JP2005290498A - Silver powder for silver clay excellent in low temperature sinterability and silver clay containing the silver powder - Google Patents
Silver powder for silver clay excellent in low temperature sinterability and silver clay containing the silver powder Download PDFInfo
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 180
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 133
- 239000004332 silver Substances 0.000 title claims abstract description 125
- 239000004927 clay Substances 0.000 title claims abstract description 108
- 239000000843 powder Substances 0.000 claims abstract description 83
- 239000011230 binding agent Substances 0.000 claims abstract description 27
- 239000004094 surface-active agent Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011812 mixed powder Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims description 68
- 238000009766 low-temperature sintering Methods 0.000 claims description 26
- 238000005245 sintering Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000005498 polishing Methods 0.000 description 13
- 239000004006 olive oil Substances 0.000 description 9
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- 239000003925 fat Substances 0.000 description 8
- 229920000609 methyl cellulose Polymers 0.000 description 8
- 239000001923 methylcellulose Substances 0.000 description 8
- 235000010981 methylcellulose Nutrition 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
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- 238000012360 testing method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
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- -1 organic acid Esters Chemical class 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
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- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- LTSWUFKUZPPYEG-UHFFFAOYSA-N 1-decoxydecane Chemical compound CCCCCCCCCCOCCCCCCCCCC LTSWUFKUZPPYEG-UHFFFAOYSA-N 0.000 description 1
- VXRUADVCBZMFSV-UHFFFAOYSA-N 2-acetyloxypropane-1,2,3-tricarboxylic acid Chemical compound CC(=O)OC(CC(O)=O)(CC(O)=O)C(O)=O VXRUADVCBZMFSV-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
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- 241000209140 Triticum Species 0.000 description 1
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- 229940028820 didecyl ether Drugs 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 238000009499 grossing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
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- 150000003378 silver Chemical class 0.000 description 1
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Abstract
Description
この発明は、低温燒結性に優れた銀粘土用銀粉末およびそ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 powder for silver clay having excellent low-temperature sintering properties and a silver clay containing the silver powder.
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、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、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。 In recent years, silver clay containing silver powder has been commercially available, and a method for producing silver jewelry or arts and crafts having a predetermined shape by forming the silver clay into a predetermined shape and sintering it has been proposed. ing. According to this method, silver clay can be freely modeled in the same way as ordinary clay work, and the modeled body obtained by modeling is dried and then transported to the place where the sintering furnace is installed. Sintering makes it possible to produce silver jewelry or arts and crafts very easily.
前記従来の銀粘土は、純度：９９．９９質量％以上の高純度からなる平均粒径：３〜２０μｍの銀粉末：５０〜９５質量％、セルローズ系水溶性バインダー：０．８〜８質量％、油脂：０．１〜３質量％、界面活性剤：０．０３〜３質量％を含有し、残りが水からなるものであることは知られている（特許文献１参照）。しかし、この従来の銀粘土は焼結性が劣るのでＡｇの融点以下でかつそれに近い温度で数時間〜十数時間という長時間保持して燒結しないと十分な強度の燒結体が得られない。銀粘土の燒結で使用する電気炉が十分に電気炉内の温度を十分高温に保持できる能力があるものであれば、十分な強度の燒結体を得ることができるが、個人で所有している電気炉は小型であり比較的加熱能力の低いものが多いところから、Ａｇの融点に近い温度に保持することができず、したがって十分な密度を得ることができないことがある。また、温度を十分高温に保持できる電気炉であっても、電気炉内の温度を正確に制御することができず、高温に上げ過ぎてＡｇの融点を越えると、銀粘土焼結体は全部もしくは一部が融け変形する。 The conventional silver clay has a purity of 99.99% by mass or more and an average particle diameter of 3 to 20 μm, a silver powder of 50 to 95% by mass, and a cellulose water-soluble binder: 0.8 to 8% by mass. It is known that fats and oils: 0.1 to 3% by mass, surfactants: 0.03 to 3% by mass, and the remainder is water (see Patent Document 1). However, since this conventional silver clay is inferior in sinterability, a sintered body with sufficient strength cannot be obtained unless it is sintered at a temperature below the melting point of Ag and at a temperature close to it for several hours to several tens of hours. If the electric furnace used for the sintering of silver clay has sufficient ability to keep the temperature inside the electric furnace sufficiently high, a sintered body with sufficient strength can be obtained, but it is owned by an individual. Since many electric furnaces are small and have a relatively low heating capacity, they cannot be maintained at a temperature close to the melting point of Ag, and therefore a sufficient density may not be obtained. Moreover, even in an electric furnace that can keep the temperature sufficiently high, the temperature in the electric furnace cannot be accurately controlled. If the temperature is raised to a high temperature and exceeds the melting point of Ag, the silver clay sintered body is entirely Or part melts and deforms.
