EP2979782B1 - Tonzusammensetzung für einen edelmetall-sinterpressling - Google Patents
Tonzusammensetzung für einen edelmetall-sinterpressling Download PDFInfo
- Publication number
- EP2979782B1 EP2979782B1 EP14774733.1A EP14774733A EP2979782B1 EP 2979782 B1 EP2979782 B1 EP 2979782B1 EP 14774733 A EP14774733 A EP 14774733A EP 2979782 B1 EP2979782 B1 EP 2979782B1
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- EP
- European Patent Office
- Prior art keywords
- clay
- precious metal
- composition
- powder
- propylene glycol
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0466—Alloys based on noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
Definitions
- the present invention relates to a clay-like composition for forming a sintered precious metal body.
- precious metal clays containing precious metal powders such as silver or gold have become commercially available, and methods have been proposed for producing precious metal jewelry and fine arts and crafts having any desired shape by making these precious metal clays into a desired arbitrary shape and then performing firing (for example, see Patent Documents 1 to 3).
- precious metal clays can be used to freely shaped forms in the same manner as typical clay work. Further, by drying the shaped body obtained by shaping the precious metal clay, and then firing the clay in a heating furnace, precious metal jewelry and fine arts and crafts and the like can be produced extremely easily.
- Patent Document 4 describes a thick film water based conductive composition comprising, based on total composition: (a) 5-40 wt.% first aqueous dispersion of polyhydroxyether polymer grafted with at least one acrylic or methacrylic monomer wherein the dispersion is 25-40 wt.% grafted polymer solids; (b) 20-80 wt.% finely divided metallic electrically conductive particles selected from the group consisting of silver, copper, nickel, silver coated copper, silver coated nickel, carbon, graphite and mixtures thereof; (c) 0-20 wt.% second aqueous dispersion of an acrylic or polyurethane polymer wherein the dispersion is 25-40 wt.% polymer solids; (d) 0-5 wt.% water soluble polymer; and wherein all of (a), (b), (c) and (d) are dispersed in water and about 1-8 wt.% co-solvent.
- Patent Document 5 describes a method for producing a metal or alloy article which comprises mixing and kneading a metal or alloy powder with an organic binder, injection molding said kneaded mixture into a shape similar to that of the desired final product, removing the organic binder, and sintering the injected product to give a metal or alloy article with high density
- the organic binder comprising (a) as an adhesive agent a kind of methylcellulose having three OH groups in glucose residue contained in the cellulose, about 2 of said three OH groups being substituted with methoxy (-OCH 3 ) groups in a weight range of 27.5 to 31.5%, in an amount of 0.5 to 3.0% by weight, (b) as a plasticizer at least one of esters of polyhydric alcohol ether compounds, propylene glycol and polyethylene oxide in an amount of 0.5 to 3.0% by weight, (c) as a lubricant or a mold release agent at least one of a wax emulsion, a stearic acid emulsion
- shaping is performed using, for example, a silver clay containing a silver powder of pure Ag.
- This type of shaping is mainly performed by hand, but as time elapses, the clay can sometimes start to dry, making processes such as bending more difficult.
- Ever increasing diversity in design and personal preferences has resulted in more complex shapes for the sintered precious metal bodies, meaning the time required for shaping these bodies has tended to increase.
- conventional materials if an attempt is made to bend a dried silver clay, then cracks appear in the surface of the clay, and further bending can result in breakage.
- rings or the like are made, the shaping must be completed within a limited time period, meaning there is a limit to the design features that are possible.
- the present invention has been developed in light of these circumstances, and was completed as a result of intensive research aimed at achieving the object described below.
- the present invention has an object of providing a clay-like composition for forming a sintered precious metal body which exhibits excellent flexibility and bendability during shaping of the precious metal clay, even after the precious metal clay has dried, and therefore enables the shaping time for bending and the like to be lengthened.
- the inventors of the present invention tested the addition of all manner of organic substances to precious metal clays (clay-like compositions for forming sintered precious metal bodies), and conducted intensive research relating to the types of additive components and the optimum amounts for those components. As a result, they discovered that by adding a prescribed amount of propylene glycol to a precious metal clay, satisfactory flexibility and bendability could be achieved during shaping of the precious metal clay, even after the precious metal clay had dried.
