EP0520465B1 - Goldfarbige gesinterte Legierung - Google Patents

Goldfarbige gesinterte Legierung Download PDF

Info

Publication number
EP0520465B1
EP0520465B1 EP92110770A EP92110770A EP0520465B1 EP 0520465 B1 EP0520465 B1 EP 0520465B1 EP 92110770 A EP92110770 A EP 92110770A EP 92110770 A EP92110770 A EP 92110770A EP 0520465 B1 EP0520465 B1 EP 0520465B1
Authority
EP
European Patent Office
Prior art keywords
weight
gold color
respect
sintered alloy
amount
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP92110770A
Other languages
English (en)
French (fr)
Other versions
EP0520465A1 (de
Inventor
Yoshio c/o Kyocera Corporation Nagato
Hiroshi c/o Kyocera Corporation Hamashima
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kyocera Corp
Original Assignee
Kyocera Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP3157206A external-priority patent/JPH059645A/ja
Priority claimed from JP3157204A external-priority patent/JPH059643A/ja
Priority claimed from JP3157205A external-priority patent/JPH059644A/ja
Priority claimed from JP3200339A external-priority patent/JPH0543966A/ja
Priority claimed from JP11765992A external-priority patent/JP3255700B2/ja
Application filed by Kyocera Corp filed Critical Kyocera Corp
Publication of EP0520465A1 publication Critical patent/EP0520465A1/de
Application granted granted Critical
Publication of EP0520465B1 publication Critical patent/EP0520465B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/04—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbonitrides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/16—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on nitrides

