KR880001630B1 - Artificial's making method of adornments - Google Patents
Artificial's making method of adornments Download PDFInfo
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- KR880001630B1 KR880001630B1 KR1019860009607A KR860009607A KR880001630B1 KR 880001630 B1 KR880001630 B1 KR 880001630B1 KR 1019860009607 A KR1019860009607 A KR 1019860009607A KR 860009607 A KR860009607 A KR 860009607A KR 880001630 B1 KR880001630 B1 KR 880001630B1
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- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
- A44C27/00—Making jewellery or other personal adornments
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
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- Manufacturing & Machinery (AREA)
- Physical Vapour Deposition (AREA)
- Adornments (AREA)
Abstract
Description
도면은 본 발명의 실시에 사용되는 이온 플레이팅(ionplating)장치의 개략 설명도.BRIEF DESCRIPTION OF THE DRAWINGS The schematic explanatory drawing of the ion plating apparatus used for implementation of this invention.
* 도면의 주요부분에 대한 부호의 설명* Explanation of symbols for main parts of the drawings
1 : 진공 용기 2 : 증발원1: vacuum vessel 2: evaporation source
3 : 피처리재 지지부 4 : 피처리재3: material to be treated 4: material to be treated
5 : 기체주입구 6 : 배기구5 gas inlet 6 exhaust port
7 : 전자 비임 발생장치 8 : 테이블7: electron beam generator 8 table
9 : 직류 전원9: DC power
본 발명은 회색에서 흑색에 이르는 다양한 흑색 색조를 가지는 손목시계 케이스, 시계줄, 안경테와 같은 장신구 제조 방법, 특히 이온 플레이팅 방법을 이용한 흑색피막형성 방법에 관한 것이다.The present invention relates to a method for producing jewelry such as a watch case, a watch band, and an eyeglass frame having a variety of black tones ranging from gray to black, particularly a method of forming a black film using an ion plating method.
종래, 이온 플레이팅 방법을 이용하여 손목시계 케이스, 시계줄, 안경테와 같은 장신구의 표면에 아름다운 흑색피막을 형성하는 기술이 알려져 있다. 예로써, 일본국 특허 공보 제56-53716호에는 감압하의 가열된 질소분위기 중에서 피처리재와 금속 티타늄 사이에 500-4000볼트의 고전압을 걸어주어 상기 피처리재의 표면상에 티타늄 질화물이 주가되는 흑색피막을 형성하는 방법이 기재되어 있으며, 또한 일본국 특허 공개 공보 60-208472호에는 아르곤, 질소 및 탄화수소 화합물을 함유한 분위기의 이온 플레이팅 방법이 기재되어 있다.Background Art Conventionally, a technique of forming a beautiful black film on the surface of jewelry such as a watch case, a watch band, and an eyeglass frame using an ion plating method is known. For example, Japanese Patent Publication No. 56-53716 discloses black titanium in which titanium nitride is mainly applied on the surface of the workpiece by applying a high voltage of 500-4000 volts between the workpiece and the metal titanium in a heated nitrogen atmosphere under reduced pressure. A method of forming a film is described, and Japanese Patent Laid-Open No. 60-208472 describes an ion plating method of an atmosphere containing argon, nitrogen, and a hydrocarbon compound.