これらの問題点を解決するために、平均粒径：２μｍ以下のＡｇ微細粉末：１５〜５０質量％を含有し、残部が平均粒径：２μmを越え１００μｍ以下のＡｇ粉末からなる混合粉末で構成された低温燒結性に優れた銀粘土用銀粉末が提供され、この銀粘土用銀粉末： ５０〜９５質量％に対して、有機系バインダ−：０．８〜８質量％を含有し、さらに必要に応じて界面活性剤：０．０３〜３質量％、油脂：０．１〜３質量％界面活性剤：０．０３〜３質量％を含有し、残りが水からなる組成を有するように混合して得られた銀粘土は、低温燒結性に優れるので、純銀の融点よりも２５０〜４１０℃低い温度（すなわち、５５０〜７１０℃未満の温度）で燒結しても十分な燒結がなされ、所望の引張り強度および密度が得られるという優れた効果を奏するものである（特許文献２参照）。
前述のように、特許文献２に記載の銀粘土は、通常、粘土細工と同じように自由に造形し、得られた造形体を乾燥したのち５５０〜７１０℃未満の低温度で燒結しても十分な燒結がなされ、所望の引張り強度および密度が得られるのであるが、前記従来の銀粘土は、造形したのち焼結すると、表面に微細な凹凸が生成されて表面白色の銀粘土焼結体が得られ、宝飾品または美術工芸品を作製するには得られた銀粘土焼結体の表面を研磨して表面を滑らかにすることにより初めて銀本来の光沢が得られるのである。しかし、この銀粘土焼結体を研磨して表面に銀本来の光沢を発現させるためには多くの労力と時間をかけて研磨する必要があり、特に、表面凹凸模様を有する銀粘土焼結体の表面を研磨して表面凹凸模様の凹部まで銀本来の光沢を発現させるのは難しく、光沢を発現させるために磁気研磨機などを用いる。磁気研磨機を用いる場合、表面の微細な凹凸によって研磨時間が大きく変わる。なお、磁気研磨機とは、非常に小さな研磨用の針を水などの液体中で磁力により撹拌し研磨するものである。したがって、現在は、一層の低温焼結が可能でありかつ銀粘土焼結体表面に容易に金属光沢を発現させることができる銀粘土が求められている。 As described above, the silver clay described in Patent Document 2 is usually freely modeled in the same manner as clay work, and the obtained model is dried and then sintered at a low temperature of 550 to 710 ° C. Sufficient sintering is achieved and desired tensile strength and density can be obtained. However, when the conventional silver clay is shaped and sintered, fine irregularities are generated on the surface, and the silver clay sintered body having a white surface. In order to produce jewelry or arts and crafts, the original gloss of silver can be obtained only by polishing the surface of the obtained silver clay sintered body and smoothing the surface. However, in order to polish this silver clay sintered body and to express the original gloss of silver on the surface, it is necessary to polish it with a lot of labor and time. In particular, the silver clay sintered body having a surface uneven pattern It is difficult to express the original gloss of silver up to the concave portions of the surface uneven pattern by polishing the surface of the surface, and a magnetic polishing machine or the like is used to express the gloss. When a magnetic polishing machine is used, the polishing time varies greatly depending on the fine irregularities on the surface. The magnetic polishing machine is one that polishes a very small polishing needle by stirring magnetically in a liquid such as water. Therefore, at present, there is a demand for silver clay that can be further sintered at a low temperature and can easily exhibit a metallic luster on the surface of the silver clay sintered body.
そこで、本発明者らは、かかる課題を解決すべく研究を行った結果、
（イ）平均粒径：１〜３０ｎｍのＡｇ超微細粉末（好ましくは平均粒径：５〜２０ｎｍのＡｇ超微細粉末）：１〜３０質量％（好ましくは、５〜１５質量％未満）に、残部が平均粒径：０．１〜３０μmのＡｇ粉末（好ましくは平均粒径：０．５〜１０μｍのＡｇ粉末）となるように混合した混合銀粉末を作製し、この混合銀粉末に有機系バインダーおよびその他を添加して作製した銀粘土は、従来の銀粘土よりも一層低い温度（５５０℃未満の温度）で燒結しても十分な燒結がなされ、しかも、この銀粘土の造形体を焼結して得られた銀粘土焼結体の表面は微細な凹凸が少なくかつ緻密であるために、少ない研磨で銀光沢を発生させることができる、
（ロ）前記銀粘土用銀粉末は、Ａｇ超微細粉末と混合するＡｇ粉末の平均粒径によって特性が変化し、一層の低温焼結が必要な場合は配合するＡｇ粉末の平均粒径を小さくし、一方、一層の焼結時の収縮が少ないことを望む場合はＡｇ粉末の平均粒径を大きくすることが好ましく、一層の低温焼結が必要な場合はＡｇ超微細粉末と混合するＡｇ粉末の平均粒径を０．５〜２μｍ未満とし、焼結時の収縮が少ないことを望む場合はＡｇ超微細粉末と混合するＡｇ粉末の平均粒径を２〜１０μｍの範囲内にすることが一層好ましい、という知見を得たのである。
Then, as a result of conducting research to solve such a problem, the present inventors,
(A) Average particle size: 1-30 nm Ag ultrafine powder (preferably average particle size: 5-20 nm Ag ultrafine powder): 1-30% by mass (preferably less than 5-15% by mass) A mixed silver powder was prepared such that the balance was an Ag powder having an average particle size of 0.1 to 30 μm (preferably an Ag powder having an average particle size of 0.5 to 10 μm). The silver clay prepared by adding a binder and others can be sufficiently sintered even when sintered at a temperature lower than that of conventional silver clay (a temperature of less than 550 ° C.). Since the surface of the silver clay sintered body obtained by bonding has few fine irregularities and is dense, silver gloss can be generated with less polishing.
