JP2004344651A - Method for manufacturing accessory in which metal is cast to surround gem, and gem suited thereto - Google Patents
Method for manufacturing accessory in which metal is cast to surround gem, and gem suited thereto Download PDFInfo
- Publication number
- JP2004344651A JP2004344651A JP2004139330A JP2004139330A JP2004344651A JP 2004344651 A JP2004344651 A JP 2004344651A JP 2004139330 A JP2004139330 A JP 2004139330A JP 2004139330 A JP2004139330 A JP 2004139330A JP 2004344651 A JP2004344651 A JP 2004344651A
- Authority
- JP
- Japan
- Prior art keywords
- jewelry
- colorant
- containing layer
- metal
- stone
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 31
- 239000002184 metal Substances 0.000 title claims abstract description 31
- 239000003086 colorant Substances 0.000 claims abstract description 53
- 238000005266 casting Methods 0.000 claims abstract description 29
- 239000004575 stone Substances 0.000 claims description 67
- 238000005058 metal casting Methods 0.000 claims description 13
- 238000010336 energy treatment Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000010437 gem Substances 0.000 claims description 6
- 229910001751 gemstone Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011253 protective coating Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 50
- 239000000049 pigment Substances 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 238000004040 coloring Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000010930 yellow gold Substances 0.000 description 3
- 229910001097 yellow gold Inorganic materials 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical group [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000005546 reactive sputtering Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 239000010938 white gold Substances 0.000 description 2
- 229910000832 white gold Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000038 blue colorant Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000010987 cubic zirconia Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000001034 iron oxide pigment Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- -1 magnesium aluminate Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
- A44C17/00—Gems or the like
- A44C17/04—Setting gems in jewellery; Setting-tools
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49588—Jewelry or locket making
- Y10T29/4959—Human adornment device making
Landscapes
- Adornments (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
本発明は、宝飾石を取囲むように金属を鋳込むことによって装身具を製造するための方法、及びこれに適した宝飾石に関する。 The present invention relates to a method for manufacturing an ornament by casting a metal around a jewel stone, and a jewel stone suitable for the method.
一般に、宝飾石を使用した装身具は、装身具の一部（台）を別個に貴金属から製造し、それを細工職人の手によって宝飾石と組合わせて形成されるが、この細工職人の手による装身具の製造方法ではコスト的に割り高となって、相対的に安価な宝飾石に適用できる装身具の製造方法ではない。これに対して、宝飾石を取囲むように金属を鋳込むことによって装身具を製造する方法は、細工職人の手を煩わせることがないため、相対的に安価な宝飾石を使用した装身具の製造に適している。 In general, jewelry using jewelry stone is manufactured by separately manufacturing a part (stand) of jewelry from precious metal and combining it with jewelry stone by a craftsman's hand. However, this method is relatively expensive, and is not a method of manufacturing accessories that can be applied to relatively inexpensive jewelry stones. On the other hand, the method of manufacturing jewelry by casting metal so as to surround the jewelry stone does not require the craftsman's hands, and therefore, the manufacture of jewelry using relatively inexpensive jewelry stones Suitable for.
宝飾石を取囲むように金属を鋳込むことによって装身具を製造する方法に使用される宝飾石として特に考えられるのは、本来の色調が人為的に補強または変化させられた石である。宝飾石の色調の変更には２つの基本的に異なった方法を利用することができる。すなわち、着色剤を宝飾石の内部に拡散させるか、または有色のたとえば顔料含有層を宝飾石と密着結合させることで可能である。 Particularly considered as jewelry stones used in the method of manufacturing jewelry by casting metal around the jewelry stones are stones whose natural colors have been artificially reinforced or altered. Two fundamentally different methods can be used to change the color of the jewelry stone. That is, it is possible by diffusing the colorant into the interior of the jewelry stone or by tightly bonding a colored, for example, pigment-containing layer to the jewelry stone.
ここでは、工業的量産にはるかに適していることから、後者の方法による着色のみに注目する。たとえば、特許文献１から、酸化コバルト、酸化アルミニウム、酸化ケイ素の蒸着によって本体に青い着色剤含有層を被着することが知られている。これらの着色剤含有層は、酸素含有雰囲気中で約３００°Ｃにて約３０分間にわたって加熱処理されはするが、冒頭に述べた、宝飾石を取囲むように金属を鋳込むことによって装身具を製造する方法の条件下では安定しない。 Here, we focus only on the latter method of coloring, as it is much more suitable for industrial mass production. For example, it is known from US Pat. No. 6,059,097 to deposit a blue colorant-containing layer on the body by vapor deposition of cobalt oxide, aluminum oxide, silicon oxide. These colorant-containing layers are heat-treated in an oxygen-containing atmosphere at about 300 ° C. for about 30 minutes, but the jewelry is cast by casting metal around the jewelry stone as described at the beginning. It is not stable under the conditions of the manufacturing method.
