JP2006274339A - Decorative part - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide decorative parts having high hardness and free from the generation of scratches in use, particularly, decorative parts composed of a pure gold (24K) base material and free from the generation of scratches caused by impact, particularly, decorative parts containing gold and having a gold color tone, and to provide a method for producing the same. <P>SOLUTION: A gold alloy having an optional composition is evaporated in inert gas plasma, and a hardened layer mainly made up of the gold alloy is formed on the surface of decorative parts such as watch exterior parts, a pierced earring, an earring, a finger-ring, a glasses frame, a pendant, a necklace, a bracelet and a brooch. Concretely, a hardened layer mainly made up of an Au-Pd-Si alloy, an Au-Pt-Si alloy, an Au-Pd-Pt-Si alloy, an Au-Pd-Ge alloy, an Au-Pt-Ge alloy or an Au-Pd-Pt-Ge alloy is formed. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a decorative part having a gold-colored hardened layer containing gold on the surface.

  Soft precious metal materials such as Au, Ag, and Pt are used for decorative parts such as watch exterior parts, earrings, earrings, rings, glasses frames, pendants, necklaces, bracelets, brooches, etc., but scratches occur during use. Deterioration of the appearance quality due to the above has been pointed out as a major problem. This is mainly due to the fact that the surface hardness of the soft noble metal material itself is as low as Vickers hardness and about Hv = 200, and various hardening treatments have been attempted with the aim of solving it.

  The watch exterior parts, earrings, earrings, rings, eyeglass frames, pendants, necklaces, bracelets, brooches and other decorative parts are required to have high decorative performance and appearance quality. Various curing treatment techniques have been attempted.

  There are two methods for curing the soft noble metal material: a method for coating a surface of the soft noble metal material and a method for curing the soft noble metal material itself.

  Examples of the method for forming a coating on the surface of the soft noble metal material include wet plating and ion plating. Especially for watch exterior parts, precious metal elements such as Rh plating, Pd plating, Ni-P plating, Ni-Pd plating, Au-Pd plating, etc. are widely used, but any plating film is softly used. The scratch has not been resolved. Further, since the color tone of these plating films is not a gold color tone but a metal color tone, there is a disadvantage that the high-quality texture is inferior. In ion plating, there is a method of coating a Pt film, Rh film, etc. The ion plating film such as Pt film, Rh film is also soft like a plating film, and there are problems in adhesion and peeling. There is a defect that it is likely to occur, and none of them has been completely solved for the film peeling problem.

  As a method for curing the soft base material itself, there is a method in which other metal elements are added to the noble metal element and alloyed to harden the noble metal material itself, but in the case of Au, 18K, 24K, etc. to which Cu and Ag are added Even in alloys, the Vickers hardness does not increase so much, and even when Cu, Ni, P or the like is added to Pd, Pt or the like and alloyed, the Vickers hardness does not increase so much. Accordingly, it has not yet been possible to eliminate scratches that occur during use.

  An Au alloy finishing layer composed of three elements of 94.0 to 98.5 wt% Au, 1.0 to 3.0 wt% Fe, and 0.5 to 3.0 wt% Pd has been proposed (for example, Patent Document 1 or Patent This is a material in which Fe and Pd are added for the purpose of achieving a gold decorative part in which an Au color tone is secured without causing metal allergy, and no mention is made regarding hardness and strength. When the authors conducted a follow-up test, only a low-hardness film having a Hv of 250 or less could be obtained.

JP-A-8-13132 (Claim 1) JP 2001-294955 A (Claim 1)

    An object of the present invention is to provide a high-hardness decorative part that does not cause scratches during use, particularly a decorative part containing gold and having a golden color tone.

  The decorative part of the present invention is a decorative part having a hardened layer on the surface of a gold substrate, and the hardened layer is a hardened layer mainly composed of a gold alloy.

  The hardened layer is any one of an Au—Pd—Si alloy, an Au—Pt—Si alloy, an Au—Pd—Pt—Si alloy, an Au—Pd—Ge alloy, an Au—Pt—Ge alloy, or an Au—Pd—Pt—Ge alloy. It is preferable that The decorative parts are preferably watch exterior parts, earrings, earrings, rings, glasses frames, pendants, necklaces, bracelets and brooches.

(Function)
There are various hardened layers mainly composed of gold alloys, all of which are characterized in that no corrosion occurs even when immersed for a long time in acids and alkalis, and the mechanical strength is high. Further, the adhesion between the gold base material as a base and the hardened layer mainly composed of a gold alloy is good, and peeling does not occur. The present invention solves the above problems by utilizing these characteristics. A hardened layer mainly composed of a high-hardness gold alloy is formed on the surface of the decorative part containing Au, and a high-hardness decorative part that does not cause scratches due to impact resistance is achieved.

  As described above, according to the present invention, a hardened layer mainly composed of a gold alloy is provided on the surface of decorative parts such as gold watch exterior parts, earrings, earrings, rings, glasses frames, pendants, necklaces, bracelets and brooches. By forming it, a high-hardness, high-corrosion-resistant gold-colored decorative part that does not cause scratches due to impact and does not corrode is achieved, and has a special effect as a surface hardening method for the decorative part.

  After processing a base material made of pure gold (24K) into various parts shapes, a gold alloy having an arbitrary alloy composition was evaporated in an arbitrary inert gas plasma atmosphere to form a hardened layer mainly composed of the gold alloy. Details of the invention are illustrated in the following examples.

(First embodiment)
This embodiment employs a technique of evaporating a gold alloy of an arbitrary composition in an arbitrary inert gas plasma atmosphere to form a hardened layer mainly composed of the gold alloy of an arbitrary composition on the surface of a base material made of pure gold (24K). .

(Example 1-27)
A first embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a schematic sectional view of a watch case 2 which is a watch exterior part. The watch case 2 is placed in a vacuum device, and after evacuating the vacuum device, Ar gas is introduced to generate Ar gas plasma, and the pressure is kept at 0.2 Pa. An alloy target was used, and a hardened layer 4 mainly composed of a gold alloy was formed on the surface of the watch case by DC sputtering. In addition, watch bezels were used as watch exterior parts, and earrings, earrings, rings, glasses frames, pendants, necklaces, bracelets and brooches were used as other decorative parts. Pure gold (24K) was used as the base material for the decorative parts.

(Comparative Example 1-9)
As Comparative Example 1-9 of the embodiment of the present invention, an Au-Pd film is wet-plated on the surface of a watch case, watch bezel, earring, ring, glasses frame, pendant, necklace, bracelet, brooch made of a pure gold (24K) base material. It was formed by the method.

  Tables 1 and 2 show the results of the hardness test, the adhesion test, the corrosion resistance test, and the comprehensive evaluation results of the decorative parts obtained in Example 1-27 and Comparative Example 1-9 of the first embodiment.

  The composition of the hardened layer mainly composed of a gold alloy was specified by EPMA (X-ray microanalysis) analysis. The hardness test was measured with a micro Vickers hardness meter, and a Vickers hardness Hv = 500 or more was accepted at a load of 1 mN. In the adhesion test, a scratch test was performed, the peel start load was measured, and a peel start load of 400 gf or more was accepted. In the corrosion resistance test, the sample was dipped in a CASS test solution for 48 hours, and no corrosion occurred at all. Those that passed all these three items were regarded as acceptable in the comprehensive evaluation results.

    As shown in Table 1, on the surface of decorative parts such as watch case, watch bezel, earrings, earrings, rings, glasses frame, pendant, necklace, bracelet, brooch made of pure gold (24K) base material, Au-Pd-Si alloy A hardened layer made of an Au—Pt—Si alloy and an Au—Pd—Pt—Si alloy was formed. The cured layer composition was identified by EPMA analysis. All of these Examples 1-27 passed when the Vickers hardness was Hv = 500 or more in the hardness test, passed when the peeling start load by the scratch test was 410 gf or more in the adhesion test, and corrosion did not occur after the CASS test even in the corrosion resistance test. As a result, all of Examples 1-27 passed in the overall evaluation result.

  On the other hand, an Au-Pd film is formed on the surface of a watch case, watch bezel, earring, ring, glasses frame, pendant, necklace, bracelet or brooch made of the pure gold (24K) base material of Comparative Example 1-9 by a wet plating method. In the corrosion resistance test, corrosion did not occur after the CASS test but passed, but in the hardness test, it failed when the Vickers hardness was Hv = 300 or less, and in the adhesion test, the peel start load was 210 gf or less. Yes, since the hardness test and the adhesion test were unacceptable in all the comparative examples, the comprehensive evaluation results were unacceptable.

(Second Embodiment)
In the present embodiment, similarly to the first embodiment, a gold alloy having an arbitrary composition is evaporated in an arbitrary inert gas plasma atmosphere, and hardening is mainly performed on the surface of the base material made of pure gold (24K). A method of forming a layer was adopted.

(Examples 28-54)
An Au alloy having an arbitrary composition in a He gas plasma atmosphere in which a base material is disposed in a vacuum device, He gas is introduced after the inside of the vacuum device is evacuated, and a pressure is maintained at 0.25 Pa. Using the target, a hardened layer mainly composed of a gold alloy was formed on the surface of various decorative parts by DC sputtering. Watch cases, watch bezels, earrings, earrings, rings, glasses frames, pendants, necklaces, bracelets and brooches were used as decorative parts. Pure gold (24K) was used as the base material for the decorative parts.

  Table 3 shows the results of the hardness test, the adhesion test, the corrosion resistance test, and the comprehensive evaluation results of the decorative parts obtained in Examples 28-54 of the second embodiment. The composition of the hardened layer, the hardness test, the adhesion test, the corrosion resistance test, and the comprehensive evaluation results were all the same evaluation criteria as the evaluation criteria evaluated in the first embodiment.

表２に示すように純金（２４Ｋ）母材からなる時計ケース、時計ベゼル、ピアス、イヤリング、指輪、メガネフレーム、ペンダント、ネックレス、ブレスレット、ブローチなど装飾部品の表面に、Ａｕ−Ｐｄ−Ｇｅ合金、Ａｕ−Ｐｔ−Ｇｅ合金およびＡｕ−Ｐｄ−Ｐｔ−Ｇｅ合金からなる硬化層を形成した。ＥＰＭＡ分析により硬化層組成を特定した。これら実施例２８−５４の全てが、硬度試験ではビッカース硬度がＨｖ＝５００以上で合格、密着性試験では引っかき試験による剥離開始荷重が４００ｇｆ以上で合格、耐蝕性試験でもＣＡＳＳ試験後に腐蝕は発生せず合格、従って総合評価結果では実施例２８−５４の全てが合格であった。

As shown in Table 2, on the surface of decorative parts such as watch cases, watch bezels, earrings, earrings, rings, glasses frames, pendants, necklaces, bracelets, brooches made of pure gold (24K) base materials, Au-Pd-Ge alloys, A hardened layer made of an Au—Pt—Ge alloy and an Au—Pd—Pt—Ge alloy was formed. The cured layer composition was identified by EPMA analysis. All of these Examples 28-54 passed when the Vickers hardness was Hv = 500 or higher in the hardness test, passed when the peel start load by the scratch test was 400 gf or higher in the adhesion test, and corrosion did not occur after the CASS test in the corrosion resistance test. As a result, all of Examples 28-54 passed in the overall evaluation result.

  The DC sputtering method was adopted as a means for evaporating the gold alloy element, but this was adopted because the alloy composition can be easily controlled, and is not limited to the DC sputtering method. The DC magnetron sputtering method, the RF magnetron Any sputtering method such as sputtering, RF sputtering, or DC sputtering may be used. In addition to the sputtering method, other PVD methods such as an ion plating method and an ion beam evaporation method may be adopted as long as the process is a dry process. Similarly, the plasma generation means may employ either the RF method or the DC method.

  In the first embodiment, the pressure of the atmosphere is 0.2 Pa in the first embodiment and 0.25 Pa in the second embodiment as a pressure condition for forming a hard layer mainly composed of a gold alloy. However, the pressure needs to be limited to the same condition. As long as plasma can be generated, the pressure may be any numerical value.

  In the first embodiment and the second embodiment, the watch case and the watch bezel have been described as specific examples as the watch exterior parts. However, the watch exterior parts are not limited to these, and the back cover, the middle ring, the crown, the buckle, etc. It is possible to form a hardened layer mainly composed of a gold alloy in any part used in the watch exterior.

  In the first embodiment and the second embodiment, the hardened layer mainly composed of a gold alloy is directly formed on a decorative part made of a pure gold (24K) base material. In order to adjust the thickness, a hardened layer mainly composed of a gold alloy may be formed after an intermediate layer is formed on a pure gold (24K) base material.

It is a cross-sectional schematic diagram of the watch case which is one Embodiment of the decorative component of this invention.

Explanation of symbols

2 Watch case 4 Hardened layer

Claims (2)

A decorative part having a hardened layer mainly composed of a gold alloy on the surface of a base material made of gold. The hardened layer is made of Au—Pd—Si alloy, Au—Pt—Si alloy, Au—Pd—Pt—Si alloy, Au—Pd—Ge alloy, Au—Pt—Ge alloy or Au—Pd—Pt—Ge alloy. 2. The decorative part according to claim 1, wherein

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