상기한 방법은 제품 표면상에 광택이 있는 흑색피막을 형성하는데 효과적이기는 하지만 다음에 같은 단점이 있다. 예를 들면, 첫번째 방법은 호닝(honing)법에 의한 피처리재의 전처리시에 사용한 글래스 비드, 알루미나 분말과 같은 피처리재의 표면상에 잔류하는 지립을 제거하기가 곤란하여 피처리재와 티타늄 증발원 사이에 고전압을 걸어주면 이상방전 또는 스퍼터링(sputtering)이 발생하고, 티타늄 질화물의 형성반응이 불안정하여 균일한 흑색 색조의 피막을 형성시키기가 어렵고, 때로는 흑색 색조에 황색 색조가 나타나기도 한다. 상기 두번째 방법의 문제점은 형성된 피막에 다소간의 탄소 성분이 함유되어 있어, 이것에 의해 피막의 응력이 증가하여 피막이 벗겨지는 원인이 된다. 또한 분위기를 형성하는 3종의 기체 비율을 정확하게 조절하기가 곤란하므로 동일한 색조를 계속해서 얻기가 어렵다.The above method is effective for forming a glossy black film on the surface of the product, but has the following disadvantages. For example, the first method is difficult to remove the abrasive grains remaining on the surface of the workpiece such as glass beads and alumina powder used during the pretreatment of the workpiece by the honing method. When a high voltage is applied to it, abnormal discharge or sputtering occurs, and the formation reaction of titanium nitride is unstable, making it difficult to form a uniform black tint, and sometimes a yellow tint appears in the black tint. The problem with the second method is that some of the carbon components are contained in the formed film, which increases the stress of the film and causes the film to peel off. In addition, since it is difficult to accurately adjust the ratio of three kinds of gases forming the atmosphere, it is difficult to continuously obtain the same color tone.
본 발명의 목적은 상기한 문제점을 해소한 이온 플레이팅법에 의해 보석과 같은 광택을 가지는 흑색 색조의 장신구의 제조방법을 제공하는 것이다.An object of the present invention is to provide a method for producing jewelry of black hue having a gloss like gemstone by the ion plating method which solves the above problems.
본 흑색 색조의 장신구 제조방법은(a)0.1-5.0용적%의 산소와 0.1-3.0용적%의 이산화탄소를 함유하는 5×10-4내지 1×10-2Torr의 압력하의 질소와 아르곤의 혼합기체 분위기 중에 전도성 표면을 가지는 피처리재를 금속티타늄의 증발원에 대항되게 유지하는 단계, (b)금속티타늄 증발원을 가열하여 티타늄을 기화시키는 단계, (c)상기 피처리재와 금속 티타늄 증발원간에 1-450볼트, 바람직하게는 10-100볼트의 전압을 걸어 주는 단계로 구성된다.This black tint jewelry production process includes (a) a mixture of nitrogen and argon under a pressure of 5 × 10 -4 to 1 × 10 -2 Torr containing 0.1-5.0 vol% oxygen and 0.1-3.0 vol% carbon dioxide Maintaining a workpiece having a conductive surface in an atmosphere against an evaporation source of metal titanium, (b) heating the metal titanium evaporation source to vaporize titanium, and (c) between the treated material and the metal titanium evaporation source. It consists of applying a voltage of 450 volts, preferably 10-100 volts.
이하, 첨부한 도면을 참고하여 본원 발명에 대해 상세히 설명한다.Hereinafter, with reference to the accompanying drawings will be described in detail with respect to the present invention.
진공 용기(1)의 아래쪽에 설치된 테이블(8)상에 금속티타늄 증발원(2)를 설치하고, 진공 용기(1)의 상부에는 호닝처리나 화학처리와 같은 표면전 처리를 한 전도성 ㅍ면을 가지는 피처리재(4)(예, 시계케이스)를 피처리재 지지부(3)에 의해 금속티타늄 증발원(2)에 대항되게 유지시킨다. 피처리재(4)는 그것이 전기 전도성일 경우 어느것이나 가능하다. 다음에, 배기구(6)을 통해 진공 용기(1)내의 공기를 배기시킨 후, 기체 주입구(2)를 통해 질소와 아르곤의 혼합기체를 주입하여 용기(1)내의 압력을 5×10-4내지 1×10-2Torr, 바람직하게는 8×10-4내지 5×10-3Torr로 유지시킨다. 주입기체가 질소와 아르곤의 혼합기체일 경우, 질소 기체가 50용적%이상이면 이들 두 기체의 용적비는 특별히 제한되지 않는다. 질소와 아르곤으로된 기체 분위기내에 산소와 이산화탄소와 같은 불순개스가 가능한한 거의 함유디어서는 안되는 종래의 이온 플레이팅 방법과는 달리 본 발명에서는 용기(1)내에 주입되는 기체내에 0.1-5.0용적%의 산소와 0.1-3.0용적%의 이산화탄소가 함유되어야 한다는 것이 그 특징이다. 상기와 같은 용기내의 분위기를 유지한 상태에서 양극인 금속티타늄 증발원(2)와 음극인 피처리물(4)간에 질류전원(9)에 의해 1-450볼트, 바람직하게는 10-100볼트의 직류전압을 걸어어준다. 종래의 기술에서는 500볼트 이상의 전압을 사용한데 비해 이와같이 비교적 낮은 전압을 걸어주는 것도 본 발명의 특징이다.A metal titanium evaporation source 2 is installed on the table 8 provided below the vacuum vessel 1, and the upper portion of the vacuum vessel 1 has a conductive surface which is subjected to surface pretreatment such as honing or chemical treatment. The treatment material 4 (e.g., a watch case) is held against the metal titanium evaporation source 2 by the treatment material support 3. The workpiece 4 can be any if it is electrically conductive. Next, after evacuating the air in the vacuum container 1 through the exhaust port 6, a mixed gas of nitrogen and argon is injected through the gas inlet 2, and the pressure in the container 1 is increased from 5 x 10 < -4 > 1 × 10 −2 Torr, preferably 8 × 10 −4 to 5 × 10 −3 Torr. When the injection gas is a mixture of nitrogen and argon, the volume ratio of these two gases is not particularly limited as long as the nitrogen gas is 50 vol% or more. In contrast to conventional ion plating methods in which a gaseous atmosphere of nitrogen and argon should contain as little as possible impurity gases such as oxygen and carbon dioxide, in the present invention, 0.1-5.0% by volume in the gas injected into the container 1 Its characteristic is that it should contain oxygen and 0.1-3.0% by volume of carbon dioxide. A direct current of 1-450 volts, preferably 10-100 volts, between the metal titanium evaporation source (2), which is the anode, and the object (4), which is the cathode, by the nitrate power source (9) while maintaining the atmosphere in the vessel as described above. Apply voltage. In the prior art, a voltage of 500 volts or more is used, but it is also a feature of the present invention to apply a relatively low voltage.
전류는 피처리재의 치수에 특별히 제한되지 않으나, 처리할 제품의 시계 케이스, 시계줄, 안경태 등과 같이 비교적 소형인 경우, 0.1-5암페어, 바람직하게는 0.5-2암페어의 전류를 유지시킨다. 이와 동시에. 금속티타늄 중발원(2)를 적절한 수단에 의해 가열하여 티타늄을 기하시키며, 기화를 효과적으로 하기위해 티타늄 증발원의 온도를 약 1600℃ 또는 1500-1700℃의 범위로 유지시켜야 한다. 금속티타늄의 증발원(2)를 가열시키는 방법은 금속티타늄의 증발원(2)에 대해 적절한 가속 전압으로 전자 비임 발생장치(7)로 부터 방출된 전자 비임에 의해 금속티타늄에 충격을 가하는 것으로, 기체 주입구(5)로 부터 주입된 기체내에 함유된 산소, 이산화탄소와 같은 비교적 낮은 이온화 포텐셜을 가지는 불순기체는 상기 전자 비임의 충격에 의해 이온화하여 형성된 피막의 색조에 영향을 주게 된다. 기체 분위기내에 존재하는 상기 불순기체에 의해 형성된 피막의 색조가 상당한 영향을 주게 된다. 기체 분위기내에 존재하는 상기 불순기체에 의해 형성된 피막의 색조가 상당한 영향을 받아 재생성과 확실성이 높은 아름다운 흑색 색조를 형성한다는 것과 피처리재에 형성된 주로 티타늄 질화물의 아름다운 흑색 피막에 다량의 산소와 탄소(20중량%이상)가 함유된다는 사실의 발견은 매우 중요한 발견이다. 일예로써, 본 발명의 방법에 따라 형성된 피막은 30중량%의 티타늄, 20중량%의 질소, 25중량%의 산소 및 20중량%의 탄소로 구성되어 있으며, 이같은 분석 결과는 산소와 탄소 화합물만을 함유한 종래 방식의 분위기에 의해 형성된 45중량%의 티타늄, 45중량%의 질소, 5중량%의 산소 및 5중량%의 탄소로 구성된 황금색조의 티타늄 질화물 피막과 명확히 구별되는 것이다.The current is not particularly limited to the dimensions of the material to be treated, but when it is relatively small, such as a watch case, watch strap, eyeglasses, etc. of the product to be treated, it maintains a current of 0.1-5 amps, preferably 0.5-2 amps. At the same time. The metal titanium medium source (2) is heated by appropriate means to geometry titanium, and the temperature of the titanium evaporation source must be maintained in the range of about 1600 ° C or 1500-1700 ° C in order to effectively vaporize. The method of heating the evaporation source (2) of metal titanium is to impinge on the metal titanium by the electron beam emitted from the electron beam generator (7) at an appropriate acceleration voltage with respect to the evaporation source (2) of the metal titanium, the gas inlet Impurity gases having relatively low ionization potentials such as oxygen and carbon dioxide contained in the gas injected from (5) affect the color tone of the film formed by ionization by the impact of the electron beam. The color tone of the film formed by the impurity gas present in the gaseous atmosphere has a significant effect. The color tone of the film formed by the impurity gas present in the gaseous atmosphere is significantly influenced to form a beautiful black color tone with high reproducibility and certainty, and a large amount of oxygen and carbon ( The fact that more than 20% by weight) is contained is a very important finding. In one example, the coating formed according to the method of the present invention is composed of 30% by weight titanium, 20% by weight nitrogen, 25% by weight oxygen and 20% by weight carbon, the analysis results containing only oxygen and carbon compounds It is clearly distinguished from the golden-colored titanium nitride film composed of 45% titanium, 45% nitrogen, 5% oxygen and 5% carbon by the conventional atmosphere.
전술한 용기(2)내의 기체분위기의 압력이 전술한 압력 범위의 하한치이하이면 금속티타늄 증발원(2)와 피처리재(4)사이의 포텐셜차가 불충분하여 이온 플레이팅에 의한 티타늄 질화물이 효과적으로 형성되지 못하며, 기체분위기의 압력이 지나치게 크면 글로우(glow)방전이 발생하여 피처리재(4)에 형성된 티타늄 질화물의 표면이 거칠어지게 된다. 금속티타늄의 증발원(2)와 피처리재(4)사이의 전류가 지나치게 크면 산소와 탄소의 함량이 적은 TiN 형성 반응이 우선함으로써 피처리재(4)에 형성된 피막의 색조가 황색이 되어 흑색의 장신구로서의 미적가치가 떨어진다.If the pressure of the gas atmosphere in the above-mentioned container 2 is below the lower limit of the above-mentioned pressure range, the potential difference between the metal titanium evaporation source 2 and the material to be treated 4 is insufficient to effectively form titanium nitride by ion plating. If the pressure of the gas atmosphere is too high, a glow discharge occurs and the surface of the titanium nitride formed on the workpiece 4 becomes rough. If the current between the evaporation source 2 of the metal titanium and the workpiece 4 is too large, the TiN formation reaction with less oxygen and carbon content takes precedence, so that the color tone of the film formed on the workpiece 4 becomes yellow and black. Aesthetic value as a trinket falls.
이하, 실시예에 의해 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
[실시예 1]Example 1
금속티타늄재의 안경테를 이온 플레이팅 용기내의 금속티타늄 증발원 상부의 지지부에 장착했다. 용기내의 공기를 배기시킨후, 제1표에 표시한 비율로 산소와 이산화탄소를 함유한 질소와 아르곤의 혼합기체를 주입하여 용기내의 압력을 5×10-3Torr로 유지했다. 양극인 금속티타늄 증발원과 음극인 피처리재 사이의 전압을 10,50,100,200 또는 400볼트로 하여 각각 1,10,15,20 또는 30암페어의 이온 저류를 발생시켰다. 다음에 금속티타늄을 10킬로볼트의 가속 전압으로 0.3암페어의 전자 비임의 충격에 의해 1600℃의 온도로 가열시켜 티타늄을 증발시킴에 의해 상기 안경테의 표면에 피막을 형성시켰다. 이와 같은 이온 플레이팅 공정을 30분간 지속했다. 형성된 피막의 광택 및 색조를 육안으로 검사한 결과, 광택이 있는 피막은 음극 전압이 50볼트 이상일때 얻어진다는 것을 알았다. 하기 제1표는 질소와 아르곤의 혼합기체 분위기내의 산소와 이산화탄소의 함량 및 음극 전압의 각 조합에서 얻어진 색조를 도표화한 것으로, 음극 전압이 400볼트일때 얻어지는 탄(scorched)색조라 함을 적색, 청색, 녹색이 혼합된 흑색색조를 뜻한다.A spectacle frame made of a metal titanium material was attached to a support on the upper part of the metal titanium evaporation source in the ion plating container. After evacuating the air in the vessel, a mixture gas of nitrogen and argon containing oxygen and carbon dioxide was injected at the ratio shown in the first table to maintain the pressure in the vessel at 5 x 10 -3 Torr. Ion storage of 1, 10, 15, 20 or 30 amperes was generated at a voltage of 10, 50, 100, 200 or 400 volts between the metal titanium evaporation source as the anode and the material to be treated as the cathode. Next, a film was formed on the surface of the spectacle frame by heating the metal titanium to a temperature of 1600 ° C by the impact of an electron beam of 0.3 amps at an acceleration voltage of 10 kilovolts and evaporating titanium. This ion plating process was continued for 30 minutes. As a result of visual inspection of the gloss and color tone of the formed film, it was found that the glossy film was obtained when the cathode voltage was 50 volts or more. Table 1 below shows the color tone obtained from each combination of oxygen and carbon dioxide content and cathode voltage in a mixed gas atmosphere of nitrogen and argon, and is called a scorched hue obtained when the cathode voltage is 400 volts. It means black tones mixed with green.
[제1표][Table 1]
[실시예 2]Example 2
이온 플레이팅 용기내의 압력을 8×10-4Torr로 유지하고, 산소와 이산화탄소의 농도는 제2표에 표시한 농도로하여 실시예 1과 동일한 시험을 실시했다. 금속티탄늄의 증발원의 온도는 1500℃였다. 피처리재와 금속티타늄 증발원 사이의 이온 전류는 10,50, 100,200 및 400볼트의 음극 전압에 대해 각각 0.5,5,10,15 및 20암페어 였다. 30분간 처리결과, 산소와 이산화탄소의 농도를 제2표에 제시된 값이하로 했을때 흑색 색조를 얻을 수 없었으며, 음극 전압이 10볼트일때 형성된 피막은 무광택이었다. 제2표는 질소와 아르곤의 혼합기체내의 산소 및 이산화탄소의 농도와 음극전압의 여러 조합에서 표면처리를한 안경테의 색조를 나타낸 것이다.The pressure in the ion plating vessel was maintained at 8 x 10 < -4 > Torr, and the same test as in Example 1 was conducted at the concentrations shown in the second table. The temperature of the evaporation source of metal titaniumium was 1500 degreeC. The ion currents between the workpiece and the metal titanium evaporation source were 0.5, 5, 10, 15 and 20 amps for cathode voltages of 10, 50, 100, 200 and 400 volts, respectively. As a result of 30 minutes of treatment, when the concentrations of oxygen and carbon dioxide were below the values shown in Table 2, no black tint was obtained, and the film formed when the cathode voltage was 10 volts was matt. The second table shows the color tone of the spectacle frames subjected to the surface treatment at various combinations of oxygen and carbon dioxide concentrations in the mixed gas of nitrogen and argon and cathode voltage.
[표 2]TABLE 2
[실시예 3]Example 3
황동제 시계 케이스에 일차로 3㎛ 두께의 니켈도금을 하고 다음에 3㎛ 두께의 팔라디움 및 합금으로 도금한 것을 피처리재로 하였다. 실험 방법은 실시예 1과 동일하게 하였으며, 질소와 아르곤의 혼합기체 분위기의 압력은 8×10-4Torr, 산소와 이산화탄소의 농도는 각각 4용적%와 3용적%로 하였다. 5암페어의 이온 전류를 발생시키기 위해 음극 전압을 50볼트로 하였으며, 금속 티타늄 증발원을 1500℃로 가열시키기 위해 10킬로볼트의 가속 전압에서 충격용 전자비임의 전류를 0.3암페어로 하였다. 그 결과 1㎛의 두께를 가진 광택이 있는 흑색 색조의 피막을 얻었다.The brass watch case was first plated with 3 탆 thick nickel and then plated with 3 탆 thick palladium and alloy as the material to be treated. Experimental method was the same as in Example 1, the pressure of the mixed gas atmosphere of nitrogen and argon was 8 × 10 -4 Torr, the concentration of oxygen and carbon dioxide was 4% by volume and 3% by volume, respectively. The cathode voltage was 50 volts to generate an ion current of 5 amps, and the current of the impact electron beam was 0.3 amps at an acceleration voltage of 10 kilovolts to heat the metal titanium evaporation source to 1500 ° C. As a result, a gloss black film having a thickness of 1 μm was obtained.
[실시예 4]Example 4
스텐레스강제 시계줄을 피처리재로 하여 전술한 실시예와 동일한 방법으로 실험을 실시했다. 질소와 아르곤의 혼합기체 분위기의 압력은 5×10-3Torr, 질소내의 산소와 이산화탄소의 농도는 동일하게 0.1용적%로 했으며, 15암페어의 이온 전류를 발생시키기 위해 음극전압을 100볼트로 하였다. 금속티타늄 증발원을 1600℃로 가열하기 위해 10킬로볼트의 가속전압에서 충격용 전자비임의 전류를 0.3암페어로 하였다. 그 결과 두께가 0.8㎛인 아름다운 회색 색조의 피막을 얻었다.The experiment was carried out in the same manner as in the above-described embodiment using a stainless steel watch band as a treated material. The pressure of the mixed gas atmosphere of nitrogen and argon was 5 × 10 -3 Torr, and the concentration of oxygen and carbon dioxide in nitrogen was equal to 0.1 vol%, and the cathode voltage was 100 volts to generate 15 amperes of ionic current. In order to heat the metal titanium evaporation source to 1600 ° C, the current of the electron beam for impact was 0.3 ampere at an acceleration voltage of 10 kilovolts. As a result, a beautiful gray tint film having a thickness of 0.8 µm was obtained.
[실시예 5]Example 5
실시예 4와 동일한 방법으로 실험을 실시했으며, 질소와 아르곤의 혼합기체 분위기내의 산소와 이산화탄소의 농도는 동일하게 2용적%로 하였다. 그 결과 아름다운 흑색 색조의 피막이 형성되었다.The experiment was conducted in the same manner as in Example 4, and the concentrations of oxygen and carbon dioxide in the mixed gas atmosphere of nitrogen and argon were equally 2 vol%. As a result, a beautiful black tint was formed.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60256108A JPS62116762A (en) | 1985-11-15 | 1985-11-15 | Production of external parts |
| JP60-256108 | 1985-11-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR870004681A KR870004681A (en) | 1987-06-01 |
| KR880001630B1 true KR880001630B1 (en) | 1988-09-03 |
Family
ID=17288001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019860009607A KR880001630B1 (en) | 1985-11-15 | 1986-11-14 | Artificial's making method of adornments |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS62116762A (en) |
| KR (1) | KR880001630B1 (en) |
| DE (1) | DE3637810C2 (en) |
| GB (1) | GB2182950B (en) |
| HK (1) | HK19390A (en) |
| SG (1) | SG11890G (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6362864A (en) * | 1986-09-02 | 1988-03-19 | Seikosha Co Ltd | Blackish-silver article |
| JP2553059B2 (en) * | 1986-12-24 | 1996-11-13 | シチズン時計株式会社 | Manufacturing method of exterior parts |
| CH673071B5 (en) * | 1988-06-24 | 1990-08-15 | Asulab Sa | |
| JP2820451B2 (en) * | 1988-11-22 | 1998-11-05 | シチズン時計株式会社 | Jewelry |
| DE102004019061B4 (en) * | 2004-04-20 | 2008-11-27 | Peter Lazarov | Selective absorber for converting sunlight to heat, a method and apparatus for making the same |
| JP5372283B1 (en) * | 2013-05-30 | 2013-12-18 | 尾池工業株式会社 | Decorative vapor deposition film and method for producing the same |
| CN104257047B (en) * | 2014-08-29 | 2015-09-30 | 浙江新光饰品股份有限公司 | Dog chain maker cut protection device |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH264574A4 (en) * | 1973-03-05 | 1977-04-29 | Suwa Seikosha Kk | Method of plating watch parts in a vacuum container |
| AT344617B (en) * | 1973-06-22 | 1978-08-10 | Plansee Metallwerk | JEWELERY PIECE, FOR EXAMPLE, WATCH BOWL, MADE OF METAL OR CERAMIC BASE MATERIAL |
| CH640886A5 (en) * | 1979-08-02 | 1984-01-31 | Balzers Hochvakuum | METHOD FOR APPLYING HARD WEAR-RESISTANT COATS ON DOCKS. |
| JPS5853716B2 (en) * | 1979-08-24 | 1983-11-30 | セイコーインスツルメンツ株式会社 | Manufacturing method for exterior parts |
| JPS56156767A (en) * | 1980-05-02 | 1981-12-03 | Sumitomo Electric Ind Ltd | Highly hard substance covering material |
| CH667605A5 (en) * | 1983-08-25 | 1988-10-31 | Vni Instrument Inst | MILLING TOOL AND METHOD FOR THE PRODUCTION THEREOF. |
| JPS6089574A (en) * | 1983-10-21 | 1985-05-20 | Mitsubishi Metal Corp | Surface-coated sintered hard alloy member for cutting tool and wear-resistant tool |
| JPS6092465A (en) * | 1983-10-27 | 1985-05-24 | Kowa Eng Kk | Method for forming black film to material to be treated |
| JPS6115967A (en) * | 1984-06-29 | 1986-01-24 | Sumitomo Electric Ind Ltd | Surface treatment |
| JPS61183458A (en) * | 1985-02-08 | 1986-08-16 | Citizen Watch Co Ltd | Black ion-plated film |
| CH664377A5 (en) * | 1986-01-16 | 1988-02-29 | Balzers Hochvakuum | DECORATIVE BLACK WEAR PROTECTIVE LAYER. |
-
1985
- 1985-11-15 JP JP60256108A patent/JPS62116762A/en active Pending
-
1986
- 1986-11-06 DE DE3637810A patent/DE3637810C2/en not_active Expired - Fee Related
- 1986-11-11 GB GB8626889A patent/GB2182950B/en not_active Expired
- 1986-11-14 KR KR1019860009607A patent/KR880001630B1/en not_active IP Right Cessation
-
1990
- 1990-02-20 SG SG118/90A patent/SG11890G/en unknown
- 1990-03-15 HK HK193/90A patent/HK19390A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| GB8626889D0 (en) | 1986-12-10 |
| JPS62116762A (en) | 1987-05-28 |
| GB2182950A (en) | 1987-05-28 |
| GB2182950B (en) | 1989-10-25 |
| SG11890G (en) | 1990-07-06 |
| DE3637810C2 (en) | 1998-05-28 |
| DE3637810A1 (en) | 1987-05-21 |
| HK19390A (en) | 1990-03-23 |
| KR870004681A (en) | 1987-06-01 |
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