着色剤含有層の被着された宝飾石は、着色剤含有層の被着中または被着後に該着色剤含有層が高エネルギ処理に付されるが、驚くべきことに、この着色剤含有層に対する高エネルギ処理によって、宝飾石の周囲への金属鋳込み時における高エネルギ処理が施されても、宝飾石の周囲への金属鋳込み時に生ずると考えられる着色剤含有層の変化が抑止され、鋳込み法で十分加工し得ることが見出されたのである。 The jewelry stone with the colorant-containing layer applied thereto is subjected to a high energy treatment during or after the application of the colorant-containing layer. , The change in the colorant-containing layer, which is considered to occur at the time of casting the metal around the jewelry stone, is suppressed even when the high energy treatment is performed at the time of casting the metal around the jewelry stone. It has been found that can be processed sufficiently.
冒頭に述べた装身具の製造に際し、宝飾石は、先ずやや長時間にわたり、鋳込まれた貴金属によって最終的に置換される蝋型が完全に焼失する温度にさらされる。この温度は７５０°Ｃのレベルにある。続いて宝飾石の表面は貴金属の鋳込み時に、該貴金属が銀ならば９５０〜１０５０°Ｃ、金ならば９５０〜１２５０°Ｃ、プラチナならば１８００〜１９００°Ｃの温度に加熱される。以下に実施例に基づいて論ずるように、金属鋳込み時になお生ずる色調変化を最小限に抑止するには、着色剤含有層の被着された宝飾石を、金属鋳込み温度にさらされる時間を短縮するか、あるいは長時間にわたって蝋型の焼失温度に加熱するか、の少なくともいずれか一方を満足させることができれば十分である。
本発明は、以上のような実状に鑑みてなされたもので、その解決しようとする課題は、宝飾石の周囲への金属鋳込み時に生ずると考えられる着色剤含有層の変化を最小限に抑止するようにして、鋳込み法で加工し得る装身具の製造方法、及びこれに適した宝飾石を提供することにある。 The present invention has been made in view of the above circumstances, and a problem to be solved is to minimize a change in a colorant-containing layer which is considered to occur at the time of metal casting around a jewelry stone. Thus, an object of the present invention is to provide a method of manufacturing an ornament that can be processed by a casting method, and a jewelry stone suitable for the method.
以上の課題を解決するために、まず、請求項いに係る発明の採った手段は、
「宝飾石を取囲むように金属を鋳込むことによって装身具を製造する方法において、金属鋳込み前の前記宝飾石に着色剤含有層を被着するとともに、この着色剤含有層の被着中または被着後にこの着色剤含有層に高エネルギ処理を付すことにより、前記宝飾石周囲への金属鋳込み時に前記着色剤含有層の変化をもたらさないようにしたことを特徴とする装身具の製造方法」
であり、請求項２に係る発明は、上記請求項１に記載の装身具の製造方法について、
「前記の高エネルギ処理は１〜２０分間にわたり９５０°Ｃ〜１２５０°Ｃの温度に加熱することを含むこと」
としたことであり、請求項３に係る発明は、上記請求項１または請求項２に記載の装身具の製造方法について、
「前記の高エネルギ処理は少なくとも１時間にわたって７００°Ｃ〜８００°Ｃの温度で加熱処理することを含むこと」
である。
In order to solve the above problems, first, means taken by the claimed invention is:
"In a method of manufacturing a jewelry by casting a metal around a jewelry stone, a colorant-containing layer is applied to the jewelry stone before metal casting, and during or during application of the colorant-containing layer. A method for manufacturing an ornament, wherein the colorant-containing layer is subjected to a high energy treatment after being worn, so that the colorant-containing layer is not changed when the metal is cast around the jewelry stone. "
The invention according to
"The high energy treatment comprises heating to a temperature of 950 ° C to 1250 ° C for 1 to 20 minutes.”
According to a third aspect of the present invention, there is provided a method for manufacturing an accessory according to the first or second aspect,
"The high energy treatment includes heat treatment at a temperature of 700 ° C. to 800 ° C. for at least one hour.”
It is.
また、請求項４に係る発明の採った手段は、上記請求項１から３までのいずれか１項に記載の装身具の製造方法について、
「前記の着色剤含有層には保護被膜が被着されること」
であり、請求項５に係る発明の採った手段は、上記請求項4に記載の装身具の製造方法について、
「前記の保護被膜にはＬｉ、Ｍｇ、Ｚｎ、Ｂ、Ｃｅ、Ｔｉ、Ｓｉ、ＺｒまたはＡｌが含まれていること」
としたことである。
According to a fourth aspect of the present invention, there is provided a method for manufacturing an accessory according to any one of the first to third aspects.