(B) The characteristics of the silver powder for silver clay change depending on the average particle diameter of the Ag powder mixed with the ultrafine Ag powder, and if further low-temperature sintering is required, the average particle diameter of the Ag powder to be blended is reduced. On the other hand, if it is desired that the shrinkage during the sintering of one layer is small, it is preferable to increase the average particle diameter of the Ag powder, and if further low-temperature sintering is required, the Ag powder mixed with the Ag ultrafine powder When it is desired that the average particle size of Ag is less than 0.5 to 2 μm and the shrinkage during sintering is small, the average particle size of the Ag powder mixed with the ultrafine Ag powder should be in the range of 2 to 10 μm. The knowledge that it is preferable was obtained.
この発明は、かかる知見にもとづいてなされたものであって、
（１）平均粒径：１〜３０ｎｍのＡｇ超微細粉末：１〜３０質量％を含有し、残部が平均粒径：０．１〜３０μmのＡｇ粉末からなる混合粉末で構成されている低温燒結性に優れた銀粘土用銀粉末、
（２）平均粒径：１〜３０ｎｍのＡｇ超微細粉末：１〜１５質量％未満を含有し、残部が平均粒径：０．１〜３０μｍのＡｇ粉末からなる混合粉末で構成されている低温燒結性に優れた銀粘土用銀粉末、
（３）平均粒径：１〜３０ｎｍのＡｇ超微細粉末：１〜１５質量％未満を含有し、残部が平均粒径：０．５〜１０μｍのＡｇ粉末からなる混合粉末で構成されたことを特徴とする低温燒結性に優れた銀粘土用銀粉末。
（４）平均粒径：１〜３０ｎｍのＡｇ超微細粉末：１〜１５質量％未満を含有し、残部が平均粒径：０．５〜２μｍ未満のＡｇ粉末からなる混合粉末で構成されている低温燒結性に優れた銀粘土用銀粉末、
（５）平均粒径：１〜３０ｎｍのＡｇ超微細粉末：１〜１５質量％未満を含有し、残部が平均粒径：２〜１０μｍのＡｇ粉末からなる混合粉末で構成されている低温燒結性に優れた銀粘土用銀粉末、に特徴を有するものである。
This invention was made based on such knowledge,
(1) Average particle size: 1-30 nm Ag ultrafine powder: 1-30% by mass Low temperature sintering composed of mixed powder consisting of Ag powder with average particle size: 0.1-30 μm Excellent silver powder for silver clay,
(2) Average particle size: 1-30 nm Ag ultrafine powder: 1 to less than 15% by mass, the balance being composed of a mixed powder consisting of Ag powder with an average particle size of 0.1 to 30 μm Silver powder for silver clay with excellent sintering properties,
(3) Average particle size: Ag ultrafine powder of 1 to 30 nm: containing less than 1 to 15% by mass, with the balance being composed of mixed powder consisting of Ag powder of average particle size: 0.5 to 10 μm Silver powder for silver clay with excellent low-temperature sintering characteristics.
(4) Average particle size: 1-30 nm Ag ultrafine powder: 1 to less than 15% by mass, with the balance being composed of a mixed powder consisting of Ag powder with an average particle size of less than 0.5 to 2 μm Silver powder for silver clay with excellent low-temperature sintering properties,
(5) Average particle size: Ag ultrafine powder of 1 to 30 nm: low temperature sintering property comprising 1 to less than 15% by mass, and the balance being composed of mixed powder consisting of Ag powder of average particle size: 2 to 10 μm It is characterized by excellent silver powder for silver clay.