Definitions

  • the present invention relates to a sintered alloy which exhibits gold color and is used for ornamental purposes.
  • the aforementioned gold-color sintered alloys are usually sintered poorly.
  • the sintering must be carried out by adding various additives such as carbides or carbonitrides of elements of the Groups 4a, 5a and 6a of periodic table.
  • the sintered products exhibit poor anti-chipping property, easily develop dropped-out particles at the time of machining for making ornaments, and make it difficult to carry out sharp-edge machining.
  • the object of the present invention therefore is to provide a sintered alloy of gold color having vivid and favorable gold color tone, high strength and hardness, excellent corrosion resistance, excellent anti-chipping property, and which permits the sharp-edge machining to be easily carried out.
  • a sintered alloy of gold color comprising a nitride of titanium or a carbonitride of titanium and metals, wherein titanium is contained in an amount of 55 to 75% by weight with respect to the whole amount, metals of the iron family and elements of the Group 6a of periodic table including at least chromium are contained in an amount of 3 to 30% by weight with respect to the whole amount, and the remainder being non-metallic elements consisting of nitrogen or nitrogen and carbon, and wherein the ratio of carbon with respect to said non-metallic elements is not greater than 10% by weight, and the ratio of chromium in the metal elements excluding titanium is not smaller than 35% by weight.
  • a sintered alloy in which metals of the iron famility and elements of the Group 6a of periodic table including at least chromium are contained in an amount of 10 to 30% by weight with respect to the whole amount, the ratio of carbon is not greater than 0.7% by weight with respect to the whole amount, and the brightness index L ⁇ and chromaticness indexes a ⁇ , b ⁇ in the L ⁇ a ⁇ b ⁇ color display system stipulated under JIS Z 8730 are L ⁇ ⁇ 10, a* ⁇ +0.4 and b ⁇ ⁇ +8.0.
  • a sintered alloy having an average crystalline particle size of not greater than 3 ⁇ m.
  • metals of the iron family include nickel, iron and cobalt
  • elements of the Group 6a of periodic table include chromium, molybdenium and tungsten
  • non-metallic elements include nitrogen and carbon.
  • Titanium is contained in an amount of 55 to 75% by weight with respect to the whole amount. If this amount is smaller than 55% by weight, the gold color tone becomes faint. If this amount becomes greater than 75% by weight, on the other hand, the sintering property is lost and the strength decreases. It is desired that titanium is contained in an amount of 60 to 70% by weight and, particularly, in an amount of 60 to 68% by weight. In the sintered product, titanium exists chiefly in the forms of TiN and TiCN that constitute hard phases.
  • Metals of the iron family and elements of the Group 6a of periodic table are contained in an amount of 3 to 30% by weight with respect to the whole amount. This is because, if this amount is smaller than 3% by weight, it becomes difficult to carry out the sintering and besides the sintered product loses strength. If the amount exceeds 30% by weight, on the other hand, the hardness of the sintered product is remarkable lost and the corrosion resistance is lost, too.
  • the metals are contained in an amount of 10 to 30% by weight and, particularly, in an amount of 12 to 23% by weight.
  • the metals of the iron family form a binder phase in the sintered product, and elements of the Group 6a of periodic table form a hard phase or a bonding phase.
  • the metals of the iron family exist at a ratio of 5 to 18% by weight and the elements of the Group 6a of periodic table exist at a ratio of 3 to 12% by weight.
  • the ratio of carbon with respect to the non-metallic elements is selected to be not greater than 10% by weight. This is because if this ratio is greater than 10% by weight, the color tone tends to become reddish rather than the gold color, and the color changes from red copper color into greyish brown with an increase in the ratio of carbon. In order to maintain vivid and favorable gold color tone, therefore, the ratio of carbon with respect to the non-metallic elements must be selected to be not greater than 10% by weight. In particular, it is desired that the ratio of carbon with respect to the non-metallic elements is not greater than 8% by weight.
  • the ratio of carbon is selected to be not greater than 0.7% by weight with respect to the whole amount. If this ratio is greater than 0.7% by weight with respect to the whole amount. If this ratio is greater than 0.7% by weight, the chromaticness indexes a ⁇ and b ⁇ become a ⁇ > +0.4 and b ⁇ ⁇ +8.0, and the color tone tends to become reddish from its original gold color, and the color changes from red copper color into greyish brown with an increase in the ratio of carbon. In particular, the chromaticness index a ⁇ changes with a change in the ratio of carbon. In order to maintain vivid and favorable gold color tone, therefore, the ratio of carbon must be not greater than 0.7% by weight with respect to the whole amount.
  • the ratio of carbon is not greater than 0.5% by weight with respect to the whole amount.
  • the amount of carbon in the sintered product is not greater than 0.7% by weight, it is recommended that the starting powder of carbide should be added in an amount as small as possible. Or, when the carbide is added in a large amount, oxides such as TiO 2 and the like should be added, such that carbon in the carbide is diffused during the baking.
  • the ratio of chromium in the metal elements excluding titanium is larger than 35% by weight and, particularly, larger than 40% by weight. If this ratio is smaller than 35% by weight, voids easily develop in the sintered product, and dropped-out particles develop remarkably during the machining such as grinding and polishing causing the strength to decrease and the corrosion resistance to decrease, too. Further, if the ratio of chromium is smaller than 35% by weight, the brightness index L in the L ⁇ a ⁇ b ⁇ color display system tends to be decreased. If the ratio of chromium with respect to the bonded metals in the sintered product is not smaller than 35% by weight, on the other hand, the sintering property is improved and the above-mentioned problems do not take place. This is attributed to that the addition of chromium improves wettability between the hard phase and the binding phase.
  • the sintered alloy of gold color has an average crystalline particle size of not greater than 8 ⁇ m and, particularly, not greater than 3 ⁇ m. If the particle size is greater than 8 ⁇ m, cracks develop remarkably and chipping develops during the grinding to such an extent that makes it difficult to carry out the sharp-edge machining. If the average crystalline particle size is not greater than 3 ⁇ m, on the other hand, it is allowed to easily carry out the sharp-edge machining. This is attributed to hat the ceramic material is brittle and is weak against impact and easily develops cracks. If the average crystalline particle size is not greater than 3 ⁇ m, however, reduced stress acts upon each particle in case stress is produced by the grinding and the dropped-out particle takes place little. The remainder inevitably includes small amounts of impurities.