- a clay-like composition for forming a sintered precious metal body (hereafter also referred to as a "precious metal clay”) according to the present invention is obtained by adding at least an organic binder such as methyl cellulose and water to a powder containing gold, silver, or a silver alloy or the like as a precious metal, and also adding at least a prescribed amount of propylene glycol as an additive component.
- the propylene glycol mentioned above is a widely-used solvent that is also used for other applications such as addition to solutions to alter the viscosity, and addition to foodstuffs or cosmetics to impart moisture retention properties.
- the effect that the addition of propylene glycol to a precious metal clay would have upon the drying of the clay during shaping was completely unknown.
- the inventors of the present invention evaluated the addition of various types and amounts of additives to clay-like compositions for forming sintered precious metal bodies, and also evaluated the characteristics of the clay-like compositions from the viewpoints of the flexibility, bendability and formability of the compositions after drying during shaping.
- a clay-like composition for forming a sintered precious metal body the clay-like composition containing at least a precious metal powder and/or a precious metal alloy powder at an amount of 50 to 95 mass%; an organic binder, an organic additive including propylene glycol, glycerol, and polyethylene glycol; and water, wherein the combined amount of the propylene glycol, the glycerol and the polyethylene glycol is 0.1 to 3.0 mass %.
- the clay-like composition for forming a sintered precious metal body according to the present invention contains at least a precious metal powder and/or a precious metal alloy powder, an organic binder, an organic additive and water, the organic additive including propylene glycol, glycerol, and polyethylene glycol, wherein the combined amount of the propylene glycol, the glycerol and the polyethylene glycol is 0.1 to 3.0mass %, and therefore the clay-like composition exhibits excellent flexibility and bendability during shaping of the precious metal clay, even after the precious metal clay has dried.
- a clay-like composition for forming a sintered precious metal body can be provided which has minimal time restrictions during working of the composition by bending or the like.
- the clay-like composition according to this embodiment contains at least a precious metal powder and/or a precious metal alloy powder, an organic binder, an organic additive and water, and in particular, contains propylene glycol as the organic additive.
- the clay-like composition also includes glycerol and polyethylene glycol as other organic additives, and the combined amount of the propylene glycol, the glycerol and the polyethylene glycol is from 0.1 to 3.0 mass %.
- the organic additive Besides the organic binder, the organic additive and water, a surface active agent, a fatty substance, and olive oil may also be added if required.
- precious metal powder and/or precious metal alloy powder used in the present embodiment gold powder, silver powder, copper powder, platinum powder, or powders of alloys of these metals can be used. Further, a mixed powder of silver powder and copper powder may also be used. In terms of silver alloy powders, a silver-copper alloy can be used particularly favorably.
- One or more of these precious metal powders and/or precious metal alloy powders function as the main component that constitutes the clay-like composition for forming a sintered precious metal body. In order to obtain a more practical clay-like composition, the amount of the powder is at least 50mass % but not more than 95mass %.
- the amount of the precious metal powder and/or precious metal alloy powder is preferably from 75 to 93mass %.
- the organic binder used in the present embodiment may be formed from one material, or a combination of two or more materials, selected from among cellulose-based binders, polyvinyl-based binders, acrylic-based binders, wax-based binders, resin-based binders, starch, gelatin and flour. Further, among the above, the organic binder is preferably formed from a cellulose-based binder, and most formed from preferably a water-soluble cellulose such as methyl cellulose. Although there are no particular limitations on the amount of the organic binder in the clay-like composition, the amount is typically from 5 to 50mass %, and preferably from 7 to 25mass %.
- Propylene glycol is included in the organic additive used in the present embodiment.
- the amount of this organic additive is less than 0.1mass %, then the flexibility tends to deteriorate when the clay-like composition dries, and the embodiment is unable to satisfactorily exhibit the anticipated effects.
- the amount of the organic additive exceeds 3.0mass %, then the formability of the clay-like composition deteriorates, and shaping the composition becomes difficult.
- the flexibility of the clay-like composition after drying can be further improved.
- the combined mass of the propylene glycol, the glycerol and the polyethylene glycol is adjusted to satisfy the range from 0.1 to 3.0mass %.
- Glycerol and polyethylene glycol are liquid substances that have both hydrophilic and lipophilic properties, and it is known that including these substances in a clay-like composition imparts viscosity to the composition.
- glycerol and a polyethylene glycol are added to the clay-like composition on the basis of the novel finding by the inventors of the present invention that by adding these substances to the clay-like composition together with propylene glycol, the effect of the invention in preventing deterioration in the flexibility of the clay-like composition upon drying can be further strengthened compared with the case where the propylene glycol is added alone.
- the amount of the organic additive in the clay-like composition is more preferably from 0.5 to 2.0mass %.
- At least one of a fatty substance, olive oil, and a surface active agent may also be added to the clay-like composition for forming a sintered precious metal body according to the present embodiment.
- the amount of oil or fat in the clay-like composition is typically from 0.01 to 0.08mass %, and preferably from 0.03 to 0.06mass %.
- the amount of olive oil in the clay-like composition is typically from 0.001 to 0.05mass %, and preferably from 0.01 to 0.03mass %.
- the amount of the surface active agent in the clay-like composition is typically from 0.001 to 0.05mass %, and preferably from 0.01 to 0.03mass %.
- oil or fat examples include organic acids (such as oleic acid, stearic acid, phthalic acid, palmitic acid, sebacic acid, acetylcitric acid, hydroxybenzoic acid, lauric acid, myristic acid, caproic acid, enanthic acid, butyric acid and capric acid), organic esters (such as organic acid esters having a methyl group, ethyl group, propyl group, butyl group, octyl group, hexyl group, dimethyl group, diethyl group, isopropyl group or isobutyl group), higher alcohols (such as octanol, nonanol and decanol), polyhydric alcohols (such as glycerol, arabitol and sorbitan), and ethers (such as dioctyl ether and didecyl ether).
- organic acids such as oleic acid, stearic acid, phthalic acid, palm
- the aforementioned surface active agent By adding and mixing the aforementioned surface active agent into the clay-like composition, the solid matter generated by the reaction between the binder and the water can be converted to powder form, and the mixability of the precious metal powder and the binder can be improved.
- a typical surface active agent may be used.
- the term "surface active agent” is a generic name for a substance that has a water-compatible portion (hydrophilic group) and an oil-compatible portion (lipophilic group, hydrophobic group) within the same molecule, and if it satisfies this definition, the aforementioned polyethylene glycol used in the present embodiment may also be considered a surface active agent.
- the term "surface active agent” excludes the polyethylene glycol added with the anticipation of achieving the characteristic effects of the present embodiment, but rather refers to sodium lauryl sulfate or a polyoxyethylene alkyl ether or the like that is added in a prescribed amount in order to achieve a dispersion or aggregation effect, a foaming or defoaming effect, a wettability improvement effect, a softening and smoothing effect, or an antistatic effect or the like.
- the sintered precious metal body can be produced by kneading the aforementioned clay-like composition for forming a sintered precious metal body, shaping the composition into a desired shape, and then firing the composition.
- a method for producing the clay-like composition described in the present embodiment is described below.
- methyl cellulose as the organic binder, and the surface active agent, olive oil, propylene glycol, glycerol, polyethylene glycol and water are stirred and mixed inside a container fitted with a stirrer.
- the resulting binder mixed solution is then introduced into a kneading device together with the precious metal powder and/or the precious metal alloy powder.
- the propylene glycol, glycerol and polyethylene glycol were added during the stirring and mixing of the binder mixed solution, but these components may also be added during kneading of the organic binder, the precious metal powder and/or precious metal alloy powder and water inside the kneading device.
- the internal walls of the stainless steel kneading container of the kneading device were coated with CrN.
- This CrN coating has excellent wear resistance as well as excellent lubricity, and can therefore suppress Fe contamination.
- the clay-like composition of the present invention is described below in further detail using a series of examples.
- methyl cellulose as the organic binder, and the surface active agent, olive oil, propylene glycol, glycerol, polyethylene glycol and water were stirred and mixed inside a container fitted with a stirrer to obtain a binder mixed solution.
- this binder mixed solution was introduced, together with a silver powder, into a stainless steel kneading device having internal walls coated with CrN.
- clay-like compositions having the formulations shown in Table 1 were prepared.
- the Meyer hardness measurement is the value determined by placing a steel ball on a clay that has been dried a prescribed amount, and dividing the load applied by the cross-sectional area of the indented portion. A lower value indicates a softer material, namely a precious metal clay that exhibits greater flexibility even upon drying.
- Each of the clay-like compositions shown in Table 1 was shaped into a sheet-like form having a length of 60 mm, a width of 5 mm and a thickness of 2 mm, and following storage in a constant-temperature constant-humidity chamber at room temperature and a humidity of 40% for the storage time shown in Table 2, the sheet was rolled into a cylindrical shape of ⁇ 17 mm, and the occurrence of cracks on the surface of the cylinder was evaluated. The evaluation results are shown in Table 2. If no cracks of 1 mm or more appeared in the surface of the precious metal clay, an evaluation of "A" was recorded, whereas if one or more cracks of 1 mm or more appeared in the surface of the precious metal clay, an evaluation of "B" was recorded. The evaluation results are shown in Table 2.
- FIG. 1 shows a photograph of the precious metal clay according to Reference Example 3, which was able to be shaped into a sheet-like form with an overall thickness of 3 mm
- FIG. 2 is a photograph showing the precious metal clay of Comparative Example 2, which when stretched, partially returned to its original form, and was not able to be shaped into a sheet-like form with an overall thickness of 3 mm.
- the evaluation results are shown in Table 2.
- the present invention is able to provide a clay-like composition for forming a sintered precious metal body which exhibits excellent flexibility and bendability during shaping of the precious metal clay, even after the precious metal clay has dried, and as a result the clay-like composition also exhibits excellent formability with minimal time restrictions during working of the composition by bending and the like.
- a sintered precious metal body can be produced by kneading the clay-like composition for forming a sintered precious metal body according to the present invention, shaping the composition into a desired shape, and then firing the composition.
Claims (1)
- Tonartige Zusammensetzung zur Bildung eines gesinterten Edelmetallkörpers, wobei die tonartige Zusammensetzung
zumindest ein Edelmetallpulver und/oder ein Edelmetallegierungspulver in einer Menge von 50 bis 95 Masse-%;
ein organisches Bindemittel;
ein organisches Additiv, einschliesslich Propylenglykol, Glycerin und Polyethylenglykol; und
Wasser,
umfasst, wobei die kombinierte Menge an Propylenglykol, Glycerin und Polyethylenglykol 0,1 bis 3,0 Masse-% beträgt.
Applications Claiming Priority (2)
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JP2013069638A JP6090664B2 (ja) | 2013-03-28 | 2013-03-28 | 貴金属焼結体用の粘土状組成物 |
PCT/JP2014/058880 WO2014157527A1 (ja) | 2013-03-28 | 2014-03-27 | 貴金属焼結体用の粘土状組成物 |
Publications (3)
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EP2979782A1 EP2979782A1 (de) | 2016-02-03 |
EP2979782A4 EP2979782A4 (de) | 2016-11-30 |
EP2979782B1 true EP2979782B1 (de) | 2018-08-22 |
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EP14774733.1A Active EP2979782B1 (de) | 2013-03-28 | 2014-03-27 | Tonzusammensetzung für einen edelmetall-sinterpressling |
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US (1) | US20160001363A1 (de) |
EP (1) | EP2979782B1 (de) |
JP (1) | JP6090664B2 (de) |
WO (1) | WO2014157527A1 (de) |
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JP6241228B2 (ja) * | 2013-11-28 | 2017-12-06 | 三菱マテリアル株式会社 | 貴金属焼結体形成用粘土状成形体 |
JP6241227B2 (ja) * | 2013-11-28 | 2017-12-06 | 三菱マテリアル株式会社 | 貴金属焼結体用粘土状組成物 |
WO2018097372A1 (ko) * | 2016-11-28 | 2018-05-31 | 마경희 | 은점토 조성물 및 그의 제조방법 |
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US3502466A (en) * | 1969-04-22 | 1970-03-24 | Ceramco Ind Products Corp | Manufacture of articles from powdered metals |
US4721599A (en) * | 1985-04-26 | 1988-01-26 | Hitachi Metals, Ltd. | Method for producing metal or alloy articles |
US4956404A (en) * | 1989-01-10 | 1990-09-11 | Josef Pelzig | Plastic composition for toys, novelty items and arts and crafts |
JP2760134B2 (ja) | 1990-05-18 | 1998-05-28 | 三菱マテリアル株式会社 | 貴金属造形用可塑性組成物 |
JPH0497940A (ja) * | 1990-08-14 | 1992-03-30 | Dow Chem Co:The | 無機粉末スラリーの製造方法 |
US5855820A (en) * | 1997-11-13 | 1999-01-05 | E. I. Du Pont De Nemours And Company | Water based thick film conductive compositions |
US6261496B1 (en) * | 1999-07-15 | 2001-07-17 | Alliedsignal Inc. | Continuous compounding of aqueous injection molding feedstocks |
JP4265127B2 (ja) | 2000-12-12 | 2009-05-20 | 三菱マテリアル株式会社 | 低温燒結性に優れた銀粘土用銀粉末およびこの銀粉末を含む銀粘土 |
JP4258370B2 (ja) | 2003-12-25 | 2009-04-30 | 三菱マテリアル株式会社 | 銀粘土焼成体表面装飾用ペースト |
JP5070808B2 (ja) * | 2005-11-11 | 2012-11-14 | 三菱マテリアル株式会社 | 太陽電池の電極形成用組成物及び該電極の形成方法並びに該形成方法により得られた電極を用いた太陽電池 |
GB2439544A (en) * | 2006-06-30 | 2008-01-02 | Janine Margar Schneider-Marsan | Firing an article made of pecious metal clay using a gas hob |
JP4741712B2 (ja) * | 2008-05-28 | 2011-08-10 | 相田化学工業株式会社 | 貴金属焼結用組成物、貴金属焼結体の製造方法及び貴金属焼結体 |
JP4573138B2 (ja) * | 2008-06-26 | 2010-11-04 | Dic株式会社 | 銀含有粉体の製造方法、銀含有粉体及びその分散液 |
US20100176339A1 (en) * | 2009-01-12 | 2010-07-15 | Chandran K S Ravi | Jewelry having titanium boride compounds and methods of making the same |
JP2011089147A (ja) * | 2009-10-20 | 2011-05-06 | Mitsubishi Materials Corp | 銀微粒子とその製造方法 |
KR20130050906A (ko) * | 2010-08-27 | 2013-05-16 | 피켐 어소시에이츠, 인코퍼레이티드 | 저온 소결성 은 나노 입자 조성물 및 상기 조성물을 이용하여 형성된 전자 물품 |
JP6241227B2 (ja) * | 2013-11-28 | 2017-12-06 | 三菱マテリアル株式会社 | 貴金属焼結体用粘土状組成物 |
-
2013
- 2013-03-28 JP JP2013069638A patent/JP6090664B2/ja active Active
-
2014
- 2014-03-27 EP EP14774733.1A patent/EP2979782B1/de active Active
- 2014-03-27 US US14/768,305 patent/US20160001363A1/en not_active Abandoned
- 2014-03-27 WO PCT/JP2014/058880 patent/WO2014157527A1/ja active Application Filing
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Also Published As
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WO2014157527A1 (ja) | 2014-10-02 |
JP6090664B2 (ja) | 2017-03-08 |
EP2979782A4 (de) | 2016-11-30 |
JP2014189896A (ja) | 2014-10-06 |
US20160001363A1 (en) | 2016-01-07 |
EP2979782A1 (de) | 2016-02-03 |
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