"A protective film is applied to the colorant-containing layer."
Means adopted by the invention according to
"The protective coating contains Li, Mg, Zn, B, Ce, Ti, Si, Zr or Al."
It was that.
さらに、請求項６に係る発明の採った手段は、上記請求項１から５までのいずれか１項に記載の装身具の製造方法について、
「宝飾石と着色剤含有層との間につなぎ層が配置されること」
であり、請求項７に係る発明の採った手段は、上記請求項１から６までのいずれか１項に記載の装身具の製造方法について、
「宝飾石１の裏面２は鋳込まれた金属４によって形成されたリング３によって保護されること」
である。
Further, the means adopted by the invention according to
"A tie layer is placed between the jewelry stone and the colorant-containing layer."
The means adopted by the invention according to
"The
It is.
そして、請求項８に係る発明の採った手段は、
「金属の鋳込みによる装身具の製造に適した宝飾石において、この宝飾石に被着され、それ自体として色が変化し得る着色剤含有層に対して高エネルギ処理を施すことにより、前記着色剤含有層の色が１２５０°Ｃ以下の温度への加熱時にもはや大幅に変化しないようにしたことを特徴とする宝飾石」
である。
The means adopted by the invention according to claim 8 is as follows:
"In a jewelry stone suitable for the manufacture of jewelry by casting metal, a high-energy treatment is applied to the colorant-containing layer that is attached to the jewelry stone and that can change its color as such, thereby containing the colorant-containing material. Jewelry stone, characterized in that the color of the layer no longer changes significantly when heated to temperatures below 1250 ° C. "
It is.
以上の通り、本発明においては、
「宝飾石を取囲むように金属を鋳込むことによって装身具を製造する方法において、金属鋳込み前の前記宝飾石に着色剤含有層を被着するとともに、この着色剤含有層の被着中または被着後にこの着色剤含有層に高エネルギ処理を付すことにより、前記宝飾石周囲への金属鋳込み時に前記着色剤含有層の変化をもたらさないようにしたこと」
にその構成上の主たる特徴があり、これにより、宝飾石の周囲への金属鋳込み時に着色剤含有層の変化を最小限に抑止することができて、鋳込み法で加工し得る装身具の製造方法を提供することができるのである。
As described above, in the present invention,
"In a method of manufacturing a jewelry by casting a metal around a jewelry stone, a colorant-containing layer is applied to the jewelry stone before metal casting, and during or during application of the colorant-containing layer. By applying a high-energy treatment to the colorant-containing layer after wearing, the colorant-containing layer is prevented from changing when the metal is cast around the jewelry stone. "
There is a main feature in its configuration, and thereby, it is possible to minimize the change in the colorant-containing layer at the time of metal casting around the jewelry stone, and to provide a method of manufacturing an ornament that can be processed by the casting method. It can be provided.
また、本発明においては、
「金属の鋳込みによる装身具の製造に適した宝飾石において、この宝飾石に被着され、それ自体として色が変化し得る着色剤含有層に対して高エネルギ処理を施すことにより、前記着色剤含有層の色が１２５０°Ｃ以下の温度への加熱時にもはや大幅に変化しないようにしたことを特徴とする宝飾石」
にその構成上の特徴があり、これにより、宝飾石の周囲への金属鋳込み時に着色剤含有層の変化を最小限に抑止することができて、鋳込み法で加工し得る装身具の製造方法を実施できるようにした宝飾石を提供することができるのである。
In the present invention,
"In a jewelry stone suitable for the manufacture of jewelry by casting metal, a high-energy treatment is applied to the colorant-containing layer that is attached to the jewelry stone and that can change its color as such, thereby containing the colorant-containing material. Jewelry stone, characterized in that the color of the layer no longer changes significantly when heated to temperatures below 1250 ° C. "
Has a feature in its configuration, thereby implementing a method of manufacturing accessories that can minimize the change of the colorant-containing layer when casting metal around the jewelry stone and can be processed by the casting method. Jewelry stones that can be provided can be provided.
以下に、図面ないし実施例を参照して、本発明のその他の詳細を詳しく説明する。 Hereinafter, other details of the present invention will be described in detail with reference to the drawings and embodiments.