この発明の銀粘土は、前記（１）〜（５）のいずれかに記載の銀粘土用銀粉末に有機系バインダーまたは有機系バインダーに油脂、界面活性剤などを添加して作られた粘土であり、したがって、この発明は、
（６）前記（１）〜（５）のいずれかに記載の銀粘土用銀粉末：５０〜９５質量％、有機系バインダ−：０．８〜８質量％を含有し、残りが水からなる低温燒結性に優れた銀粘土、
（７）前記（１）〜（５）のいずれかに記載の銀粘土用銀粉末：５０〜９５質量％、有機系バインダー：０．８〜８質量％、界面活性剤：０．０３〜３質量％を含有し、残りが水からなる低温燒結性に優れた銀粘土、
（８）（１）〜（５）のいずれかに記載の銀粘土用銀粉末：５０〜９５質量％、有機系バインダー：０．８〜８質量％、油脂：０．１〜３質量％を含有し、残りが水からなる低温燒結性に優れた銀粘土、
（９）（１）〜（５）のいずれかに記載の銀粘土用銀粉末：５０〜９５質量％、有機系バインダー：０．８〜８質量％、油脂：０．１〜３質量％、界面活性剤：０．０３〜３質量％を含有し、残りが水からなる低温燒結性に優れた銀粘土、に特徴を有するものである。
The silver clay of the present invention is a clay made by adding an organic binder to the silver clay silver powder according to any one of the above (1) to (5), or an oil or fat, a surfactant or the like to the organic binder. Therefore, this invention is
(6) Silver powder for silver clay according to any one of (1) to (5): 50 to 95% by mass, organic binder: 0.8 to 8% by mass, with the remainder being water. Silver clay with excellent low-temperature sintering properties,
(7) Silver powder for silver clay according to any one of (1) to (5): 50 to 95% by mass, organic binder: 0.8 to 8% by mass, surfactant: 0.03 to 3 Silver clay with excellent low-temperature sintering properties, containing mass% and the balance being water
(8) Silver powder for silver clay according to any one of (1) to (5): 50 to 95% by mass, organic binder: 0.8 to 8% by mass, fat / oil: 0.1 to 3% by mass Contains silver clay with excellent low-temperature sintering properties, the balance being water
(9) Silver powder for silver clay according to any one of (1) to (5): 50 to 95% by mass, organic binder: 0.8 to 8% by mass, fat / oil: 0.1 to 3% by mass, Surfactant: It is characterized by silver clay containing 0.03 to 3% by mass and the rest being water and having excellent low-temperature sintering properties.
この発明の銀粘土は、従来銀粘土に比べて一層低温度で燒結することができ、さらに銀粘土を燒結して得られた銀粘土焼結体の表面に銀本来の光沢を発現させるための研磨作業を軽減することができ、より多くの人が銀粘土を使用して簡単に美術工芸品や宝飾品をつくることができるなど優れた効果を奏するものである。 The silver clay of the present invention can be sintered at a temperature lower than that of conventional silver clay, and further to express the original gloss of silver on the surface of the sintered silver clay obtained by sintering the silver clay. The polishing work can be reduced, and more people can easily produce arts and crafts and jewelry using silver clay.
この発明の銀粘土用銀粉末に含まれるＡｇ超微細粉末およびＡｇ粉末の限定理由を説明する。
Ａｇ超微細粉末：
この発明の銀粘土用銀粉末に平均粒径：１〜３０ｎｍのＡｇ超微細粉末を添加することにより、低温焼結性に一層寄与し、さらに得られた銀粘土焼結体の表面が緻密となり、研磨による光沢の発現が容易となる。しかし、添加するＡｇ超微細粉末の平均粒径が１ｎｍ以下であると粒子同士の凝集が顕著となり、０．１〜３０μｍのＡｇ粉末と均一に混ぜることが困難となり、低温焼結性の効果が小さくなるので好ましくなく、一方、平均粒径が３０ｎｍを越えると低温焼結性の効果が少なく、研磨による光沢の発現には従来品と同等の労力を有するので３０ｎｍを越える超微粉末を用いても効果がないのでことによるものである。かかる平均粒径：１〜３０ｎｍのＡｇ超微細粉末は１質量％以上入っていれば十分に低温焼結に寄与することができるが、３０質量％を越えて含有すると、銀粘土用銀粉末の表面積が大きくなり過ぎてバインダー量が大量に必要となり、収縮率が大きくなり過ぎて予想した寸法および形状の大きさからかけ離れた寸法および形状を有する銀粘土焼結体が得られるので好ましくなく、また収縮率を小さくすべくバインダー量を少なくすると、粘土としての造形性が低下し、パサパサした粉末になってしまうので好ましくない。したがって、この発明の銀粘土用銀粉末に含まれるＡｇ超微細粉末は、平均粒径：１〜３０ｎｍ、１〜３０質量％に定めた。この発明の銀粘土用銀粉末に含まれるＡｇ超微細粉末の一層好ましい範囲は、平均粒径：５〜２０ｎｍ、５〜１５質量％未満である。
The reasons for limitation of the ultrafine Ag powder and Ag powder contained in the silver clay silver powder of the present invention will be described.
Ag ultrafine powder:
By adding an Ag ultrafine powder having an average particle size of 1 to 30 nm to the silver powder for silver clay of the present invention, the surface of the obtained silver clay sintered body becomes denser, further contributing to low-temperature sinterability. The glossiness by polishing becomes easy. However, if the average particle diameter of the added Ag ultrafine powder is 1 nm or less, the aggregation of the particles becomes remarkable and it becomes difficult to mix uniformly with the Ag powder of 0.1 to 30 μm. On the other hand, if the average particle size exceeds 30 nm, the effect of low-temperature sinterability is small, and the gloss development by polishing has the same effort as conventional products, so use ultrafine powder exceeding 30 nm. This is because there is no effect. When the Ag ultrafine powder having an average particle size of 1 to 30 nm is contained in an amount of 1% by mass or more, it can sufficiently contribute to low-temperature sintering. Since the surface area becomes too large, a large amount of binder is required, the shrinkage rate becomes too large, and a silver clay sintered body having a size and shape far from the expected size and shape can be obtained. If the amount of the binder is reduced in order to reduce the shrinkage rate, the formability as clay is lowered, and the powder becomes crusty. Accordingly, the Ag ultrafine powder contained in the silver clay silver powder of the present invention was determined to have an average particle size of 1 to 30 nm and 1 to 30% by mass. The more preferable range of the Ag ultrafine powder contained in the silver powder for silver clay of the present invention is an average particle size of 5 to 20 nm and less than 5 to 15% by mass.
Ａｇ粉末：
この発明の銀粘土用銀粉末に含まれる残りのＡｇ粉末を平均粒径：０．１〜３０μmのＡｇ粉末としたのは、この平均粒径を有するＡｇ粉末は通常市販されているＡｇ粉末であり、この市販のＡｇ粉末の内でも平均粒径：０．１〜２μｍ未満のＡｇ粉末を使用すると一層低温度で焼結することができるようになり、一方、平均粒径：２〜３０μｍのＡｇ粉末を使用すると、焼結体の収縮率を減少させることができる。Ａｇ粉末が０．１μｍ以下であると造形性を得るためのバインダーを多く必要とするため収縮も大きく、得られる低温焼結性の効果に比べて製造コストが高く不適である。３０μｍを越えると焼結性に劣り、５５０℃以下の温度の焼結で十分な強度が得られないため不適である。
Ag powder:
The remaining Ag powder contained in the silver clay silver powder of the present invention was made into an Ag powder having an average particle size of 0.1 to 30 μm because the Ag powder having this average particle size is a commercially available Ag powder. Yes, among these commercially available Ag powders, if an Ag powder having an average particle size of less than 0.1 to 2 μm is used, it becomes possible to sinter at a lower temperature, while an average particle size of 2 to 30 μm. When Ag powder is used, the shrinkage rate of the sintered body can be reduced. When the Ag powder is 0.1 μm or less, a large amount of binder is required for obtaining the moldability, and thus the shrinkage is large, which is unsuitable because the production cost is high as compared with the obtained low-temperature sinterability effect. If it exceeds 30 μm, the sinterability is inferior, and it is not suitable because sufficient strength cannot be obtained by sintering at a temperature of 550 ° C. or lower.
この発明の銀粘土用銀粉末は平均粒径：１〜３０ｎｍのＡｇ超微細粉末（好ましくは平均粒径：５〜２０ｎｍのＡｇ超微細粉末）のＡｇ超微細粉末と平均粒径：０．１〜３０μｍ（好ましくは０．５〜１０μｍ）のＡｇ粉末とを混合した混合銀粉末で構成されているから、この発明の銀粘土用銀粉末の粒度分布曲線は平均粒径：１〜３０ｎｍ（好ましくは５〜２０ｎｍ）の範囲内にピークを少なくとも一つ持ち、さらに平均粒径：０．１〜３０μｍ（好ましくは０．５〜１０μｍ）の範囲内にピークを少なくとも一つ持つ。 The silver powder for silver clay of the present invention has an Ag ultrafine powder having an average particle diameter of 1 to 30 nm (preferably an Ag ultrafine powder having an average particle diameter of 5 to 20 nm) and an average particle diameter of 0.1. Since it is composed of mixed silver powder mixed with Ag powder of ˜30 μm (preferably 0.5-10 μm), the particle size distribution curve of the silver powder for silver clay of the present invention has an average particle size of 1-30 nm (preferably Has at least one peak in the range of 5 to 20 nm), and further has at least one peak in the range of average particle size: 0.1 to 30 μm (preferably 0.5 to 10 μm).
この発明の低温燒結性に優れた銀粘土に含まれる前記（１）〜（５）記載の銀粘土用銀粉末の量を５０〜９５質量％に限定したのは、５０質量％未満ではＡｇ粉末同士の接触妨げられるため、焼結開始に時間がかかる上にＡｇ粉末の接触を妨げていた空間を埋めるため大きな収縮が起き、多くの場合変形や歪みが発生し、また得られた焼成体の金属光沢を示すに十分な効果が得られず、一方、９５質量％を越えて含有すると粘土としての伸びおよび強度が低下するようになるので好ましくないからである。銀粘土用銀粉末の含有量の一層好ましい範囲は７０〜９５質量％である。 The amount of the silver powder for silver clay described in the above (1) to (5) contained in the silver clay excellent in low temperature sintering of the present invention is limited to 50 to 95% by mass. Since the contact between each other is hindered, it takes a long time to start sintering, and a large shrinkage occurs in order to fill the space that prevented the contact of the Ag powder. In many cases, deformation and distortion occur. This is because a sufficient effect for exhibiting the metallic luster cannot be obtained, and on the other hand, if the content exceeds 95% by mass, the elongation and strength as clay are lowered, which is not preferable. A more preferable range of the content of the silver powder for silver clay is 70 to 95% by mass.
この発明の低温燒結性に優れた銀粘土に含まれる有機系バインダーは、セルロース系バインダー、ポリビニール系バインダー、アクリル系バインダー、ワックス系バインダー、樹脂系バインダー、澱粉、ゼラチン、小麦粉などいかなるバインダーを使用してもよいが、セルロース系バインダー、特に水溶性セルロースが最も好ましい。これらバインダーは、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するが、その添加量は０．８質量％未満では効果がなく、一方、８質量％を越えて含有すると、得られた造形体に微細なひび割れが発生し、光沢も減少するので好ましくない。したがって、この発明の低温燒結性に優れた銀粘土に含まれるバインダーは、０．８〜８質量％に定めた。バインダー含有量の一層好ましい範囲は０．８〜５質量％である。 The organic binder contained in the silver clay excellent in low temperature sintering of the present invention uses any binder such as cellulose binder, polyvinyl binder, acrylic binder, wax binder, resin binder, starch, gelatin, wheat flour, etc. However, cellulosic binders, particularly water-soluble cellulose, are most preferred. These binders are added in order to quickly gel when heated to facilitate the shape retention of the shaped body. However, the amount added is less than 0.8% by mass, while there is no effect, while the content exceeds 8% by mass. Then, fine cracks are generated in the obtained shaped body, and gloss is also reduced, which is not preferable. Therefore, the binder contained in the silver clay having excellent low-temperature sintering properties of the present invention is set to 0.8 to 8% by mass. A more preferable range of the binder content is 0.8 to 5% by mass.
前記界面活性剤は必要に応じて添加し、添加する場合の添加量は０．０３〜３質量％が好ましい。また、添加する界面活性剤の種類は特に限定されるものではなく、通常の界面活性剤を使用することができる。 The surfactant is added as necessary, and the amount added is preferably 0.03 to 3% by mass. Moreover, the kind of surfactant to add is not specifically limited, A normal surfactant can be used.
前記油脂も必要に応じて添加し、添加する場合の添加量は０．１〜３質量％が好ましい。添加する油脂は有機酸（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）などがある。 The fats and oils are also added as necessary, and the amount added is preferably 0.1 to 3% by mass. Fats and oils to be added are 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 Esters (organic acid esters having methyl, ethyl, propyl, butyl, octyl, hexyl, dimethyl, diethyl, isopropyl, and isobutyl groups), higher alcohols (octanol, nonanol, decanol), polyvalent Examples include alcohol (glycerin, arabit, sorbitan), ether (dioctyl ether, didecyl ether) and the like.
平均粒径：５μｍのアトマイズＡｇ粉末（以下、アトマイズＡｇ粉末という）を用意し、さらに、有機系バインダーとしてメチルセルローズ、界面活性剤、油脂としてオリーブ油および水を用意した。 Atomized Ag powder (hereinafter referred to as atomized Ag powder) having an average particle size of 5 μm was prepared, and methyl cellulose as a binder, surfactant, and olive oil and water as fats and oils were prepared.
表１に示される平均粒径を有するＡｇ超微細粉末を含むコロイドに表１に示される平均粒径：５．０μｍのアトマイズＡｇ粉末を混合、撹拌し、得られた混合体にさらに分散剤除去剤（アセトン、ヘキサン）を投入して固液分離し、得られた混合粉末を回収することにより表１に示される配合組成を有する銀粘土用銀粉末を作製した。
このようにして得られた銀粘土用銀粉末に対して、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：残部となるように配合し混練することにより本発明銀粘土１〜７および比較銀粘土１〜４を作製した。
The colloid containing Ag ultrafine powder having the average particle size shown in Table 1 is mixed with the atomized Ag powder having an average particle size of 5.0 μm shown in Table 1 and stirred, and the resulting mixture is further removed with a dispersant. An agent (acetone, hexane) was added to perform solid-liquid separation, and the obtained mixed powder was recovered to prepare a silver clay silver powder having the composition shown in Table 1.
Methyl cellulose, surfactant, olive oil and water are added to the silver clay powder thus obtained. Silver powder for silver clay: 85% by mass, methyl cellulose: 4.5% by mass, interface The present invention silver clays 1 to 7 and comparative silver clays 1 to 4 were prepared by blending and kneading so that the activator: 1.0% by mass, olive oil: 0.3% by mass, and water: the balance.
比較のために、平均粒径：１．０μｍのアトマイズＡｇ粉末を用意し、この平均粒径：１．０μｍのアトマイズＡｇ粉末：３０質量％、残部：平均粒径：５．０μｍのアトマイズＡｇ粉末となるように配合し混合して従来の銀粘土用銀粉末を作製した。
この従来の銀粘土用銀粉末に対して、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、従来の銀粘土用銀粉末：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：残部となる配合し混練することにより従来銀粘土を作製した。
For comparison, an atomized Ag powder having an average particle size of 1.0 μm was prepared. This atomized Ag powder having an average particle size of 1.0 μm: 30% by mass, and the balance: an atomized Ag powder having an average particle size of 5.0 μm. A conventional silver clay powder was prepared by mixing and mixing.
Methyl cellulose, surfactant, olive oil and water are added to the conventional silver clay silver powder, and the conventional silver clay silver powder: 85% by mass, methyl cellulose: 4.5% by mass, surfactant. : 1.0% by mass, olive oil: 0.3% by mass, and water: the balance were mixed and kneaded to prepare a conventional silver clay.
これら本発明銀粘土１〜７、比較銀粘土１〜４および従来銀粘土を造形し、得られた造形体を４００℃の低温度で１０分間燒結することにより縦：３ｍｍ、横：４ｍｍ、長さ：６５ｍｍの寸法を有する試験片燒結体を作製し、得られた試験片燒結体の引張り強さおよびビッカース硬さを測定し、その測定結果を表１に示した。
さらに試験片焼結体を磁気研磨器にかけ、試験片焼結体の表面を研磨して表面に形成された白い層を除去し、目視による同一光度を発現するまでの時間を測定し、その結果を表１に示した。
By forming these silver clays 1 to 7, comparative silver clays 1 to 4 and conventional silver clay of the present invention and sintering the obtained shaped body at a low temperature of 400 ° C. for 10 minutes, the length: 3 mm, the width: 4 mm, and the length The test piece sintered body having a dimension of 65 mm was prepared, the tensile strength and Vickers hardness of the obtained test piece sintered body were measured, and the measurement results are shown in Table 1.
Furthermore, the test piece sintered body was put on a magnetic polishing machine, the surface of the test piece sintered body was polished to remove the white layer formed on the surface, and the time until the same luminous intensity was visually observed was measured. Is shown in Table 1.
表１から明らかなように、（Ａ）平均粒径：５．０μｍを有するアトマイズＡｇ粉末に対して平均粒径：１〜３０ｎｍのＡｇ超微細粉末を１〜３０質量％配合した銀粘土用銀粉末を含む本発明銀粘土１〜７で作製した試験片焼結体は、平均粒径：１μｍの球状のＡｇ微細粉末を３０質量％配合した銀粘土用銀粉末を含む従来銀粘土で作製した試験片焼結体に比べて引張強さおよびビッカース硬さが格段に優れているところから、この発明の銀粘土は、従来の焼結温度よりも一層低い焼結温度で焼結でき、さらに本発明銀粘土１〜７で作製した試験片焼結体は従来で作製した試験片焼結体に比べて短時間の磁気研磨で銀本来の光沢を発現させることができる、（Ｂ）しかし、この発明の条件から外れた比較銀粘土１〜４で作製した試験片焼結体は好ましくない特性が現れる、ことが分かる。 As is clear from Table 1, (A) silver clay silver, in which 1 to 30% by mass of an Ag ultrafine powder having an average particle diameter of 1 to 30 nm is blended with an atomized Ag powder having an average particle diameter of 5.0 μm. Test specimen sintered bodies made of the present invention silver clays 1 to 7 containing powder were made of conventional silver clay containing silver powder for silver clay containing 30% by mass of spherical Ag fine powder having an average particle diameter of 1 μm. Since the tensile strength and Vickers hardness are remarkably superior compared to the specimen sintered body, the silver clay of the present invention can be sintered at a sintering temperature lower than the conventional sintering temperature. Invented silver clay 1-7 specimen sintered bodies can exhibit the original luster of silver by magnetic polishing in a short time compared to the conventionally produced specimen sintered bodies, (B) A specimen sintered body made of comparative silver clays 1 to 4 deviating from the conditions of the invention was It can be seen that undesirable characteristics appear.
実施例１と同様にして平均粒径：５．０μｍを有するアトマイズＡｇ粉末に対し、平均粒径：１０ｎｍを有するＡｇ超微細粉末を１０質量％配合し混合してなる銀粘土用銀粉末を作製し、得られた銀粘土用銀粉末に対して、メチルセルローズ、界面活性剤、オリーブ油および水を表２に示される割合で添加し、本発明銀粘土８〜１３を作製した。 In the same manner as in Example 1, a silver powder for silver clay was prepared by mixing and mixing 10% by mass of an Ag ultrafine powder having an average particle size: 10 nm with respect to an atomized Ag powder having an average particle size: 5.0 μm. Then, methyl cellulose, surfactant, olive oil and water were added to the obtained silver powder for silver clay in the proportions shown in Table 2 to prepare silver clays 8 to 13 of the present invention.
これら本発明銀粘土８〜１３を造形し、４５０℃の温度で３０分間燒結することにより縦：３ｍｍ、横：４ｍｍ、長さ：６５ｍｍの寸法を有する試験片燒結体を作製し、得られた試験片燒結体の引張り強さ、ビッカース硬さおよび目視による同一光度を発現するまでの時間を測定し、その結果を表２に示した。 These silver clays 8 to 13 of the present invention were formed and sintered at a temperature of 450 ° C. for 30 minutes to produce a test piece sintered body having dimensions of 3 mm in length, 4 mm in width, and 65 mm in length. The tensile strength, the Vickers hardness, and the time until visual appearance of the same luminous intensity were measured, and the results are shown in Table 2.
表２に示される結果から、界面活性剤、オリーブ油のうち何れかを含まない銀粘土であっても、十分な低温燒結性が得られることが分かる。 From the results shown in Table 2, it can be seen that sufficient low-temperature sintering properties can be obtained even with silver clay that does not contain any of surfactant and olive oil.
表３に示される平均粒径の異なるアトマイズＡｇ粉末を用意し、これらにアトマイズＡｇ粉末対して実施例１で用意した平均粒径：１０ｎｍを有するＡｇ超微細粉末を１０質量％となるように配合し混合してなる銀粘土用銀粉末を作製し、得られた銀粘土用銀粉末に対して、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：残部となるように配合し混練することにより本発明銀粘土１４〜１７および比較銀粘土５〜６を作製した。 Atomized Ag powders having different average particle diameters shown in Table 3 were prepared, and the Ag ultrafine powder having an average particle diameter of 10 nm prepared in Example 1 for the atomized Ag powder was blended so as to be 10% by mass. Then, a silver powder for silver clay is prepared, and methyl cellulose, surfactant, olive oil and water are added to the obtained silver powder for silver clay, and silver powder for silver clay: 85% by mass, Methyl cellulose: 4.5% by mass, surfactant: 1.0% by mass, olive oil: 0.3% by mass, and water: the remainder is blended and kneaded so that the present silver clay 14-17 and comparative silver Clays 5-6 were prepared.
これら本発明銀粘土１４〜１７および比較銀粘土５〜６を造形し、４５０℃の温度で３０分間燒結することにより縦：３ｍｍ、横：４ｍｍ、長さ：６５ｍｍの寸法を有する試験片燒結体を作製し、得られた試験片燒結体の引張り強さ、ビッカース硬さおよび目視による同一光度を発現するまでの時間を測定し、その結果を表３に示した。 These silver clays 14 to 17 and comparative silver clays 5 to 6 of the present invention are formed and sintered at a temperature of 450 ° C. for 30 minutes, whereby a test piece sintered body having dimensions of 3 mm in length, 4 mm in width, and 65 mm in length. Was measured, and the tensile strength, Vickers hardness, and time until visual appearance of the same luminous intensity were measured. The results are shown in Table 3.
表３に示される結果から、平均粒径：０．１〜３０μｍを有するアトマイズＡｇ粉末に対して平均粒径：１０ｎｍのＡｇ超微細粉末を１０質量％配合した銀粘土用銀粉末を含む本発明銀粘土１４〜１７で作製した試験片焼結体は、平均粒径：０．０５μｍのアトマイズＡｇ粉末を配合した銀粘土用銀粉末を含む比較銀粘土５および平均粒径：３５μｍのアトマイズＡｇ粉末を配合した銀粘土用銀粉末を含む比較銀粘土６で作製した試験片焼結体に比べて優れた特性を示すところから、アトマイズＡｇ粉末の平均粒径は０．１〜３０μｍの範囲内にあることが好ましいことが分かる。
From the results shown in Table 3, the present invention comprises silver powder for silver clay in which 10% by mass of Ag ultrafine powder having an average particle size of 10 nm is mixed with an atomized Ag powder having an average particle size of 0.1 to 30 μm. The sintered specimens made of silver clays 14 to 17 are comparative silver clay 5 containing silver powder for silver clay in which an atomized Ag powder having an average particle diameter of 0.05 μm is blended and an atomized Ag powder having an average particle diameter of 35 μm. The average particle size of the atomized Ag powder is in the range of 0.1 to 30 μm because it shows superior characteristics compared to the sintered compact of the test piece made of comparative silver clay 6 containing silver powder for silver clay containing It can be seen that it is preferable.
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| JP2007154235A (en) * | 2005-12-02 | 2007-06-21 | Mitsubishi Materials Corp | Unbaked compact for ring |
| 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 |
| JP2018111885A (en) * | 2005-08-03 | 2018-07-19 | ユニバシダデ デ サンチャゴ デ コンポステラ | Atomic quantum clusters, production method thereof and methods of use thereof |
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2004
- 2004-04-01 JP JP2004109149A patent/JP2005290498A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2018111885A (en) * | 2005-08-03 | 2018-07-19 | ユニバシダデ デ サンチャゴ デ コンポステラ | Atomic quantum clusters, production method thereof and methods of use thereof |
| JP7190818B2 (en) | 2005-08-03 | 2022-12-16 | ユニバシダデ デ サンチャゴ デ コンポステラ | Atomic Quantum Clusters, Methods of Making Them and Methods of Using Them |
| JP2007154235A (en) * | 2005-12-02 | 2007-06-21 | Mitsubishi Materials Corp | Unbaked compact for ring |
| JP4720465B2 (en) * | 2005-12-02 | 2011-07-13 | 三菱マテリアル株式会社 | Unfired ring compact |
| 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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