  • the sintered alloy of gold color of the present invention is obtained by mixing a nitride of titanium and a carbonitride of titanium as starting powders together with metals of the iron family and elements of the Group 6a of periodic table. The mixture is then pulverized in an organic solvent such as acetone for a predetermined period of time. Then, an organic binder is added thereto in a predetermined amount, and the mixture is molded into a desired shape by the press molding, injection molding or extrusion molding. The molded article is then placed in a non-oxidizing atmosphere heated at a temperature of 250°C to 500°C to remove the binder therefrom, followed by baking at a predetermined temperature.
  • a nitride of titanium and a carbonitride of titanium having a particle size of 0.5 to 3.0 ⁇ m, nickel and cobalt having a particle size of 0.1 to 1.0 ⁇ m which are metals of the iron family, as well s chromium, WC, Cr 3 C 2 and Mo(Mo 2 C) having a particle size of 1.0 to 10.0 ⁇ m which are elements of the Group 6a of periodic table, are weighed and mixed, and are pulverized in an organic solvent such as acetone for about 20 to 100 hours and, particularly, for 48 to 72 hours.
  • the mixture is then molded into a desired shape by the press molding, injection molding or extrusion molding.
  • the molded article is placed in a non-oxidizing atmosphere at a predetermined temperature to remove the organic binder, followed by vacuum-baking in a vacuum heating furnace at a predetermined temperature to obtain the sintered alloy of gold color. It is desired that the vacuum-baking is carried out for 0.5 to 5 hours.
  • tungsten and chromium are added as starting carbide powders but do not stay as metallic chromium or metallic tungsten in the form of solid solution in the bonded metals, or do not stay in the form of solid solution in TiN or TiCN, or do not exist in the form of WC or Cr 3 O 2 in the step of baking.
  • the baking is carried out at a temperature of 1300° to 1800°C in an atmosphere of a degree of vacuum of 10 -1 to 10 -4 Torr or in various atmosphere of reduced pressure or without pressure.
  • the baking is continued for 0.5 to 5 hours though it may vary depending upon the size of the sample.
  • the surface of the sintered product is polished like a mirror surface using a diamond paste or the like to obtain vivid and favorable gold color with luster.
  • the sintered alloy can be used for ornamental purposes such as of watch cases, watch bands, necklaces, brooches, memorial medals and buttons, and for cutlery, fishing tools and printing tools.
  • TiN having a particle size of 2 ⁇ m, TiCN having a particle size of 2 ⁇ m, chromium having a particle size of 3 ⁇ m, molybdenum having a particle size of 4 ⁇ m, nickel having a particle size of 1 ⁇ m and cobalt having a particle size of 1 ⁇ m were used as starting material powders, and were weighed and mixed in a manner that the ratios of amount of the metals in the final sintered products were as shown in Table 1.
  • the mixtures were pulverized in an organic solvent such as acetone for about 68 hours and, after paraffin was added thereto in an amount of 4 to 5% by weight, were molded Under the application of pressure of 1.5 tons/cm 2 into a desired shape.
  • the molded articles were placed in a non-oxidizing atmosphere heated at a temperature of 300°C to remove the organic binder, and were then baked in vacuum in a vacuum heating furnace having a degree of vacuum of 10 -2 Torr at a temperature of 1450°C for one hour. Compositions of the thus obtained final sintered products were analyzed by the ICP emission spectroanalysis. The results were as shown in Table 1. Table 1 Sample No.
  • the surfaces of the sintered products were ground and polished like a mirror.
  • the samples were then tested for their color tone, bending strength, Vickers' hardness (Hv), anti-chipping property and corrosion resistance.
  • the bending strength was measured in accordance with the three-point bending test stipulated under JIS R 1601, the Vickers' hardness was measured in compliance with the testing method of JIS Z 2244, and the anti-corrosion testing was carried out by using human sweat (pH 4.7) in compliance with the standards of the ISO (International Standardization Organization) as a corrosive solution, immersing the lower half of the mirror surface-polished sample in the human sweat maintained at 40°C + 2°C for 24 hours, and the conditions of the polished surfaces of the samples after immersed were observed.
  • human sweat pH 4.7
  • ISO International Standardization Organization
  • the color tone was measured and evaluated by using an L ⁇ a ⁇ b ⁇ optical color difference meter (manufactured by Minolta Co.), i.e., by using a high-functional-color color difference meter (in compliance with JIS Z 8722) of the 45° ring illumination vertical light-receiving system.
  • the anti-chipping property was evaluated in terms of a maximum chipping width of when the mirror surface-polished sample was creep-ground. The results were as shown in Table 2 and 3.
  • TiN having a particle size of 1.2 ⁇ m, TiCN having a particle size of 1.5 ⁇ m, Cr 3 C 2 having a particle size of 7.0 ⁇ m, WC having a particle size of 9.0 ⁇ m, nickel having a particle size of 3.0 ⁇ m, and cobalt having a particle size of 4.0 ⁇ m were used as starting material powders, and were weighed and mixed in a manner that the ratios of amounts of the metals in the final sintered products were as shown in Table 1.
  • the mixtures were pulverized in an organic solvent such as acetone for about 68 hours and, after paraffin was added thereto in an amount of 4 to 5% by weight, were molded under the application of pressure of 1.5 tons/cm 2 into a desired shape.
  • the molded articles were placed in a non-oxidizing atmosphere heated at a predetermined temperature to remove the organic binder, and were then baked in vacuum in a vacuum heating furnace having a degree of vacuum of 10 -2 Torr at a temperature of 1450°C for one hour.
  • the thus obtained final sintered products were analyzed by the ICP emission spectroanalysis. The results were as shown in Table 4.
  • the surfaces of the sintered products were ground and polished like a mirror.
  • the samples were then tested for their color tone, bending strength, Vickers' hardness (Hv), porosity, average crystalline size, anti-chipping property and corrosion resistance.
  • the bending strength was measured in accordance with the three-point bending test stipulated under JIS R 1601, the Vickers' hardness was measured in compliance with the testing method of JIS Z 2244, and the porosity was measured according to the Archimedes' method.
  • the anti-corrosion testing was carried out by using human sweat (pH 4.7) in compliance with the standards of the ISO (International Standardization Organization) as a corrosive solution, immersing the lower half of the mirror surface-polished sample in the human sweat maintained at 40°C + 2°C for 24 hours, and the conditions of the polished surfaces of the samples after immersed were observed.
  • the average crystalline particle size was calculated from an S.E.M photograph of the sintered product.
  • the anti-chipping property was indicated in terms of a maximum chipping width of when the mirror surface-polished sample was creep-ground. The results were as shown in Table 5.
  • an open circle ⁇ represents high-density products with the porosity of smaller than 5% and a mark X represents low-density products with the porosity of greater than 5%.
  • an open circle ⁇ represents the products without any discoloration or corrosion, and a mark X represents the products that were discolored and corroded.
  • an open circle ⁇ represents the products that could be favorably sharp-edge machined, and a mark X represents the products that developed chipping and could not be sharp-edge machined.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Adornments (AREA)
  • Ceramic Products (AREA)