宝飾石の周囲への金属の鋳込みによる装身具の製造はそれ自体公知に属する。図１に示したように、宝飾石１は成形材料５の中に埋め込まれ、他方、金属枠用の場所確保材としてさしあたり蝋６が使用される。続いて蝋6は約７５０°Ｃへの加熱によって追い出され、こうして図2に示した空洞７が生ずる。この空洞7には最後に図３に示したように、宝飾石１を取囲む金属４が充填される。
The production of jewelry by casting metal around jewelry stones is known per se. As shown in FIG. 1, the
装身具の一例として図１〜３には指輪が表されているが、ただし本発明は宝飾石の表面、特にその裏面２（図４、参照）に、金属4の鋳込みによって損傷され得るような着色剤含有層が被着されているのであれば常に適用することが可能である。 A ring is shown as an example of the accessory in FIGS. If the agent-containing layer is applied, it can always be applied.
本発明による装身具の製造方法を適用するための前提条件は先ず、宝飾石自体が金属の鋳込み時にその光学的特性を保持していることである。たとえばガラスや水晶には耐熱着色剤含有層を容易に被着することができるとはいえ、通常のガラスでは前記の温度に際して融解してしまうであろう。水晶は蝋を焼失させるための通例の温度ですでに曇りを生じてしまうであろう。 A prerequisite for applying the method for manufacturing an accessory according to the present invention is that the jewelry stone itself retains its optical properties when the metal is cast. For example, glass or quartz can easily be coated with a heat-resistant colorant-containing layer, but ordinary glass will melt at the above temperatures. Quartz will already be clouded at the usual temperatures for burning off wax.
そこで、基本的に適した宝飾石、たとえば酸化ジルコニウムに着色剤含有層が被着される。このために最もよく使用される方法は物理蒸着、スパッタ、化学蒸着等である。特に反応性スパッタにより、加熱が容易な支持体に大半の無機顔料を比較的低温でも直接に被着することが可能である。 There, a colorant-containing layer is applied to basically suitable jewelry stones, for example zirconium oxide. The most commonly used methods for this are physical vapor deposition, sputtering, chemical vapor deposition and the like. In particular, reactive sputtering allows most inorganic pigments to be directly applied to relatively easily heated supports at relatively low temperatures.
宝飾石の着色には特に、無機有色顔料として基本的組成の知られている着色剤、特に、“条痕”を有する無機材料が適していると考えられる。こうした着色剤はセラミック釉がけならびにガラスの表面着色に関連して知られている。特に、ルチル−スズ石型構造、ジルコン型構造、バデレイ石型構造、コランダム-赤鉄鉱型構造、カンラン石型構造、スピネル型構造、ざくろ石型構造および灰チタン石型構造を有した酸化物系顔料ベースの着色剤含有層が適切である。窒化物系および特に酸窒化物系顔料ベースの着色剤含有層も同じくこの装身具の製造方法に非常に適していると思われ、また炭化物系および酸化炭素系ベースの着色剤含有層もそうである。硫化物系、硫酸塩系、リン酸塩系、シアン化合物系ならびに金属コロイド系ベースの着色剤含有層は特別な包埋を必要とするが、これらは鋳込み温度近傍もしくは鋳込み温度をぎりぎり下回る融点を有している場合にも適している。 It is considered that a coloring agent having a basic composition known as an inorganic colored pigment, particularly an inorganic material having "streaks", is particularly suitable for coloring jewelry stone. Such colorants are known in connection with ceramic glazes as well as glass surface coloring. In particular, an oxide system having a rutile-stannite type structure, a zircon type structure, a baddeleyite type structure, a corundum-hemite structure, an olivine type structure, a spinel type structure, a garnet type structure and a perovskite type structure A pigment-based colorant-containing layer is suitable. Colorant-containing layers based on nitrides and especially oxynitride pigments also appear to be very suitable for the process of making this accessory, as are colorant-containing layers based on carbides and carbon oxides. . Colorant-containing layers based on sulfides, sulfates, phosphates, cyanides, and metal colloids require special embedding, which have melting points near or just below the casting temperature. It is also suitable if you have one.
このようにして準備された宝飾石が図１〜３に示した装身具の製造方法で引き続き加工された場合には、好ましくないしかも非常に不都合な宝飾石の色変を生ずることとなろう。こうした色変は米国宝石学会[Ｇｅｍｏｌｏｇｉｃａｌ Ｉｎｓｔｉｔｕｒｅ ｏｆ Ａｍｅｒｉｃａ]の“着色石格付け制度[Ｃｏｌｏｒｅｄ Ｓｔｏｎｅ Ｇｒａｄｉｎｇ Ｓｙｓｔｅｍ]”に準拠して数値化される。この場合、色相、“色調”(明暗)および彩度が評価される。本発明によって達成される効果の主眼は、着色皮膜の特別な後処理がなければ前記の基準の少なくともいずれか一つにつき金属鋳込み時に２ポイント以上の変化を生ずると考えられる石が今や最高でも２ポイント、通例せいぜい１ポイントのずれしか示さない点にある。これは蝋型の焼失時と金属の鋳込み時に生ずる負荷を先取りする高エネルギ処理によって達成される。 If the jewelry stones prepared in this way were subsequently processed by the method of making jewelry shown in FIGS. 1 to 3, it would result in an undesirable and very inconvenient color change of the jewelry stones. These color changes are quantified in accordance with the "Colored Stone Grading System" of the Geological Institute of America. In this case, the hue, “hue” (light and dark) and saturation are evaluated. The main effect of the present invention is that stones, which would otherwise produce more than two points of change during metal casting for at least one of the above criteria without special post-treatment of the colored coating, are now at most 2 The point is that it typically shows at most one point shift. This is achieved by a high energy treatment which preempts the loads which occur during the burning out of the wax mold and during the casting of the metal.
続いて以下に、本発明による装身具の製造方法を実施するための幾つかの例を示す。その際、使用される顔料の表示は米国化学学会のＣＡＳ登録番号の記載によって行う。高温用に適した顔料はウルマン[Ｕｌｌｍａｎｎ]、工業化学百科事典１９８６、Ａ５巻、特にｐ.５４６／５４７に挙げられている。これらの着色剤含有層はすべて本発明により直接にかまたは適切な中間層、包埋層または被覆層の選定により金属鋳込み時にもはや色変しないようにして作り出すことができる。 Next, several examples for carrying out the method for manufacturing an accessory according to the present invention will be described below. In this case, the pigment used is indicated by the description of the CAS registration number of the American Chemical Society. Pigments suitable for high temperatures are listed in Ullmann, Encyclopedia of Industrial Chemistry 1986, Volume A5, especially pages 546/547. All of these colorant-containing layers can be produced according to the invention either directly or by the selection of a suitable intermediate layer, embedding layer or covering layer so that they no longer discolor during metal casting.
例１ （比較試験）
立方体のジルコニアに、上述した特許文献１に記載の方法に従って、約３５重量%の酸化コバルト、１０％の酸化アルミニウム、残りは酸化ケイ素から成る層が蒸着によって被着された。続いての熱処理により層の着青が実現された。この着色剤含有層の被着された宝飾石に後処理なしで金属鋳込みを行った場合、１４ｃｔイエローゴールド合金の鋳込み温度（約１０５０°Ｃ）にて宝飾石の色変が生じた。
Example 1 (Comparative test)
A layer consisting of about 35% by weight of cobalt oxide, 10% of aluminum oxide and the balance silicon oxide was deposited by vapor deposition on cubic zirconia according to the method described in the above-mentioned patent document. Subsequent heat treatment resulted in the layer bluening. When metal casting was performed on the jewelry stone with the colorant-containing layer applied thereto without post-treatment, the color change of the jewelry stone occurred at a casting temperature of 14 ct yellow gold alloy (about 1050 ° C.).
新たに、被着済みの宝飾石が１０分間にわたり１２００°Ｃに加熱され、続いて１時間にわたって７５０°Ｃ（蝋型焼失温度に相当）にて加熱処理された。前記の熱処理により、１４ｃｔパラジウム−ホワイトゴールド合金の鋳込み温度（１２５０°Ｃ）時にも一度として爾後の変化は生じなかった。 The newly applied jewelry stone was heated to 1200 ° C. for 10 minutes, followed by heat treatment at 750 ° C. (corresponding to the wax-type burnout temperature) for 1 hour. Due to the above heat treatment, no further change occurred once even at the casting temperature (1250 ° C.) of the 14 ct palladium-white gold alloy.
例２ （比較試験）
ジルコニアにＣＡＳ ６８１８６−８５−６の組成の顔料（緑色セン晶石、Ｃｏ2ＴｉＯ4）がやや過剰のＴｉｏ2とともに反応性スパッタにより低温にて蒸着された。１４ｃｔパラジウム−ホワイトゴールド合金の鋳込み時に明確に視認可能な緑色被着層の色変が生じた。
Example 2 (Comparative test)
A pigment of the composition CAS 68186-85-6 (green sensite, Co 2 TiO 4 ) was deposited on zirconia at a low temperature by reactive sputtering with a slight excess of TiO 2 . During casting of the 14 ct palladium-white gold alloy, a clearly visible color change of the green deposited layer occurred.
これに対して、前記の層が1分間にわたり１２００°Ｃで加熱処理された場合には、前記の宝飾石は鋳込み時に視認可能な色変を示さなかった。 In contrast, when the layer was heat treated at 1200 ° C. for one minute, the jewelry stone did not show a visible color change upon casting.
これに対して、１２００°Ｃで調質された宝飾石が１４ｃｔイエローゴールド合金メルト中に鋳込まれた場合には、それにもかかわらず褐色がかった色変が生じた。この色変は着色剤含有層が合金と直接に接触していた周縁部でもっとも激しかった。 In contrast, when the jewelry stone tempered at 1200 ° C. was cast into a 14 ct yellow gold alloy melt, it nevertheless developed a brownish color change. This color change was most pronounced at the periphery where the colorant-containing layer was in direct contact with the alloy.
着色剤含有層にさらにアルミン酸マグネシウムから成る保護層が被着され、この宝飾石が１２００°Ｃで加熱処理された場合には、高温のイエローゴールド合金と直接に接していた箇所でも色調の変化は生じなかった。 When a protective layer made of magnesium aluminate is further applied to the colorant-containing layer, and the jewelry stone is heated at 1200 ° C., the color tone changes even in a portion directly in contact with the high-temperature yellow gold alloy. Did not occur.
例３:
薄いＳｉＯ2層上に酸化鉄系顔料を酸化アルミニウムから成る包埋母材とともに被着することにより、顔料ＣＡＳ ６８１８７−３５−９（渇鉄鉱、Ｆｅ2Ｏ3）ベースの着色剤含有層が温度安定化されかつ化学的・機械的耐性が付与されて形成された。１２００°Ｃでの１０分間にわたる処理に続いて７５０°Ｃにて２時間にわたる後処理が行われた。このようにして包埋されて熱処理された顔料の色調はもはや純粋な顔料の色と正確には同じではないが、その代わりこの色は金属鋳込み時にも変化しなかった。
Example 3:
Thin iron oxide pigment on the SiO 2 layer with embedding matrix consisting of aluminum oxide by depositing pigment CAS 68187-35-9 (渇鉄ore, Fe 2 O 3) based colorant-containing layer is temperature Formed with stabilized and chemical and mechanical resistance. A 10 minute treatment at 1200 ° C. was followed by a 2 hour post treatment at 750 ° C. The color tone of the pigments embedded and heat-treated in this way is no longer exactly the same as the color of the pure pigment, but instead this color does not change upon metal casting.
例４:
ジルコニアに顔料ＣＡＳ ６８１８７−０５−３、組成式Ｃｏ2ＳｎＯ4の灰青スピネルによる被着が行われた。約１２５ｍｍの顔料層は酸化アルミニウムから成る厚い保護層で被覆され、１分間にわたり１２００°Ｃに加熱された。続いてこの宝飾石は空気中で３０分間にわたって７５０°Ｃにて加熱処理された。生じた着色青は純銀中への鋳込み時にも保たれていた。
Example 4:
Zirconia was coated with a pigment CAS 68187-05-3 and a grayish blue spinel of the composition formula Co 2 SnO 4 . A pigment layer of about 125 mm was covered with a thick protective layer of aluminum oxide and heated to 1200 ° C. for 1 minute. The gemstone was then heat treated at 750 ° C. for 30 minutes in air. The resulting colored blue was retained during casting into pure silver.
前記の例のそれぞれにおいて、宝飾石の着色剤含有層は金属鋳込み時に生ずる温度によって損傷され得るだけではないとの点が明らかになった。むしろ宝飾石と着色剤含有層との間の界面および特に着色剤含有層の外面にも望ましくない変化が生じ得るが、そうした変化は分離層によって回避することが可能である。これによって特に、真正色の宝飾石の場合にも金属鋳込み時に光沢が損なわれ得るとの事実が顧慮される。 In each of the foregoing examples, it was found that the colorant-containing layer of the jewelry stone could not only be damaged by the temperatures that occur during metal casting. Rather, undesired changes may also occur at the interface between the gemstone and the colorant-containing layer, and especially at the outer surface of the colorant-containing layer, but such changes can be avoided by the separating layer. This takes into account, in particular, the fact that even in the case of authentic jewelry stones, the luster can be impaired during metal casting.
宝飾石の着色コートされた裏面も機械的作用、特に研磨材またはその他の装身具の衝撃作用ならびにダイアモンド砥粒の摩耗作用から保護しようとする場合には、図４に示したように、宝飾石の裏面が鋳込み金属によって形成されたリングによって取囲まれるようにすることができる。 If the colored coated back side of the jewelry stone is also to be protected from mechanical action, particularly the impact action of abrasives or other jewelry as well as the wear action of diamond abrasive grains, as shown in FIG. The back surface can be surrounded by a ring formed by a cast metal.
１ 宝飾石
２ 裏面
３ リング
４ 金属
５ 成形材料
６ 蝋
７ 空洞
DESCRIPTION OF
Claims (8)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ATA800/2003 | 2003-05-23 | ||
| AT0080003A AT412402B (en) | 2003-05-23 | 2003-05-23 | METHOD FOR PRODUCING A JEWEL PIECE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004344651A true JP2004344651A (en) | 2004-12-09 |
| JP4707968B2 JP4707968B2 (en) | 2011-06-22 |
Family
ID=32686613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004139330A Expired - Lifetime JP4707968B2 (en) | 2003-05-23 | 2004-05-10 | Method for manufacturing jewelry that casts metal so as to surround jewelry stone, and jewelry stone suitable for this |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20040231158A1 (en) |
| EP (1) | EP1479308B1 (en) |
| JP (1) | JP4707968B2 (en) |
| KR (1) | KR20040100911A (en) |
| CN (1) | CN1572541B (en) |
| AT (1) | AT412402B (en) |
| HK (1) | HK1072750A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014121609A (en) * | 2012-12-21 | 2014-07-03 | Omega Sa | Decorative component and method for manufacturing the same |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7526928B1 (en) | 2002-11-04 | 2009-05-05 | Azotic Coating Technology, Inc. | Multi-color gemstones and gemstone coating deposition technology |
| KR100742158B1 (en) * | 2006-01-04 | 2007-07-24 | 이미운 | a display grill stand |
| US9084457B2 (en) * | 2011-06-03 | 2015-07-21 | Krush To Pleve Llc | Multiple piece jewelry piece and method of manufacture |
| CN102406290B (en) * | 2011-10-20 | 2014-05-07 | 牟小燕 | Fantastic artificial jewelry and preparation method thereof |
| ITVR20120007A1 (en) * | 2012-01-13 | 2013-07-14 | Patros S R L | PRODUCT MANUFACTURED FOR JEWELERY AND / OR THE WALL AND / OR THE ZIRCONIC OXIDE-BASED JEWELERY AND ITS METHOD |
| WO2015010142A1 (en) * | 2013-07-26 | 2015-01-29 | D. Swarovski Kg | Method for fastening precious stones |
| CN106086970A (en) * | 2016-06-17 | 2016-11-09 | 钟福龙 | A kind of processing method of natural jade spar class bijouterie |
| CN112368790B (en) * | 2018-02-22 | 2024-04-26 | 通用工程与研究有限责任公司 | Magnetocaloric alloy for magnetic refrigeration applications |
| CN108297600A (en) * | 2018-03-26 | 2018-07-20 | 中国地质大学（武汉） | The special Electric soldering pen of pyrography |
| CN108618288A (en) * | 2018-05-21 | 2018-10-09 | 深圳市萃华珠宝首饰有限公司 | A kind of bullion processing method |
| CN111318614B (en) * | 2018-12-16 | 2022-03-29 | 青岛丰和工艺品有限公司 | Metal diamond-inlaid jewel ornament, method and die |
| EP3797635A1 (en) | 2019-09-24 | 2021-03-31 | D. Swarovski KG | Decorative articles having a changeable observed colour effect |
| CN112410773B (en) * | 2020-11-02 | 2022-11-25 | 山东恒银珠宝有限公司 | Gold antique finishing method and antique gold |
| DE102021100591B3 (en) | 2021-01-13 | 2022-02-17 | Friedrich Erodierservice GmbH | Manufacturing process for a piece of jewelery and a piece of jewellery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3837884A (en) * | 1971-07-12 | 1974-09-24 | Balzers Patent Beteilig Ag | Method of producing blue colored transparent layers |
| JPS61206404A (en) * | 1985-03-07 | 1986-09-12 | カミユ・リシヤルド | Inlay of jewel and quasi-jewel |
| WO1998048944A1 (en) * | 1997-04-25 | 1998-11-05 | Richard Pollak | Method for enhancing the color of minerals useful as gemstones |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2623192B2 (en) * | 1976-05-24 | 1980-01-31 | J.E. Hammer & Soehne, 7530 Pforzheim | Method for setting precious stones in jewelry bodies made of precious metal |
| DE3908472C1 (en) * | 1989-03-15 | 1991-01-31 | Alois Ach Oberoesterreich At Lechner | Process for producing mounts from metals for precious and semiprecious stones |
| US5188679A (en) * | 1990-07-19 | 1993-02-23 | Kretchmer Steven D | Metal compression-spring gemstone mountings |
| DE4140121C2 (en) * | 1991-12-05 | 1994-06-30 | Manfred Mueller | Process for the production of set, cast jewelry |
| US5690477A (en) * | 1996-07-08 | 1997-11-25 | Nili Jewelry, Corp. | Invisible setting method for jewelry |
| CN1194198A (en) * | 1997-03-21 | 1998-09-30 | 尼立珠宝股份有限公司 | Invisible setting method for jewelry |
| US6376031B1 (en) * | 1998-04-24 | 2002-04-23 | Richard Pollak | Method for enhancing the color of minerals useful as gemstones |
| CH693662A5 (en) * | 1998-09-02 | 2003-12-15 | Nelson Jewellery Arts Co Ltd | Piece of jewelry. |
| US6997014B2 (en) * | 2002-11-04 | 2006-02-14 | Azotic Coating Technology, Inc. | Coatings for gemstones and other decorative objects |
-
2003
- 2003-05-23 AT AT0080003A patent/AT412402B/en not_active IP Right Cessation
-
2004
- 2004-04-19 EP EP04009191A patent/EP1479308B1/en not_active Expired - Lifetime
- 2004-05-03 US US10/836,249 patent/US20040231158A1/en not_active Abandoned
- 2004-05-10 JP JP2004139330A patent/JP4707968B2/en not_active Expired - Lifetime
- 2004-05-12 KR KR1020040033349A patent/KR20040100911A/en not_active Application Discontinuation
- 2004-05-21 CN CN2004100453972A patent/CN1572541B/en not_active Expired - Lifetime
-
2005
- 2005-06-29 HK HK05105494.5A patent/HK1072750A1/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3837884A (en) * | 1971-07-12 | 1974-09-24 | Balzers Patent Beteilig Ag | Method of producing blue colored transparent layers |
| JPS61206404A (en) * | 1985-03-07 | 1986-09-12 | カミユ・リシヤルド | Inlay of jewel and quasi-jewel |
| WO1998048944A1 (en) * | 1997-04-25 | 1998-11-05 | Richard Pollak | Method for enhancing the color of minerals useful as gemstones |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014121609A (en) * | 2012-12-21 | 2014-07-03 | Omega Sa | Decorative component and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| US20040231158A1 (en) | 2004-11-25 |
| AT412402B (en) | 2005-02-25 |
| JP4707968B2 (en) | 2011-06-22 |
| CN1572541B (en) | 2010-04-28 |
| KR20040100911A (en) | 2004-12-02 |
| EP1479308B1 (en) | 2012-05-23 |
| EP1479308A1 (en) | 2004-11-24 |
| HK1072750A1 (en) | 2005-09-09 |
| ATA8002003A (en) | 2004-07-15 |
| CN1572541A (en) | 2005-02-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4707968B2 (en) | Method for manufacturing jewelry that casts metal so as to surround jewelry stone, and jewelry stone suitable for this | |
| RU2621229C2 (en) | Ceramic element encrusted by decoration of composite ceramics | |
| TWI388950B (en) | A piece for technical and/or decorative use and method of manufacturing a piece for technical and/or decorative use | |
| EP3035129A1 (en) | Method for producing a decorated element of a timepiece or piece of jewellery, and element produced by the method | |
| US4599251A (en) | Decorated article, method of fabricating the same and substrates used in connection therewith | |
| KR100581670B1 (en) | Dental construct and method of producing the same | |
| JPH10130068A (en) | Ceramic structure and its production | |
| RU2436746C2 (en) | Mass of crystal glass with decorative effect of dichromatic nature | |
| CN109942189A (en) | A kind of dark metal glaze ceramics of environmental-friendly lead-free and its manufacture craft | |
| US5127835A (en) | Process for preparation of dental crown restoration and kit for use in carrying out said process | |
| KR20220145278A (en) | Method for producing a ceramic part with a mother-of-pearl effect, particularly for watchmaking | |
| CN111574065A (en) | Coloured watch glass | |
| EP3226082B1 (en) | Timepiece movement component | |
| JPH02185934A (en) | Gold alloy capable of coloring bright brown and coloring method therefor | |
| CN212280226U (en) | Enamel gem ornament decoration | |
| CN117230343A (en) | Customization method of transparent enamel without K gold color | |
| JP6997328B2 (en) | Watch dials and methods for making them | |
| JPH03100159A (en) | Platinum alloy to be brightly blackened and method for blackening the same | |
| JP2007254849A (en) | Metallic oxide film, and member coated with the metallic oxide film | |
| JP3088978U (en) | Titanium coating muffler | |
| Li | Porcelain Techniques in Ancient China | |
| JPH02185935A (en) | Gold alloy capable of coloring bright black and coloring method therefor | |
| JPH1128112A (en) | Ornament and its production | |
| JP2018057683A (en) | Manufacturing method for cloisonne ware | |
| CN111358127A (en) | Enamel gem ornament decoration and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070508 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20091117 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20100209 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20100209 |
|
| A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20100223 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100312 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20100615 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20101014 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20101025 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110118 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110120 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110215 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110316 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4707968 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: R3D03 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |