anionic, cationic, and nonionic, can be used. As fats and oils, organic acids (oleic acid, stearic acid, phthalic acid, palmitic acid, sepacic acid, acetylcitric acid, hydroxybenzoic acid, lauric acid, myristic acid, caproic acid, enanthic acid, butyric acid, capric acid), organic Acid ester (organic acid ester having methyl group, ethyl group, propyl group, butyl group, octyl group, hexyl group, dimethyl group, diethyl group, isopropyl group, isobutyl group), higher alcohol (octanol, nonanol, decanol), many 1 type or 2 types selected from the group consisting of a monohydric alcohol (glycerin, arabit, sorbitan), ether (dioctyl ether, didecyl ether), or the above organic acid, organic acid ester, higher alcohol, polyhydric alcohol and ether A mixture of the above (for example, oleic acid No olive oil), and the like.
上記銀粉末を含む銀粘土では、この銀粘土を６００℃程度と比較的低い温度で焼成すると、第２銀粒子が焼結せずに第１銀粒子が焼結して、第１銀粒子が第２銀粒子を結合するため、収縮率の小さい焼結体が得られる。一方、この銀粘土を９００℃程度と比較的高い温度で焼成すると、第１銀粒子が焼結するとともに、第２銀粒子が僅かに焼結し始めるけれども、第２銀粒子の平均粒径が大径であるため焼結し難く、収縮率の小さい焼結体を得ることができる。この結果、上記と同様に、焼結体の収縮率が小さく、かつ６００〜９００℃と広い温度範囲で焼成しても焼結体の収縮率が殆ど変化せず、収縮率の小さい焼結体を得ることができる。 In the silver clay containing the silver powder, when the silver clay is fired at a relatively low temperature of about 600 ° C., the first silver particles are sintered without the second silver particles being sintered. Since the second silver particles are bonded, a sintered body having a small shrinkage rate is obtained. On the other hand, when this silver clay is fired at a relatively high temperature of about 900 ° C., the first silver particles are sintered and the second silver particles begin to sinter slightly. Since it has a large diameter, it is difficult to sinter and a sintered body having a small shrinkage rate can be obtained. As a result, similar to the above, the shrinkage of the sintered body is small, and even when fired in a wide temperature range of 600 to 900 ° C., the shrinkage of the sintered body hardly changes, and the sintered body has a small shrinkage rate. Can be obtained.
次に本発明の実施例を比較例とともに詳しく説明する。
＜実施例１＞
先ず平均粒径０．１μｍで半値幅０．３０μｍの化学還元法により作製した第１銀粒子を用意し、平均粒径４０μｍ、半値幅３０μｍ、比表面積０．０７ｍ2／ｇのアトマイズ法により作製した第２銀粒子を用意した。また有機系バインダとしてメチルセルロースを、界面活性剤としてソルスパース２０，０００（アビシア株式会社製）を、油脂としてオリーブ油を用意し、更に水を用意した。次に第１銀粒子４０重量％と第２銀粒子６０重量％とを混合して銀粉末を作製した。更にこの銀粉末９０重量％と、メチルセルロース１．２重量％と、ソルスパース２０，０００（界面活性剤）０．０５重量％と、オリーブ油０．５重量％と、水８．２５重量％とを混合して銀粘土を得た。この銀粘土を実施例１とした。なお、上記第１銀粒子及び第２銀粒子の平均粒径はMICROTRAC FRA型粒度分析計（LEED & NORTHRUP社製）を用いてそれぞれ測定し、第１銀粒子及び第２銀粒子の半値幅はMICROTRAC FRA型粒度分析計（LEED & NORTHRUP社製）を用いて測定した粒度分布に基づいてそれぞれ算出した。
Next, examples of the present invention will be described in detail together with comparative examples.
<Example 1>
First, first silver particles prepared by a chemical reduction method having an average particle size of 0.1 μm and a half width of 0.30 μm are prepared, and prepared by an atomizing method having an average particle size of 40 μm, a half width of 30 μm, and a specific surface area of 0.07 m 2 / g. Second silver particles prepared were prepared. Further, methylcellulose was prepared as an organic binder, Solsperse 20,000 (manufactured by Avicia Co., Ltd.) as a surfactant, olive oil as an oil and fat, and water. Next, 40% by weight of the first silver particles and 60% by weight of the second silver particles were mixed to prepare a silver powder. Furthermore, 90% by weight of this silver powder, 1.2% by weight of methylcellulose, 0.05% by weight of Solsperse 20,000 (surfactant), 0.5% by weight of olive oil, and 8.25% by weight of water are mixed. To obtain silver clay. This silver clay was designated as Example 1. The average particle size of the first silver particles and the second silver particles was measured using a MICROTRAC FRA particle size analyzer (manufactured by LEED & NORTHRUP). The half width of the first silver particles and the second silver particles was Each was calculated based on the particle size distribution measured using a MICROTRAC FRA type particle size analyzer (manufactured by LEED & NORTHRUP).
＜実施例２＞
第１銀粒子の平均粒径を０．２μｍとし、第１銀粒子の半値幅を０．３５μｍとしたことを除いて、実施例１と同様にして銀粘土を作製した。この銀粘土を実施例２とした。
＜実施例３＞
第１銀粒子の平均粒径を０．４μｍとし、第１銀粒子の半値幅を０．６μｍとしたことを除いて、実施例１と同様にして銀粘土を作製した。この銀粘土を実施例３とした。
＜実施例４＞
第１銀粒子の平均粒径を０．５μｍとし、第１銀粒子の半値幅を０．８μｍとしたことを除いて、実施例１と同様にして銀粘土を作製した。この銀粘土を実施例４とした。
<Example 2>
A silver clay was prepared in the same manner as in Example 1 except that the average particle diameter of the first silver particles was 0.2 μm and the half width of the first silver particles was 0.35 μm. This silver clay was designated as Example 2.
<Example 3>
A silver clay was produced in the same manner as in Example 1 except that the average particle diameter of the first silver particles was 0.4 μm and the half width of the first silver particles was 0.6 μm. This silver clay was designated as Example 3.
<Example 4>
A silver clay was produced in the same manner as in Example 1 except that the average particle diameter of the first silver particles was 0.5 μm and the half width of the first silver particles was 0.8 μm. This silver clay was designated as Example 4.
＜実施例５＞
第１銀粒子の平均粒径を０．３μｍとし、第１銀粒子の半値幅を０．４５μｍとし、第２銀粒子の平均粒径を３０μｍとし、第２銀粒子の半値幅を０．２０μｍとし、第２銀粒子の比表面積を０．０９ｍ2／ｇとしたことを除いて、実施例１と同様にして銀粘土を作製した。この銀粘土を実施例５とした。
＜実施例６＞
第２銀粒子の平均粒径を３０μｍとし、第２銀粒子の半値幅を３０μｍとし、第２銀粒子の比表面積を０．０７ｍ2／ｇとしたことを除いて、実施例５と同様にして銀粘土を作製した。この銀粘土を実施例６とした。
＜実施例７＞
第２銀粒子の平均粒径を５０μｍとし、第２銀粒子の半値幅を６０μｍとし、第２銀粒子の比表面積を０．４５ｍ2／ｇとしたことを除いて、実施例５と同様にして銀粘土を作製した。この銀粘土を実施例７とした。
＜実施例８＞
第２銀粒子の平均粒径を６０μｍとし、第２銀粒子の半値幅を８０μｍとし、第２銀粒子の比表面積を０．０２ｍ2／ｇとしたことを除いて、実施例５と同様にして銀粘土を作製した。この銀粘土を実施例８とした。
<Example 5>
The average particle size of the first silver particles is 0.3 μm, the half width of the first silver particles is 0.45 μm, the average particle size of the second silver particles is 30 μm, and the half width of the second silver particles is 0.20 μm. A silver clay was prepared in the same manner as in Example 1 except that the specific surface area of the second silver particles was 0.09 m 2 / g. This silver clay was designated as Example 5.
<Example 6>
The same as Example 5 except that the average particle size of the second silver particles was 30 μm, the half width of the second silver particles was 30 μm, and the specific surface area of the second silver particles was 0.07 m 2 / g. To make silver clay. This silver clay was taken as Example 6.
<Example 7>
The same as Example 5 except that the average particle size of the second silver particles was 50 μm, the half width of the second silver particles was 60 μm, and the specific surface area of the second silver particles was 0.45 m 2 / g. To make silver clay. This silver clay was designated as Example 7.
<Example 8>
The same as Example 5 except that the average particle size of the second silver particles was 60 μm, the half width of the second silver particles was 80 μm, and the specific surface area of the second silver particles was 0.02 m 2 / g. To make silver clay. This silver clay was designated as Example 8.
＜実施例９＞
第２銀粒子の平均粒径を４０μｍとし、第２銀粒子の半値幅を３０μｍとし、第２銀粒子の比表面積を０．０７ｍ2／ｇとし、第１銀粒子３０重量％と第２銀粒子７０重量％とを混合して銀粉末を作製したたことを除いて、実施例５と同様にして銀粘土を作製した。この銀粘土を実施例９とした。
＜実施例１０＞
第１銀粒子３５重量％と第２銀粒子６５重量％とを混合して銀粉末を作製したたことを除いて、実施例９と同様にして銀粘土を作製した。この銀粘土を実施例１０とした。
＜実施例１１＞
第１銀粒子４５重量％と第２銀粒子５５重量％とを混合して銀粉末を作製したたことを除いて、実施例９と同様にして銀粘土を作製した。この銀粘土を実施例１１とした。
＜実施例１２＞
第１銀粒子５０重量％と第２銀粒子５０重量％とを混合して銀粉末を作製したたことを除いて、実施例９と同様にして銀粘土を作製した。この銀粘土を実施例１２とした。
<Example 9>
The average particle size of the second silver particles is 40 μm, the half-value width of the second silver particles is 30 μm, the specific surface area of the second silver particles is 0.07 m 2 / g, 30% by weight of the first silver particles and the second silver A silver clay was prepared in the same manner as in Example 5 except that a silver powder was prepared by mixing 70% by weight of the particles. This silver clay was designated as Example 9.
<Example 10>
A silver clay was prepared in the same manner as in Example 9 except that 35% by weight of the first silver particles and 65% by weight of the second silver particles were mixed to prepare a silver powder. This silver clay was taken as Example 10.
<Example 11>
A silver clay was prepared in the same manner as in Example 9 except that 45% by weight of the first silver particles and 55% by weight of the second silver particles were mixed to prepare a silver powder. This silver clay was designated as Example 11.
<Example 12>
A silver clay was prepared in the same manner as in Example 9 except that 50% by weight of the first silver particles and 50% by weight of the second silver particles were mixed to prepare a silver powder. This silver clay was designated as Example 12.
＜比較例１＞
第１銀粒子の平均粒径を０．０５μｍとし、第１銀粒子の半値幅を０．２５μｍとしたことを除いて、実施例１と同様にして銀粘土を作製した。この銀粘土を比較例１とした。
＜比較例２＞
第１銀粒子の平均粒径を０．８μｍとし、第１銀粒子の半値幅を１．３μｍとしたことを除いて、実施例１と同様にして銀粘土を作製した。この銀粘土を比較例２とした。
＜比較例３＞
第１銀粒子の平均粒径を０．３μｍとし、第１銀粒子の半値幅を０．４５μｍとし、第２銀粒子の平均粒径を２０μｍとし、第２銀粒子の半値幅を１５μｍとし、第２銀粒子の比表面積を０．０９ｍ2／ｇとしたことを除いて、実施例１と同様にして銀粘土を作製した。この銀粘土を比較例３とした。
＜比較例４＞
第２粒子の平均粒径を７０μｍとし、第２銀粒子の半値幅を１５０μｍとし、第２銀粒子の比表面積を０．０２ｍ2／ｇとしたことを除いて、比較例３と同様にして銀粘土を作製した。この銀粘土を比較例４とした。
＜比較例５＞
第２銀粒子の平均粒径を４０μｍとし、第２銀粒子の半値幅を３０μｍとし、第２銀粒子の比表面積を０．０７ｍ2／ｇとし、第１銀粒子２０重量％と第２銀粒子８０重量％とを混合して銀粉末を作製したたことを除いて、比較例３と同様にして銀粘土を作製した。この銀粘土を比較例５とした。
＜比較例６＞
第１銀粒子６０重量％と第２銀粒子４０重量％とを混合して銀粉末を作製したたことを除いて、比較例５と同様にして銀粘土を作製した。この銀粘土を比較例６とした。
<Comparative Example 1>
A silver clay was produced in the same manner as in Example 1 except that the average particle diameter of the first silver particles was 0.05 μm and the half width of the first silver particles was 0.25 μm. This silver clay was designated as Comparative Example 1.
<Comparative example 2>
A silver clay was produced in the same manner as in Example 1 except that the average particle diameter of the first silver particles was 0.8 μm and the half width of the first silver particles was 1.3 μm. This silver clay was designated as Comparative Example 2.
<Comparative Example 3>
The average particle size of the first silver particles is 0.3 μm, the half width of the first silver particles is 0.45 μm, the average particle size of the second silver particles is 20 μm, and the half width of the second silver particles is 15 μm, A silver clay was prepared in the same manner as in Example 1 except that the specific surface area of the second silver particles was 0.09 m 2 / g. This silver clay was designated as Comparative Example 3.
<Comparative example 4>
The same as Comparative Example 3, except that the average particle size of the second particles was 70 μm, the half width of the second silver particles was 150 μm, and the specific surface area of the second silver particles was 0.02 m 2 / g. Silver clay was prepared. This silver clay was designated as Comparative Example 4.
<Comparative Example 5>
The average particle size of the second silver particles is 40 μm, the half-value width of the second silver particles is 30 μm, the specific surface area of the second silver particles is 0.07 m 2 / g, 20% by weight of the first silver particles and the second silver A silver clay was prepared in the same manner as in Comparative Example 3 except that 80% by weight of the particles were mixed to prepare a silver powder. This silver clay was designated as Comparative Example 5.
<Comparative Example 6>
A silver clay was prepared in the same manner as in Comparative Example 5, except that 60% by weight of the first silver particles and 40% by weight of the second silver particles were mixed to prepare a silver powder. This silver clay was designated as Comparative Example 6.
＜比較試験１及び評価＞
実施例１〜１２及び比較例１〜６の銀粘土を所定の形状に造形し、得られた造形体を６００℃の低温度で３０分間燒結することにより、縦×横×長さがそれぞれ３ｍｍ×４ｍｍ×６５ｍｍである直方体状の焼結体を作製し、これらの焼結体の線収縮率を測定した。また上記実施例１〜１２及び比較例１〜６の銀粘土を所定の形状に造形し、得られた造形体を９００℃の低温度で１０分間燒結することにより、縦×横×長さがそれぞれ３ｍｍ×４ｍｍ×６５ｍｍである直方体状の焼結体を作製し、これらの焼結体の線収縮率を測定した。これらの結果を表１に示す。
<Comparative test 1 and evaluation>
The silver clays of Examples 1 to 12 and Comparative Examples 1 to 6 are shaped into a predetermined shape, and the obtained shaped bodies are sintered at a low temperature of 600 ° C. for 30 minutes, whereby the length × width × length is 3 mm each. A rectangular parallelepiped sintered body having a size of 4 mm × 65 mm was produced, and the linear shrinkage rate of these sintered bodies was measured. Further, the silver clays of Examples 1 to 12 and Comparative Examples 1 to 6 are shaped into a predetermined shape, and the obtained shaped body is sintered at a low temperature of 900 ° C. for 10 minutes, whereby the length × width × length is A rectangular parallelepiped sintered body of 3 mm × 4 mm × 65 mm was prepared, and the linear shrinkage rate of these sintered bodies was measured. These results are shown in Table 1.
表１から明らかなように、比較例２及び３では９００℃１０分の焼成条件における線収縮率が６００℃３０分焼成時における線収縮率に対して５．８％及び７．３％と大きくなった。また比較例１及び比較例３〜５では、線収縮率の変化は比較的小さいけれども、比較例１及び６では膨れが発生し、比較例４及び５では焼結強度が不十分であった。これに対し、実施例１〜１２では、平均粒径が０．１〜０．５μｍである第１銀粒子を２０〜５０重量％と、平均粒径が３０〜６０μｍである第２銀粒子を８０〜５０重量％としたので、６００℃３０分の焼成条件においても十分な焼結強度が得られ、９００℃１０分の焼成条件においても膨れの問題も起きない上、線収縮率の増加が６００℃３０分焼成時と比べて４％以内に収まり、広い温度範囲で低収縮であってかつその線収縮率が安定していることが判った。 As is clear from Table 1, in Comparative Examples 2 and 3, the linear shrinkage rate at 900 ° C. for 10 minutes and the linear shrinkage rate at 600 ° C. for 30 minutes was as large as 5.8% and 7.3%, respectively. became. In Comparative Example 1 and Comparative Examples 3 to 5, although the change in the linear shrinkage rate was relatively small, in Comparative Examples 1 and 6, swelling occurred, and in Comparative Examples 4 and 5, the sintering strength was insufficient. On the other hand, in Examples 1-12, 20-50 weight% of the 1st silver particle whose average particle diameter is 0.1-0.5 micrometer, and the 2nd silver particle whose average particle diameter is 30-60 micrometers are used. Since 80 to 50% by weight, sufficient sintering strength can be obtained even under firing conditions of 600 ° C. for 30 minutes, and there is no problem of swelling even under firing conditions of 900 ° C. for 10 minutes, and the linear shrinkage rate is increased. It was found that it was within 4% of that at 600 ° C. for 30 minutes, low shrinkage over a wide temperature range, and stable linear shrinkage.
＜実施例１３＞
先ず、平均粒径０．４μｍで半値幅０．５μｍの化学還元法により作製した第１銀粒子を用意し、平均粒径４０μｍ、半値幅が５０μｍ、真球度が８％、比表面積が０．０７ｍ2／ｇの水アトマイズ法により作製した第２銀粒子を用意した。また有機バインダとしてメチルセルロースを、界面活性剤としてソルスパース２０，０００（アビシア株式会社製）を、油脂としてオリーブ油を用意し、更に水を用意した。次に第１銀粒子４０重量％と混合して銀粉末を作製した。更にこの銀粉末９０重量％と、メチルセルロース１．２重量％と、ソルスパース２０，０００を０．５重量％と、オリーブ油０．５重量％と、水８．２５重量％とを混合して銀粘土を得た。この銀粘土を実施例１３とした。
<Example 13>
First, first silver particles prepared by a chemical reduction method having an average particle diameter of 0.4 μm and a half width of 0.5 μm are prepared. The average particle diameter is 40 μm, the half width is 50 μm, the sphericity is 8%, and the specific surface area is 0. Second silver particles prepared by a water atomization method of 0.07 m 2 / g were prepared. Further, methylcellulose was prepared as an organic binder, Solsperse 20,000 (manufactured by Avicia Co., Ltd.) as a surfactant, olive oil as an oil and fat, and water. Next, it mixed with 40 weight% of 1st silver particles, and produced silver powder. Further, 90% by weight of this silver powder, 1.2% by weight of methylcellulose, 0.5% by weight of Solsperse 20,000, 0.5% by weight of olive oil and 8.25% by weight of water were mixed to give silver clay. Got. This silver clay was designated as Example 13.
＜実施例１４＞
第１銀粒子の半値幅を０．４μｍとしたことを除いて、実施例１３と同様にして銀粘土を作製した。この銀粘土を実施例１４とした。
＜実施例１５＞
第１銀粒子の半値幅を０．６μｍとしたことを除いて、実施例１３と同様にして銀粘土を作製した。この銀粘土を実施例１５とした。
＜実施例１６＞
第１銀粒子の半値幅を０．８μｍとしたことを除いて、実施例１３と同様にして銀粘土を作製した。この銀粘土を実施例１６とした。
<Example 14>
Silver clay was produced in the same manner as in Example 13 except that the half width of the first silver particles was 0.4 μm. This silver clay was designated as Example 14.
<Example 15>
A silver clay was produced in the same manner as in Example 13 except that the half width of the first silver particles was 0.6 μm. This silver clay was determined as Example 15.
<Example 16>
A silver clay was produced in the same manner as in Example 13 except that the half width of the first silver particles was 0.8 μm. This silver clay was determined as Example 16.
＜実施例１７＞
第１銀粒子の半値幅を０．５μｍとし、第２銀粒子の半値幅を２０μｍとし、第２銀粒子の比表面積を０．０４としたことを除いて、実施例１３と同様にして銀粘土を作製した。この銀粘土を実施例１７とした。
＜実施例１８＞
第１銀粒子の半値幅を０．５μｍとし、第２銀粒子の半値幅を４０μｍとし、第２銀粒子の比表面積を０．０６としたことを除いて、実施例１３と同様にして銀粘土を作製した。この銀粘土を実施例１８とした。
＜実施例１９＞
第１銀粒子の半値幅を０．５μｍとし、第２銀粒子の半値幅を６０μｍとし、第２銀粒子の比表面積を０．０８ｍ2／ｇとしたことを除いて、実施例１３と同様にして銀粘土を作製した。この銀粘土を実施例１９とした。
<Example 17>
In the same manner as in Example 13, except that the half width of the first silver particles was 0.5 μm, the half width of the second silver particles was 20 μm, and the specific surface area of the second silver particles was 0.04. Clay was made. This silver clay was designated as Example 17.
<Example 18>
Silver as in Example 13 except that the half width of the first silver particles was 0.5 μm, the half width of the second silver particles was 40 μm, and the specific surface area of the second silver particles was 0.06. Clay was made. This silver clay was designated as Example 18.
<Example 19>
Same as Example 13 except that the half width of the first silver particles was 0.5 μm, the half width of the second silver particles was 60 μm, and the specific surface area of the second silver particles was 0.08 m 2 / g. A silver clay was prepared. This silver clay was determined as Example 19.
＜実施例２０＞
第１銀粒子の半値幅を０．５μｍとし、第２銀粒子の半値幅を８０μｍとし、第２銀粒子の比表面積を０．１０ｍ2／ｇとしたことを除いて、実施例１３と同様にして銀粘土を作製した。この銀粘土を実施例２０とした。
＜実施例２１＞
第１銀粒子の半値幅を０．５μｍとし、第２銀粒子の真球度を５．０％とし、第２銀粒子の比表面積を０．０６ｍ2／ｇとしたことを除いて、実施例１３と同様にして銀粘土を作製した。この銀粘土を実施例２１とした。
＜実施例２２＞
第１銀粒子の半値幅を０．５μｍとし、第２銀粒子の真球度を１０．０％とし、第２銀粒子の比表面積を０．０８ｍ2／ｇとしたことを除いて、実施例１３と同様にして銀粘土を作製した。この銀粘土を実施例２２とした。
<Example 20>
Same as Example 13 except that the half width of the first silver particles was 0.5 μm, the half width of the second silver particles was 80 μm, and the specific surface area of the second silver particles was 0.10 m 2 / g. A silver clay was prepared. This silver clay was referred to as Example 20.
<Example 21>
Except that the half width of the first silver particles was 0.5 μm, the sphericity of the second silver particles was 5.0%, and the specific surface area of the second silver particles was 0.06 m 2 / g. A silver clay was prepared in the same manner as in Example 13. This silver clay was taken as Example 21.
<Example 22>
Except that the half width of the first silver particles was 0.5 μm, the sphericity of the second silver particles was 10.0%, and the specific surface area of the second silver particles was 0.08 m 2 / g. A silver clay was prepared in the same manner as in Example 13. This silver clay was determined as Example 22.
＜比較例７＞
第１銀粒子の半値幅を１．０μｍとしたことを除いて、実施例１３と同様にして銀粘土を作製した。この銀粘土を比較例７とした。
＜比較例８＞
第１銀粒子の半値幅を０．５μｍとし、第２銀粒子の半値幅を９０μｍとし、第２銀粒子の比表面積を０．０９ｍ2／ｇとしたことを除いて、実施例１３と同様にして銀粘土を作製した。この銀粘土を比較例８とした。
＜比較例９＞
第１銀粒子の半値幅を０．５μｍとし、第２銀粒子の真球度１２．０％とし、第２銀粒子の比表面積を１．１０ｍ2／ｇとしたことを除いて、実施例１３と同様にして銀粘土を作製した。この銀粘土を比較例９とした。
<Comparative Example 7>
A silver clay was prepared in the same manner as in Example 13 except that the half width of the first silver particles was 1.0 μm. This silver clay was designated as Comparative Example 7.
<Comparative Example 8>
Same as Example 13 except that the half width of the first silver particles was 0.5 μm, the half width of the second silver particles was 90 μm, and the specific surface area of the second silver particles was 0.09 m 2 / g. A silver clay was prepared. This silver clay was designated as Comparative Example 8.
<Comparative Example 9>
Example, except that the half width of the first silver particles was 0.5 μm, the sphericity of the second silver particles was 12.0%, and the specific surface area of the second silver particles was 1.10 m 2 / g. In the same manner as in Example 13, silver clay was prepared. This silver clay was designated as Comparative Example 9.
＜比較試験２及び評価＞
実施例１〜１２及び比較例１〜６の銀粘土を所定の形状に造形し、得られた造形体を６００℃の低温度で３０分間燒結することにより、縦×横×長さがそれぞれ３ｍｍ×４ｍｍ×６５ｍｍである直方体状の焼結体を作製し、これらの焼結体の線収縮率を測定した。また上記実施例１３〜２２及び比較例７〜９の銀粘土を所定の形状に造形し、得られた造形体を９００℃の低温度で１０分間燒結することにより、縦×横×長さがそれぞれ３ｍｍ×４ｍｍ×６５ｍｍである直方体状の焼結体を作製し、これらの焼結体の線収縮率を測定した。これらの結果を表２に示す。
<Comparative test 2 and evaluation>
The silver clays of Examples 1 to 12 and Comparative Examples 1 to 6 are shaped into a predetermined shape, and the obtained shaped bodies are sintered at a low temperature of 600 ° C. for 30 minutes, whereby the length × width × length is 3 mm each. A rectangular parallelepiped sintered body having a size of 4 mm × 65 mm was produced, and the linear shrinkage rate of these sintered bodies was measured. In addition, the silver clays of Examples 13 to 22 and Comparative Examples 7 to 9 were formed into a predetermined shape, and the obtained shaped body was sintered at a low temperature of 900 ° C. for 10 minutes, whereby the length × width × length was A rectangular parallelepiped sintered body of 3 mm × 4 mm × 65 mm was prepared, and the linear shrinkage rate of these sintered bodies was measured. These results are shown in Table 2.
表２から明らかなように、実施例１３〜２２では、半値幅が０．２〜０．８μｍである第１銀粒子を２０〜５０重量％と、半値幅が２０〜８０μｍであり、なおかつその真球度が１０．０％以下である第２銀粒子を８０〜５０重量％としたので、６００℃３０分の焼成条件においても十分な焼結強度が得られ、９００℃１０分の焼成条件においても膨れの問題も起きない上、線収縮率の増加が６００℃３０分焼成時と比べて４％以内に収まり、広い温度範囲で低収縮であってかつその線収縮率が安定していることが判った。 As apparent from Table 2, in Examples 13 to 22, the first silver particles having a half-value width of 0.2 to 0.8 μm are 20 to 50% by weight, and the half-value width is 20 to 80 μm. Since the second silver particles having a sphericity of 10.0% or less were 80 to 50% by weight, sufficient sintering strength was obtained even under firing conditions of 600 ° C. for 30 minutes, and firing conditions of 900 ° C. for 10 minutes. In addition, the problem of blistering does not occur, and the increase in the linear shrinkage rate is within 4% compared to the case of baking at 600 ° C. for 30 minutes, and the linear shrinkage rate is stable over a wide temperature range with low shrinkage. I found out.
Claims (5)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106180675A (en) * | 2015-05-05 | 2016-12-07 | 光洋应用材料科技股份有限公司 | Silver clay |
| CN107052327A (en) * | 2017-04-06 | 2017-08-18 | 广州市尤特新材料有限公司 | A kind of silver-colored clay silver powder and the silver-colored clay comprising the silver powder |
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2005
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106180675A (en) * | 2015-05-05 | 2016-12-07 | 光洋应用材料科技股份有限公司 | Silver clay |
| CN107052327A (en) * | 2017-04-06 | 2017-08-18 | 广州市尤特新材料有限公司 | A kind of silver-colored clay silver powder and the silver-colored clay comprising the silver powder |
| CN107052327B (en) * | 2017-04-06 | 2019-07-05 | 广州市尤特新材料有限公司 | A kind of silver clay silver powder and the silver-colored clay comprising the silver powder |
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