Claims (9)

  1. Ein Titannitrid oder Titancarbonnitrid und Metalle enthaltende goldfarbige gesinterte Legierung, worin Titan in einer Menge von 55 bis 75 Gew.-%, bezogen auf die Gesamtmenge, Metalle der Eisenfamilie und Elemente der Gruppe 6a des Periodensystems einschließlich zumindest Chrom in einer Menge von 3 bis 30 Gew.-%, bezogen auf die Gesamtmenge enthalten, und der Rest aus Stickstoff oder Stickstoff und Kohlenstoff enthaltende nichtmetallische Elemente sind und worin das Kohlenstoffverhältnis hinsichtlich der nichtmetallischen Elemente nicht größer als 10 Gew.-% und das Chromverhältnis in den Metallelementen ausschließlich Titan nicht kleiner als 35 Gew.-% ist.
  2. Goldfarbige gesinterte Legierung nach Anspruch 1, worin die Metalle der Eisenfamilie und die Elemente der Gruppe 6a des Periodensystems einschließlich zumindest Chrom in einer Menge von 10 bis 30 Gew.-%, bezogen auf die Gesamtmenge, enthalten, das Kohlenstoffverhältnis nicht größer als 0,7 Gew.-%, bezogen auf die Gesamtmenge, und der Helligkeitsindex L und die Chromatizitätsindizes a*, b* in dem gemäß JIS Z 8730 festgelegten L*a*b*-Farbdisplaysystem L*≥ 10, a*≤ +0,4 und b* ≥ +8,0 sind.
  3. Goldfarbige gesinterte Legierung nach Anspruch 2, worin Titan in einer Menge von 60 bis 68 Gew.-%, bezogen auf die Gesamtmenge, vorliegt.
  4. Goldfarbige gesinterte Legierung nach Anspruch 2, worin die Metalle der Eisenfamilie und die Elemente der Gruppe 6a des Periodensystems in Mengen von 12 bis 23 Gew.-%, bezogen auf die Gesamtmenge, vorliegen.
  5. Goldfarbige gesinterte Legierung nach Anspruch 2, worin die Metalle der Eisenfamilie in einem Verhältnis von 5 bis 18 Gew.-% und die Elemente der Gruppe 6a des Periodensystems in einem Verhältnis von 3 bis 12 Gew.-%, bezogen auf die Gesamtmenge, vorliegen.
  6. Goldfarbige gesinterte Legierung nach Anspruch 1, worin die gesinterte Legierung eine durchschnittliche Teilchengröße von nicht größer als 3 µm hat.
  7. Goldfarbige gesinterte Legierung nach Anspruch 6, worin das Chromverhältnis in den Metallelementen ausschließlich Titan nicht kleiner als 40 Gew.-% ist.
  8. Goldfarbige gesinterte Legierung nach Anspruch 6, worin Titan in einer Menge von 60 bis 70 Gew.-%, bezogen auf die Gesamtmenge, vorliegt.
  9. Goldfarbige gesinterte Legierung nach Anspruch 6, worin das Kohlenstoffverhältnis bezüglich der nichtmetallischen Elemente nicht größer als 8 Gew.-% ist.
EP92110770A 1991-06-27 1992-06-26 Goldfarbige gesinterte Legierung Expired - Lifetime EP0520465B1 (de)

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
JP157204/91 1991-06-27
JP157206/91 1991-06-27
JP3157206A JPH059645A (ja) 1991-06-27 1991-06-27 金色焼結合金
JP3157204A JPH059643A (ja) 1991-06-27 1991-06-27 金色焼結合金
JP157205/91 1991-06-27
JP3157205A JPH059644A (ja) 1991-06-27 1991-06-27 金色焼結合金
JP3200339A JPH0543966A (ja) 1991-08-09 1991-08-09 金色焼結合金
JP200339/91 1991-08-09
JP117659/92 1992-05-11
JP11765992A JP3255700B2 (ja) 1992-05-11 1992-05-11 金色焼結合金

Publications (2)

Publication Number Publication Date
EP0520465A1 EP0520465A1 (de) 1992-12-30
EP0520465B1 true EP0520465B1 (de) 1996-12-27

Family

ID=27526775

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92110770A Expired - Lifetime EP0520465B1 (de) 1991-06-27 1992-06-26 Goldfarbige gesinterte Legierung

Country Status (3)

Country Link
EP (1) EP0520465B1 (de)
KR (1) KR100239844B1 (de)
DE (1) DE69216156T2 (de)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE9116669U1 (de) * 1991-07-23 1993-06-17 WMF Württembergische Metallwarenfabrik AG, 7340 Geislingen Besteckteile aus Metall
US5925197A (en) * 1992-01-24 1999-07-20 Sandvik Ab Hard alloys for tools in the wood industry
SE9202194D0 (sv) * 1992-07-17 1992-07-17 Sandvik Ab Hard alloys for tools in the wood industry
US6684759B1 (en) 1999-11-19 2004-02-03 Vladimir Gorokhovsky Temperature regulator for a substrate in vapor deposition processes
AU7169100A (en) * 1999-11-19 2001-05-24 Gorokhovsky, Vladimir Temperature regulator for a substrate in vapour deposition processes
US6871700B2 (en) 2000-11-17 2005-03-29 G & H Technologies Llc Thermal flux regulator
JP4596692B2 (ja) * 2001-06-28 2010-12-08 京セラ株式会社 焼結合金及びその製造方法
US7211338B2 (en) * 2003-12-19 2007-05-01 Honeywell International, Inc. Hard, ductile coating system
JP5342740B2 (ja) * 2005-09-27 2013-11-13 京セラ株式会社 装飾部品用セラミックスおよびこれを用いた時計用装飾部品
WO2008048343A2 (en) * 2006-02-14 2008-04-24 Dynamet Technology, Inc. Homogeneous titanium tungsten alloys produced by powder metal technology
EP2423343A4 (de) * 2009-04-24 2012-11-07 Kyocera Corp Keramik für zierelement und zierelement damit
WO2015183990A2 (en) * 2014-05-27 2015-12-03 Frederick Goldman, Inc. Titanium-based alloys and articles formed from such alloys

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6029443A (ja) * 1983-07-28 1985-02-14 Kyocera Corp 装飾用金色焼結合金
JPH0711043B2 (ja) * 1988-10-28 1995-02-08 京セラ株式会社 サーメット工具の製造方法
JP2775298B2 (ja) * 1989-06-28 1998-07-16 京セラ株式会社 サーメット工具

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 80, no. 16, April 22, 1974, Columbus, Ohio, USA YONEYA KATSUTOSHI et al. "Hard alloy for ornament" page 233, column 2, abstract-no. 86 647c; & Japan. Kokai 73 94, 607 *
CHEMICAL ABSTRACTS, vol. 95, no. 2, July 13, 1981, Columbus, Ohio, USA MITSUBISHI METAL CORP. "Ornamental hard sintered alloys" page 250, column 2, abstract-no. 11 128k; & Jpn. Kokai Tokkyo Koho 81 09, 352 *
CHEMICAL ABSTRACTS, vol. 99, no. 14, October 03, 1983, Columbus, Ohio, USA TOSHIBA TUNGALOY CO. "Ornamental golden-colored titanium monoxide-base composites" page 252, column 2, abstract-no. 109 451t; & Jpn. Kokai Tokkyo Koho JP 58 91,145 *

Also Published As

Publication number Publication date
EP0520465A1 (de) 1992-12-30
KR100239844B1 (ko) 2000-01-15
DE69216156D1 (de) 1997-02-06
DE69216156T2 (de) 1997-07-03

Similar Documents

Publication Publication Date Title
US7578867B2 (en) Ceramic sintered product and method for production thereof, and decorative member using the ceramic sintered product
EP0520465B1 (de) Goldfarbige gesinterte Legierung
JP5342740B2 (ja) 装飾部品用セラミックスおよびこれを用いた時計用装飾部品
US4589917A (en) Decorative golden sintered alloy
JPS61106743A (ja) 装飾用銀色焼結合金
JP3255744B2 (ja) 金色焼結体およびその製造方法
KR100385208B1 (ko) 은색 소결제품 및 그 제조방법
JP4596692B2 (ja) 焼結合金及びその製造方法
US4639426A (en) Decorative hard golden ceramic article
JP3255700B2 (ja) 金色焼結合金
US4702769A (en) Sintered alloy for decoration
JP3020663B2 (ja) 印 鑑
US20230250517A1 (en) Component for timepiece or piece of jewellery made of cermet
JP3450949B2 (ja) 金色焼結体
JPH05156403A (ja) 金色焼結合金
JPH059644A (ja) 金色焼結合金
JP3285635B2 (ja) Ｔａ−Ｂ−Ｃ系焼結体およびその製造方法
JP3255811B2 (ja) 銀色焼結体およびその製造方法
JPH059643A (ja) 金色焼結合金
JP3481777B2 (ja) 金色焼結体
US20230304133A1 (en) Cermet decorative item
JPH059645A (ja) 金色焼結合金
JP3255767B2 (ja) 金色焼結体およびその製造方法
JP3336138B2 (ja) 銀色焼結体
JPH0543966A (ja) 金色焼結合金

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): CH DE LI

17P Request for examination filed

Effective date: 19930525

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 19960206

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE LI

REF Corresponds to:

Ref document number: 69216156

Country of ref document: DE

Date of ref document: 19970206

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: E. BLUM & CO. PATENTANWAELTE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Owner name: KYOCERA CORPORATION

Free format text: KYOCERA CORPORATION#5-22, KITA INOUE-CHO HIGASHINO#YAMASHINA-KU KYOTO-SHI (JP) -TRANSFER TO- KYOCERA CORPORATION#5-22, KITA INOUE-CHO HIGASHINO#YAMASHINA-KU KYOTO-SHI (JP)

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20100625

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20110614

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69216156

Country of ref document: DE

Effective date: 20120103

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120103

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL