JPH0570990A - Ornamental member - Google Patents
Ornamental memberInfo
- Publication number
- JPH0570990A JPH0570990A JP3236340A JP23634091A JPH0570990A JP H0570990 A JPH0570990 A JP H0570990A JP 3236340 A JP3236340 A JP 3236340A JP 23634091 A JP23634091 A JP 23634091A JP H0570990 A JPH0570990 A JP H0570990A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- compound
- plating layer
- white
- coating
- 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
Landscapes
- Electroplating Methods And Accessories (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、装飾部材のメッキ構成
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plating structure for a decorative member.
【0002】[0002]
【従来の技術】従来の携帯時計、メガネフレームなどの
装飾部材のTi化合物、Cr化合物被膜による表面処
理の被膜構成は、合金素材表面に 下地メッキとして 耐食性等の基本品質を有する
Ni、NiーP等のメッキ層を被覆した後、該表面に
所望の色調を有する Ti化合物、Cr化合物被膜のメ
ッキ層を被覆した装飾部材。2. Description of the Related Art The conventional coating composition of a surface treatment with a Ti compound or Cr compound coating on a decorative member such as a portable watch or an eyeglass frame has a basic quality such as corrosion resistance as an undercoat on an alloy material surface.
After coating a plating layer of Ni, Ni-P, etc., on the surface
A decorative member coated with a plating layer of a Ti compound or Cr compound coating having a desired color tone.
【0003】 前記 の装飾部材の下地メッキ層の
表面に PdーNi等の白色メッキ層またはAu−N
i、Au−Ni−In等の金色メッキ層を積層して、さ
らに該メッキ層上に、Ti化合物、Cr化合物被膜を部
分選択的に被覆積層し、金色または白色とTi化合物、
Cr化合物被膜色との二色に仕上げた装飾部材。A white plating layer such as Pd-Ni or Au-N is formed on the surface of the base plating layer of the decorative member.
i, Au-Ni-In, or other gold-plated layer is laminated, and a Ti compound or Cr compound coating is partially and selectively coated on the plated layer.
A decorative member finished in two colors including the Cr compound coating color.
【0004】 前記の装飾部材の下地メッキ層の表
面に、色調の異なるTi化合物とCr化合物被膜の中か
ら選ばれた任意の被膜の組合せによって、多色に仕上げ
られた装飾部材が主流であった。[0004] A decoration member having a multi-colored finish on the surface of the base plating layer of the above-mentioned decoration member was mainly used by combining arbitrary coatings selected from Ti compound and Cr compound coatings having different color tones. ..
【0005】[0005]
【発明が解決しようとする課題】しかし、前述の装飾部
材では、TiまたはCr化合物被膜の下に Ni含有メ
ッキを使用しているため、一部のNiアレルギー体質の
人が携帯した際に、かぶれ、肌荒れなどの炎症を起こす
ことがあるという欠点を有していた。However, in the above-mentioned decorative member, since the Ni-containing plating is used under the Ti or Cr compound coating, when some people with Ni allergy constitution carry the rash. However, it has a drawback that it may cause inflammation such as rough skin.
【0006】本発明は、これらの課題を解決するもの
で、その目的とするところは、装飾部材としての耐食性
等の基本品質を有し、かつ 最表面に 所望のTi化合
物またはCr化合物色、金色とTiまたはCr化合物色
の二色、白色とTiまたはCr化合物色の二色、金色と
白色とTiまたはCr化合物色の三色、または Tiあ
るいはCr化合物色から選ばれた任意の多色を有し、更
に下地にNiを含有しないメッキ層で構成し、Niによ
る肌荒れ等の炎症を起こさない装飾部材を提供すること
にある。The present invention is intended to solve these problems, and an object thereof is to have a basic quality such as corrosion resistance as a decorative member, and a desired Ti compound or Cr compound color or gold color on the outermost surface. And two colors of Ti or Cr compound color, two colors of white and Ti or Cr compound color, three colors of gold color and white and Ti or Cr compound color, or any multicolor selected from Ti or Cr compound color. Further, the present invention is to provide a decorative member which is composed of a plating layer which does not contain Ni as a base and which does not cause inflammation such as rough skin due to Ni.
【0007】[0007]
【課題を解決するための手段】本発明の装飾部材は、 合金素材の表面上に Cu、Co、Pd,Ag、I
n、Pd−Co、PdーAg、Sn−Cu、SnーZ
n、AgーSn、Pb−Sn、Cu−Sn−Znメッキ
の内の一種または二種以上の下地メッキ層を被覆構成
し、該表面上に Ti化合物またはCr化合物被膜が形
成されていることを特徴とする。The decorative member of the present invention comprises: Cu, Co, Pd, Ag, I on the surface of an alloy material.
n, Pd-Co, Pd-Ag, Sn-Cu, Sn-Z
n, Ag-Sn, Pb-Sn, Cu-Sn-Zn plating is formed by coating one or more undercoating layers, and a Ti compound or Cr compound coating is formed on the surface. Characterize.
【0008】 の下地メッキ層上に、Au−Co、
Au−Pd、Au−Sn、Au−Pd−Cu、Au−P
d−In、Au−Co−In、Au−Ag−Cu、Ag
−Au、Au−Cu、Auメッキの内の一種または二種
以上の金色メッキ層を被覆積層し、該金色メッキ層上に
Ti化合物またはCr化合物被膜が全面または部分選択
的に形成されていることを特徴とする。Au-Co,
Au-Pd, Au-Sn, Au-Pd-Cu, Au-P
d-In, Au-Co-In, Au-Ag-Cu, Ag
-A gold, Au-Cu, or Au plating of one or more of gold plating layers is coated and laminated, and a Ti compound or Cr compound coating is formed on the gold plating layer entirely or partially. Is characterized by.
【0009】 の下地メッキ層上に、Pd−Co、
Pd、Pt、Rh、Ru、Crメッキの内の一種または
二種以上の白色メッキ層を被覆積層し、該白色メッキ層
上にTi化合物またはCr化合物被膜が、全面または部
分選択的に形成されていることを特徴とする。On the undercoat plating layer of Pd-Co,
One or more white plating layers of Pd, Pt, Rh, Ru, and Cr plating are laminated by coating, and a Ti compound or Cr compound coating is formed on the whole or a partial selective surface of the white plating layer. It is characterized by being
【0010】 の下地メッキ層上に、Pd−Co、
Pd、Pt、Rh、Ru、Crメッキの内の一種または
二種以上の白色メッキ層を部分選択的に被覆積層し、該
金色メッキ層または白色メッキ層上に、Ti化合物また
はCr化合物被膜が、部分選択的に形成されていること
を特徴とする。Pd-Co,
One or more white plating layers of Pd, Pt, Rh, Ru, and Cr plating are partially and selectively coated and laminated, and a Ti compound or Cr compound coating is formed on the gold plating layer or the white plating layer. It is characterized by being formed partially.
【0011】 の白色メッキ層上に、Au−Co、
Au−Pd、Au−Sn、Au−Pd−Cu、Au−P
d−In、Au−Co−In、Au−Ag−Cu、Ag
−Au、Au−Cu、Auメッキの内の一種または二種
以上の金色メッキ層を部分選択的に被覆積層し、該白色
メッキ層または該金色メッキ層上にTi化合物またはC
r化合物被膜が部分選択的に形成されていることを特徴
とする。Au-Co, on the white plated layer of
Au-Pd, Au-Sn, Au-Pd-Cu, Au-P
d-In, Au-Co-In, Au-Ag-Cu, Ag
-Au, Au-Cu, Au plating of one kind or two or more kinds among Au plating is partially and selectively laminated to form a Ti compound or C on the white plating layer or the gold plating layer.
It is characterized in that the r compound film is formed partially selectively.
【0012】 の下地メッキ層上または の金色
メッキ層上 または の白色メッキ層上にに Ti化
合物またはCr化合物被膜の中から選ばれた色調の異な
る二種以上の被膜を積層し、少なくとも該化合物被膜の
最上層を部分選択的に 剥離し多色に仕上げたことを特
徴とする。On the undercoat plating layer, on the gold plating layer, or on the white plating layer, two or more kinds of films having different color tones selected from Ti compound or Cr compound films are laminated, and at least the compound film The uppermost layer is peeled off selectively and finished in multiple colors.
【0013】[0013]
【作用】本発明の上記構成によれば、Niを使用しない
メッキ構成であるから、一部のNiアレルギー体質の人
が携帯した際に、汗に含まれる塩化ナトリウム等の電解
質が、Niの溶出を助長せしめ、イオン化して、皮膚が
それを吸収し Niアレルギーを起こし、かぶれてく
る現象を防止し、しかも 耐食性等の基本品質および
装飾性を満足させる。According to the above construction of the present invention, since the plating construction does not use Ni, when some Ni-allergic persons carry it, the electrolyte such as sodium chloride contained in sweat elutes Ni. It promotes and ionizes the skin, absorbs it by the skin, causes Ni allergies, prevents the phenomenon of rashes, and also has basic qualities such as corrosion resistance.
Satisfy the decorativeness.
【0014】[0014]
【実施例】以下本発明について、[実施例群A][実施
例群B][実施例群C][実施例群D][実施例群E]
および[実施例群F]に基づいて 説明する。Examples [Example group A] [Example group B] [Example group C] [Example group D] [Example group E]
And [Example group F].
【0015】[実施例群A]図1から図2は 本発明請
求項1の[実施例群A]の装飾部材の被膜構成を示す断
面図である。黄銅あるいは亜鉛合金により形成された時
計用外装部品を素材とし、該素材表面上に 一種または
二種以上の下地メッキ層を 表1〜表2に示したメッキ
条件にて被覆形成した。さらに、該下地メッキ層を被覆
した素材を基板とし、該基板を 真空排気されたイオン
プレーティング装置中で、アルゴンガスを導入し、2.
5Paの圧力に保持し基板への負の印加電圧0.5Kv
で5分間イオンボンバードメントを行い、基板表面上の
クリーニングを行った。次にアルゴンガスを排出し、真
空室内を1.0×10-2Paに戻した後、電子ビーム加
熱により純Tiまたは純Crを蒸発させ、反応性ガスと
してN2ガス、C2H2ガス、O2ガスの内の少なくとも一
種のガスを一定量導入し、Ti化合物またはCr化合物
の被膜を形成させた。被膜の厚みは 1μmとなる様純
Tiまたは純Crの蒸発時間によりコントロールした。
被膜の色調は表3に示す条件にて蒸発金属と反応ガスの
種類を適宜選択しコントロールした。図1〜 図2に示
した各々の被膜構成毎に 本発明実施例No.1〜N
o.30、比較例No.1〜No.7との合計37例を
サンプルとし時計用外装部品に用い、携帯時計を完成さ
せた後、Ni非溶出性、密着性、耐摩耗性および耐食性
について評価した結果と 被膜構成等をまとめて表4〜
表5に整理した。[Example Group A] FIGS. 1 and 2 are sectional views showing the coating composition of the decorative member of [Example Group A] according to claim 1 of the present invention. A watch exterior part made of brass or a zinc alloy was used as a material, and one or more kinds of base plating layers were formed on the surface of the material under the plating conditions shown in Tables 1 and 2. Further, a material coated with the base plating layer is used as a substrate, and argon gas is introduced into the substrate in an evacuated ion plating apparatus, and 2.
Negative voltage applied to the substrate is 0.5Kv with the pressure kept at 5Pa
Ion bombardment was performed for 5 minutes to clean the substrate surface. Next, argon gas was discharged, and the inside of the vacuum chamber was returned to 1.0 × 10 -2 Pa. Then, pure Ti or pure Cr was evaporated by electron beam heating, and N 2 gas or C 2 H 2 gas was used as a reactive gas. A certain amount of at least one of O 2 and O 2 gas was introduced to form a film of Ti compound or Cr compound. The thickness of the coating was controlled by the evaporation time of pure Ti or pure Cr so as to be 1 μm.
The color tone of the coating film was controlled by appropriately selecting the types of evaporated metal and reaction gas under the conditions shown in Table 3. For each of the coating configurations shown in FIGS. 1 to N
o. 30, Comparative Example No. 1-No. The total of 37 samples including No. 7 was used as a watch exterior part, and a mobile watch was completed, and then the results of evaluation of Ni non-elution, adhesion, wear resistance, and corrosion resistance, and the coating composition are summarized in Table 4 ~
It is arranged in Table 5.
【0016】[0016]
【表1】 [Table 1]
【0017】[0017]
【表2】 [Table 2]
【0018】[0018]
【表3】 [Table 3]
【0019】[0019]
【表4】 [Table 4]
【0020】[0020]
【表5】 [Table 5]
【0021】前述の 表4〜 表5に示す評価特性に対
する評価基準を 表6に示す。Table 6 shows the evaluation criteria for the evaluation characteristics shown in Tables 4 to 5 above.
【0022】[0022]
【表6】 [Table 6]
【0023】次に、各評価特性の 評価方法について以
下述べる。Next, the evaluation method of each evaluation characteristic will be described below.
【0024】評価に当たっては、基本的には JIS
Hー8622の装飾用金および金合金メッキに準じて行
った。[0024] In the evaluation, basically JIS
It was performed in accordance with H-8622 decorative gold and gold alloy plating.
【0025】被膜厚は、JIS Hー8521の 顕微
鏡断面試験方法により 層の厚さを求めた。The film thickness was determined by the microscopic cross-section test method of JIS H-8521.
【0026】耐摩耗性は、牛皮上に携帯時計の側面を密
着させ 500g荷重を携帯時計に加えながら、5cm
ストロークにて3万回擦って摩耗させた携帯時計側面の
被膜の摩耗程度を確認した。The wear resistance is 5 cm while the side of the mobile watch is brought into close contact with the cowhide and a load of 500 g is applied to the mobile watch.
The degree of wear of the coating on the side surface of the mobile watch, which was abraded by rubbing 30,000 strokes, was confirmed.
【0027】密着性は、携帯時計をバイスにて両端より
圧縮荷重を加え、折曲部が90゜以上になるようにして
折曲部の被膜の剥離程度を調べた。The adhesion was examined by applying a compressive load from both ends with a vise of a portable watch so that the bent portion was 90 ° or more, and the degree of peeling of the coating film at the bent portion was examined.
【0028】耐食性については、人工汗、人工海水(3
%NaCl)中に携帯時計完成品を40℃×90%の温
湿雰囲気中で20時間 携帯時計の半分を浸漬し、腐食
および変色の発生を調べた。Regarding corrosion resistance, artificial sweat, artificial seawater (3
% Of NaCl), the half of the portable watch was immersed in a hot and humid atmosphere of 40 ° C. × 90% for 20 hours, and the occurrence of corrosion and discoloration was examined.
【0029】Ni検出方法については、デンマークの
「ニッケル含有製品販売禁止行政命令」472条(19
89年6月27日付け)に定められた許容基準「遊離の
ニッケルが0.5μg/cm2/週以下」を 満足して
いるかどうか、該法令に定められた検出方法(1%ジメ
チルグリオキシムエチルアルコール溶液と 10%アン
モニア水を用い 綿布上に それぞれの溶液を2滴ずつ
滴下し、その布で30秒間一定の動作で試料の表面を擦
りつけ、薄い赤から明るい赤の範囲での 赤色変化の程
度を見る。そして、赤い色を検出しない場合は、0.5
μg/cm2/週以下とみなす。)で評価した。(薄い
赤から明るい赤の範囲での赤色変化は、Ni最少溶出検
出量が 0.5μg/cm2/週を 越えていることを
示す)。For the method of detecting Ni, refer to Denmark's “Administrative Order for Prohibition of Sales of Nickel-Containing Products” Article 472 (19
Whether or not the acceptance standard “free nickel is 0.5 μg / cm 2 / week or less” defined in June 27, 1989) is satisfied, and the detection method (1% dimethylglyoxime) specified by the law is satisfied. Using an ethyl alcohol solution and 10% ammonia water, drop 2 drops of each solution on a cotton cloth, rub the surface of the sample with the cloth for 30 seconds with constant movement, and change the red color from light red to bright red. And if you don't detect the red color, 0.5
It is considered to be less than or equal to μg / cm 2 / week. ) Was evaluated. (A red change in the range from light red to bright red indicates that the minimum detected amount of Ni elution exceeds 0.5 μg / cm 2 / week).
【0030】本発明における前記本発明[実施例群A]
の実施例No.1〜No.30のサンプルにおいて、黄
銅あるいは亜鉛合金を素材とした 新規の被膜構成によ
る携帯時計完成品は、装飾的価値の高い色調を呈し、N
i検出試験においては、すべて 全く検出されず Ni
によるアレルギーに対し 高い防止効果が確認できた。
さらに人工汗および人工海水の耐食試験にて腐食の発生
が見られず、また 折り曲げによる密着性試験 および
牛皮による耐摩耗性試験においては、本発明実施例N
o.1〜No.30のいずれにおいても、密着性品質、
耐摩耗性品質は、時計用外装部品として十分であった。
次に 比較例No.1〜No.7のNiを含有したメッ
キを被覆した従来構成は、Ni検出試験において 強い
Niの溶出があり Niアレルギーに対する防止効果は
無いといえる。また、比較例において 密着性、耐摩耗
性および耐食性については、携帯時計として十分であっ
た。The present invention in the present invention [Example group A]
Example No. 1-No. In 30 samples, the finished watch made of brass or zinc alloy with a new coating composition has a color tone of high decorative value.
In the i detection test, all were not detected
A high preventive effect against allergy due to
In addition, no corrosion was found in the corrosion resistance test of artificial sweat and artificial seawater, and in the adhesion test by bending and the abrasion resistance test by cowhide, the invention Example N was used.
o. 1-No. In any of 30, the adhesion quality,
The abrasion resistance quality was sufficient for exterior parts for watches.
Next, in Comparative Example No. 1-No. It can be said that the conventional structure in which the plating containing Ni of No. 7 is coated has a strong elution of Ni in the Ni detection test and has no effect of preventing Ni allergy. In addition, the adhesiveness, wear resistance, and corrosion resistance of the comparative example were sufficient for mobile watches.
【0031】以上 図1〜図2に示した被覆構成を応用
した本発明の[実施例群A]について述べた。The [Example group A] of the present invention to which the coating structure shown in FIGS. 1 and 2 is applied has been described above.
【0032】なお、以下述べる[実施例郡B]〜[実施
例郡F]で用いる下地メッキ層およびイオンプレーティ
ング層の処理条件は、各々 表1〜表2、および表3と
同様に行った。また 評価基準については 表6に示す
内容で、同様の評価を行った。The treatment conditions of the undercoat plating layer and the ion plating layer used in [Example group B] to [Example group F] described below were the same as those in Tables 1 to 2 and Table 3, respectively. .. The evaluation criteria are as shown in Table 6, and the same evaluation was performed.
【0033】[実施例群B]図3〜図4は、本発明請求
項2の[実施例群B]の装飾部材の被膜構成を示す断面
図である。黄銅あるいは亜鉛合金により形成された時計
用外装部品を素材とし、該素材上に 一種または二種以
上の下地メッキ層を被覆し、次に該下地メッキ層上に
一種または二種以上の表7〜表8に示す金色メッキ層を
被覆し、さらに金色メッキ層の表面上にイオンプレーテ
ィング被膜を全面または部分選択的に被覆構成した。図
3〜図4に示した各々のメッキ構成毎に 本発明[実施
例群B]の実施例No.31〜No.54、比較例N
o.8〜No.13の合計30例をサンプルとし 時計
用外装部品を用い携帯時計を完成させた後、Ni非溶出
性・耐摩耗性・密着性および耐食性について評価した結
果と メッキ構成等をまとめて表9〜表10に整理し
た。[Example Group B] FIGS. 3 to 4 are sectional views showing the coating composition of the decorative member of [Example Group B] according to claim 2 of the present invention. A watch exterior part made of brass or zinc alloy is used as a material, and one or more undercoating layers are coated on the material, and then the undercoating layer is applied.
One or two or more kinds of gold-plated layers shown in Tables 7 to 8 were coated, and the surface of the gold-plated layers was entirely or partially selectively coated with an ion plating film. The example No. of the present invention [Example group B] is set for each plating configuration shown in FIGS. 31-No. 54, Comparative Example N
o. 8 to No. A total of 30 samples of 13 samples were used to complete a mobile watch using exterior parts for a watch, and the results of evaluating Ni non-elution, wear resistance, adhesion, and corrosion resistance, and the plating composition are summarized in Tables 9 to 9. I arranged it in 10.
【0034】[0034]
【表7】 [Table 7]
【0035】[0035]
【表8】 [Table 8]
【0036】[0036]
【表9】 [Table 9]
【0037】[0037]
【表10】 [Table 10]
【0038】さて、前記本発明[実施例群B]の実施例
No.31〜No.54のサンプルにおいては、[実施
例群A]と同様に、Ni検出試験においては Niの溶
出が全く見られず Niアレルギーに対し高い防止効果
が確認できた。また、密着性・耐摩耗性・耐食性につい
ても 携帯時計として十分であった。次に比較例No.
8〜No.13については、下地メッキ層、金色メッキ
層の少なくとも一層以上に Ni含有メッキを使用して
いるため Ni検出試験にてNiの溶出が見られ、いず
れもNiアレルギーに対する防止効果が見られなかっ
た。しかし 耐摩耗性・密着性・耐食性については 携
帯時計として十分であった。Now, Example No. 1 of the above-mentioned [Example group B] of the present invention. 31-No. In the sample No. 54, as in the case of [Example group A], no Ni elution was observed in the Ni detection test, and a high effect of preventing Ni allergy was confirmed. The adhesiveness, wear resistance and corrosion resistance were also sufficient for mobile watches. Next, Comparative Example No.
8 to No. Regarding No. 13, since Ni-containing plating was used for at least one of the base plating layer and the gold-plated layer, Ni was eluted in the Ni detection test, and no effect of preventing Ni allergy was observed. However, the wear resistance, adhesion, and corrosion resistance were sufficient for mobile watches.
【0039】以上 図3〜図4に示した被覆構成を応用
した本発明の[実施例群B]について述べた。なお 以
下述べる[実施例群C]〜[実施例群F]で用いる金色
メッキ層の処理条件は 表7〜表8と全く同様に行っ
た。[Example group B] of the present invention to which the coating structure shown in Figs. 3 to 4 is applied has been described above. The treatment conditions of the gold-plated layers used in [Example group C] to [Example group F] described below were exactly the same as those in Tables 7 to 8.
【0040】[実施例群C]図5〜図6は、本発明請求
項3の[実施例群C]の装飾部材の被膜構成を示す断面
図である。黄銅あるいは亜鉛合金により形成された時計
用外装部品を素材とし、該素材上に 一種または二種以
上の下地メッキ層を被覆し、次に該下地メッキ層上に
一種または二種以上の 表11に示す白色メッキ層を被
覆し、さらに白色メッキ層の表面上に、イオンプレーテ
ィング被膜を 全面または部分選択的に被覆積層した。
図5〜図6に示した各々のメッキ構成毎に本発明[実施
例群C]の実施例No.55〜No.70、比較例N
o.14〜No.15の合計18例をサンプルとし 時
計用外装部品を用い携帯時計を完成させた後、Ni非溶
出性、耐摩耗性、密着性および耐食性について評価した
結果と メッキ構成等をまとめて表12〜表13に整理
した。[Example Group C] FIGS. 5 to 6 are sectional views showing the coating composition of the decorative member of [Example Group C] according to claim 3 of the present invention. A watch exterior part made of brass or zinc alloy is used as a material, and one or more undercoating layers are coated on the material, and then the undercoating layer is applied.
One kind or two or more kinds of white plating layers shown in Table 11 were coated, and the surface of the white plating layer was further coated with an ion plating coating, either entirely or partially selectively.
The embodiment No. of the present invention [embodiment group C] for each plating configuration shown in FIGS. 55 to No. 70, Comparative Example N
o. 14-No. A total of 18 samples of 15 samples were used to complete a mobile watch using exterior parts for a watch, and the results of evaluating Ni non-elution property, wear resistance, adhesion and corrosion resistance and the plating composition are summarized in Tables 12 to 12. I arranged it in 13.
【0041】[0041]
【表11】 [Table 11]
【0042】[0042]
【表12】 [Table 12]
【0043】[0043]
【表13】 [Table 13]
【0044】本発明[実施例群C]の実施例No.55
〜No.70のサンプルにおいては、[実施例群A]と
同様に、Ni検出試験においては Niの溶出が全く見
られずNiアレルギーに対し高い防止効果が確認でき
た。また、密着性・耐摩耗性・耐食性についても 時計
用外装部品として十分であった。次に比較例No.14
〜No.15については、下地メッキ層、白色メッキ層
の少なくとも一層以上にNi含有メッキを使用している
ため、Ni検出試験にてNiの溶出が見られ、いずれも
Niアレルギーに対する防止効果が見られなかった。し
かし、耐摩耗性・密着性・耐食性については 時計用外
装部品として十分であった。Example No. 4 of the present invention [Example group C]. 55
~ No. Similar to [Example group A], in the 70 sample, no Ni elution was observed in the Ni detection test, and a high effect of preventing Ni allergy was confirmed. Also, the adhesiveness, wear resistance, and corrosion resistance were sufficient for exterior parts for watches. Next, Comparative Example No. 14
~ No. Regarding No. 15, since Ni-containing plating was used for at least one of the base plating layer and the white plating layer, Ni elution was found in the Ni detection test, and no effect of preventing Ni allergy was observed. .. However, the wear resistance, adhesion, and corrosion resistance were sufficient for exterior parts for watches.
【0045】以上 図5〜図6に示した被覆構成を応用
した本発明の[実施例群C]について述べた。なお 以
下に述べる[実施例群D]〜[実施例群F]で用いる白
色メッキ層の処理条件は 表11と全く同様に行った。[Example group C] of the present invention to which the coating structure shown in FIGS. 5 to 6 is applied has been described above. The processing conditions of the white plating layers used in [Example group D] to [Example group F] described below were exactly the same as in Table 11.
【0046】[実施例群D]図7〜図8は、本発明請求
項4の[実施例群D]の装飾部材の被膜構成を示す断面
図である。黄銅あるいは亜鉛合金により形成された時計
用外装部品を素材とし、該素材上に 一種または二種以
上の下地メッキ層を被覆し、次に該下地メッキ層上に
一種または二種以上の表7〜表8に示す金色メッキ層を
被覆し、さらに金色メッキ層の表面上に、表11に示す
白色メッキ層を部分選択的に積層し、さらに 金色メッ
キ層上または部分白色メッキ層上にイオンプレーティン
グ被膜を部分選択的に被覆積層した。図7〜図8に示し
た各々のメッキ構成毎に本発明[実施例群D]の実施例
No.71〜No.85、比較例No.16〜No.1
9の合計19例をサンプルとし 時計用外装部品を用い
携帯時計を完成させた後、Ni非溶出性、耐摩耗性、密
着性および耐食性について評価した結果と メッキ構成
等をまとめて表14〜表15に整理した。[Example Group D] FIGS. 7 to 8 are sectional views showing the coating composition of the decorative member of [Example Group D] of Claim 4 of the present invention. A watch exterior part made of brass or zinc alloy is used as a material, and one or more undercoating layers are coated on the material, and then the undercoating layer is applied.
One or more kinds of gold-plated layers shown in Tables 7 to 8 are coated, and the white-plated layer shown in Table 11 is partially and selectively laminated on the surface of the gold-plated layer. An ion plating coating was partially and selectively laminated on the partially white plated layer. The embodiment No. of the present invention [embodiment group D] for each plating configuration shown in FIGS. 71 to No. 85, Comparative Example No. 16-No. 1
After a mobile timepiece was completed by using a total of 19 samples of 9 as the sample and using exterior parts for timepieces, the results of evaluating Ni non-elution, wear resistance, adhesion and corrosion resistance, and the plating composition, etc. are summarized in Table 14 to Table. I arranged it in 15.
【0047】[0047]
【表14】 [Table 14]
【0048】[0048]
【表15】 [Table 15]
【0049】本発明[実施例群D]の実施例No.71
〜No.85のサンプルにおいては、[実施例群A]と
同様に、Ni検出試験においては Niの溶出が全く見
られずNiアレルギーに対し高い防止効果が確認でき
た。また、密着性・耐摩耗性・耐食性についても 時計
用外装部品として十分であった。次に 比較例No.1
6〜No.19については、下地メッキ層、金色・白色
メッキ層の少なくとも一層以上に Ni含有メッキを使
用しているため、Ni検出試験にてNiの溶出が見ら
れ、いずれもNiアレルギーに対する防止効果が見られ
なかった。しかし、耐摩耗性・密着性・耐食性について
は 時計用外装部品として十分であった。Example No. 4 of the present invention [Example group D]. 71
~ No. In the sample No. 85, as in the case of [Example group A], no Ni elution was observed in the Ni detection test, and a high effect of preventing Ni allergy was confirmed. Also, the adhesiveness, wear resistance, and corrosion resistance were sufficient for exterior parts for watches. Next, in Comparative Example No. 1
6-No. For No. 19, since Ni-containing plating is used for at least one of the base plating layer and the gold / white plating layer, Ni elution was found in the Ni detection test, and all had the effect of preventing Ni allergy. There wasn't. However, the wear resistance, adhesion, and corrosion resistance were sufficient for exterior parts for watches.
【0050】[実施例群E]図9〜図10は、本発明請
求項5の[実施例群E]の装飾部材の被膜構成を示す断
面図である。黄銅あるいは亜鉛合金により形成された時
計用外装部品を素材とし、該素材上に 一種または二種
以上の下地メッキ層を被覆し、次に該下地メッキ層上に
一種または二種以上の表11示す白色メッキ層を被覆
し、さらに白色メッキ層の表面上に、表7〜表8に示す
金色メッキ層を部分選択的に積層し、さらに 白色メッ
キ層上または部分金色メッキ層上にイオンプレーティン
グ被膜を部分選択的に被覆積層した。図9〜図10に示
した各々のメッキ構成毎に本発明[実施例群E]の実施
例No.86〜No.101、比較例No.20〜N
o.23の合計20例をサンプルとし 時計用外装部品
を用い携帯時計を完成させた後、Ni非溶出性、耐摩耗
性、密着性および耐食性について評価した結果とメッキ
構成等をまとめて表16〜表17に整理した。[Embodiment Group E] FIGS. 9 to 10 are sectional views showing the coating composition of the decorative member of [Embodiment Group E] of claim 5 of the present invention. A watch exterior part made of brass or zinc alloy is used as a material, and one or more undercoating layers are coated on the material, and then one or more than one kind is shown in Table 11 below. A white plating layer is coated, and the gold plating layers shown in Tables 7 to 8 are partially and selectively laminated on the surface of the white plating layer, and the ion plating film is further formed on the white plating layer or the partial gold plating layer. Was partially selectively coated and laminated. The embodiment No. of the present invention [Embodiment group E] is set for each plating configuration shown in FIGS. 86-No. 101, Comparative Example No. 20-N
o. A total of 20 samples of 23 samples were used to complete the mobile timepiece using the timepiece exterior parts, and the results of evaluation of Ni non-elution, wear resistance, adhesion and corrosion resistance, and the plating composition, etc. are summarized in Tables 16 to 16. Sorted out in 17.
【0051】[0051]
【表16】 [Table 16]
【0052】[0052]
【表17】 [Table 17]
【0053】本発明[実施例群E]の実施例No.86
〜No.101のサンプルにおいては、[実施例群A]
と同様に、Ni検出試験においては Niの溶出が全く
見られずNiアレルギーに対し高い防止効果が確認でき
た。また、密着性・耐摩耗性・耐食性についても 時計
用外装部品として十分であった。次に比較例No.20
〜No.23については、下地メッキ層、金色・白色メ
ッキ層の少なくとも一層以上に Ni含有メッキを使用
しているため、Ni検出試験にてNiの溶出が見られ、
いずれもNiアレルギーに対する防止効果が見られなか
った。しかし、耐摩耗性・密着性・耐食性については
時計用外装部品として十分であった 。 [実施例群F]図11〜図12は、本発明請求項6
の[実施例群F]の装飾部材の被膜構成を示す断面図で
ある。黄銅あるいは亜鉛合金により形成された時計用外
装部品を素材とし、該素材上に 一種または二種以上の
下地メッキ層を被覆し、次に該下地メッキ層上に 必要
に応じて 一種または二種以上の表7〜表8に示す金色
メッキ層を被覆し、該金色メッキ または 下地メッキ
の表面上に、イオンプレーティング被膜を全面に積層
し、さらに 該イオンプレーティング被膜と色調を異に
するイオンプレーティング被膜を 部分選択的に 積層
した。図11〜図12に示した各々のメッキ構成毎に本
発明[実施例群F]の実施例No.102〜No.11
3、比較例No.24〜No.26の合計15例をサン
プルとし 時計用外装部品を用い携帯時計を完成させた
後、Ni非溶出性、耐摩耗性、密着性および耐食性につ
いて評価した結果と メッキ構成等をまとめて表18〜
表19に整理した。Example No. 7 of the present invention [Example group E]. 86
~ No. In the sample of 101, [Example group A]
Similarly, in the Ni detection test, no Ni elution was observed and a high effect of preventing Ni allergy was confirmed. Also, the adhesiveness, wear resistance, and corrosion resistance were sufficient for exterior parts for watches. Next, Comparative Example No. 20
~ No. For No. 23, since Ni-containing plating is used for at least one of the base plating layer and the gold / white plating layer, Ni elution was found in the Ni detection test,
None of them showed a protective effect against Ni allergy. However, regarding wear resistance, adhesion and corrosion resistance
It was sufficient as an exterior part for watches. [Example Group F] FIGS.
FIG. 6 is a cross-sectional view showing a coating configuration of a decorative member of [Example group F] of FIG. A watch exterior part made of brass or zinc alloy is used as a material, and one or more undercoating layers are coated on the material, and then one or more undercoating layers are formed on the undercoating layer as needed. Of the gold-plated layer shown in Table 7 to Table 8 above, an ion-plating film is laminated on the entire surface of the gold-plated or underplating, and an ion-plating layer having a color tone different from that of the ion-plating film is formed. The coating was partially selectively laminated. For each of the plating configurations shown in FIGS. 102-No. 11
3, Comparative Example No. 24-No. After completion of the mobile timepiece using the timepiece exterior parts, using a total of 15 cases of 26 samples, the results of evaluation of Ni non-elution property, wear resistance, adhesion and corrosion resistance and the plating composition are summarized in Table 18-
It is arranged in Table 19.
【0054】[0054]
【表18】 [Table 18]
【0055】[0055]
【表19】 [Table 19]
【0056】本発明[実施例群F]の実施例No.10
2〜No.113のサンプルにおいては、[実施例群
A]と同様に、Ni検出試験においては Niの溶出が
全く見られずNiアレルギーに対し高い防止効果が確認
できた。また、密着性・耐摩耗性・耐食性についても
時計用外装部品として十分であった。次に 比較例N
o.24〜No.26については、Ni含有メッキを被
覆した従来構成においては、Ni検出試験において N
iの溶出があり、Niアレルギーに対する防止効果は無
いと居る。また 比較例において密着性・耐摩耗性およ
び耐食性については 携帯時計として十分であった。以
上 図11〜図12に示した被膜構成を応用した本発明
の[実施例群F]について述べた。Example No. 6 of the present invention [Example group F]. 10
2 to No. In the sample of No. 113, as in the case of [Example group A], no Ni elution was observed in the Ni detection test, and a high effect of preventing Ni allergy was confirmed. Also, regarding adhesion, wear resistance and corrosion resistance
It was sufficient as an exterior part for watches. Next, Comparative Example N
o. 24-No. Regarding No. 26, in the conventional structure coated with the Ni-containing plating, N was detected in the Ni detection test.
It is said that i is eluted and there is no protective effect against Ni allergy. In addition, the adhesion, wear resistance and corrosion resistance of the comparative example were sufficient for a mobile watch. The [Example group F] of the present invention to which the coating structure shown in FIGS. 11 to 12 is applied has been described above.
【0057】[0057]
【発明の効果】以上述べたように 本発明によれば、T
i化合物被膜またはCr化合物被膜が全面または部分選
択的に被覆されている装飾部材において、下地メッキ層
としてCu、Co、Pd、Ag、In、Pd−Co、P
d−Ag、Sn−Cu、Sn−Zn、Pb−Sn、Ag
−Sn、Cu−Sn−Znメッキの内の一種または二種
を用い、該下地メッキ層に積層する場合の金色メッキ層
として Au−Co、Au−Pd、Au−Sn、Au−
Pd−Cu、Au−Pd−In、Au−Co−In、A
u−Ag−Cu、Au−Cu、Auメッキの内の一種ま
たは二種、白色メッキとして Pd−Co、Pd、P
t、Rh、Ru、Crメッキの内の一種または二種を用
い 構成したことを特徴とすることから、次のような効
果を有する。As described above, according to the present invention, T
In a decorative member in which an i compound film or a Cr compound film is entirely or partially selectively coated, Cu, Co, Pd, Ag, In, Pd-Co, P is used as a base plating layer.
d-Ag, Sn-Cu, Sn-Zn, Pb-Sn, Ag
One or two of --Sn and Cu--Sn--Zn plating are used, and Au--Co, Au--Pd, Au--Sn, Au--as a gold-colored plating layer when laminated on the base plating layer.
Pd-Cu, Au-Pd-In, Au-Co-In, A
One or two of u-Ag-Cu, Au-Cu, and Au plating, Pd-Co, Pd, P as white plating
Since it is characterized by using one or two of t, Rh, Ru, and Cr plating, it has the following effects.
【0058】Niを使用しないメッキ構成であるから、
一部のNiアレルギー体質の人が携帯した際に、汗に含
まれる塩化ナトリウム等の電解質が Niの溶出を助長
せしめ、イオン化して、皮膚がそれを吸収しニッケルア
レルギーを起こし、かぶれてくるような現象を防止し、
しかも 密着性・耐食性・耐摩耗性およびデザインバラ
ェティーに富んだ時計用外装・メガネフレーム、指輪、
ネックレス、イヤリング等の装飾部材を提供できる。こ
のように 本発明の効果は極めて大きい。Since the plating structure does not use Ni,
When carried by some people with Ni allergies, electrolytes such as sodium chloride contained in sweat promote the elution of Ni and ionize it, causing the skin to absorb it and cause nickel allergy, causing rashes. Prevent the phenomenon,
Moreover, the exterior of watches, eyeglass frames, rings, which are rich in adhesion, corrosion resistance, wear resistance and design variety,
It is possible to provide decorative members such as necklaces and earrings. As described above, the effect of the present invention is extremely large.
【図1】 本発明の[実施例群A]の装飾部材の被膜構
成を示す断面図。FIG. 1 is a cross-sectional view showing a coating structure of a decorative member of [Example group A] of the present invention.
【図2】 本発明の[実施例群A]の装飾部材の被膜構
成を示す断面図。FIG. 2 is a cross-sectional view showing a coating structure of a decorative member of [Example group A] of the present invention.
【図3】 本発明の[実施例群B]の装飾部材の被膜構
成を示す断面図。FIG. 3 is a cross-sectional view showing a coating structure of a decorative member of [Example group B] of the present invention.
【図4】 本発明の[実施例群B]の装飾部材の被膜構
成を示す断面図。FIG. 4 is a cross-sectional view showing a coating structure of a decorative member of [Example group B] of the present invention.
【図5】 本発明の[実施例群C]の装飾部材の被膜構
成を示す断面図。FIG. 5 is a cross-sectional view showing a coating structure of a decorative member of [Example group C] of the present invention.
【図6】 本発明の[実施例群C]の装飾部材の被膜構
成を示す断面図。FIG. 6 is a cross-sectional view showing a coating structure of a decorative member of [Example group C] of the present invention.
【図7】 本発明の[実施例群D]の装飾部材の被膜構
成を示す断面図。FIG. 7 is a cross-sectional view showing a coating structure of a decorative member of [Example group D] of the present invention.
【図8】 本発明の[実施例群D]の装飾部材の被膜構
成を示す断面図。FIG. 8 is a cross-sectional view showing a coating structure of a decorative member of [Example group D] of the present invention.
【図9】 本発明の[実施例群E]の装飾部材の被膜構
成を示す断面図。FIG. 9 is a cross-sectional view showing the coating structure of a decorative member of [Example group E] of the present invention.
【図10】 本発明の[実施例群E]の装飾部材の被膜
構成を示す断面図。FIG. 10 is a cross-sectional view showing the coating structure of a decorative member of [Example group E] of the present invention.
【図11】 本発明の[実施例群F]の装飾部材の被膜
構成を示す断面図。FIG. 11 is a cross-sectional view showing a coating configuration of a decorative member of [Example group F] of the present invention.
【図12】 本発明の[実施例群F]の装飾部材の被膜
構成を示す断面図。FIG. 12 is a cross-sectional view showing the coating structure of a decorative member of [Example group F] of the present invention.
1・・・・・・素材 2・・・・・・下地メッキ層 1 3・・・・・・イオンプレーティング層 1 4・・・・・・下地メッキ層 2 5・・・・・・金色メッキ層 1 6・・・・・・金色メッキ層 2 7・・・・・・部分イオンプレーティング層 1 8・・・・・・白色メッキ層 1 9・・・・・・白色メッキ層 2 10・・・・・・部分白色メッキ層1 11・・・・・・部分金色メッキ層1 1 ・ ・ Material 2 ・ ・ ・ ・ Undercoating layer 1 3 ・ ・ ・ ・ Ion plating layer 1 4 ・ ・ ・ ・ Undercoating layer 2 5 ・ ・ ・ ・ ・ ・ ・ ・ Gold color Plating layer 1 6 ··· Gold color plating layer 2 7 ··· Partial ion plating layer 18 ··· White plating layer 1 9 ··· White plating layer 2 10 --- Partial white plating layer 1 11 --- Partial gold plating layer 1
───────────────────────────────────────────────────── フロントページの続き (72)発明者 真保 晃 長野県諏訪市大和3丁目3番5号セイコー エプソン株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akira Maho 3-3-5 Yamato, Suwa-shi, Nagano Seiko Epson Corporation
Claims (6)
Ag、In、Pd−Co、PdーAg、Sn−Cu、S
nーZn、AgーSn、Pb−Sn、Cu−Sn−Zn
メッキの内の一種または二種以上の下地メッキ層を被覆
構成し、該表面上に Ti化合物またはCr化合物被膜
が形成されていることを特徴とする装飾部材。1. Cu, Co, Pd, on the surface of the alloy material,
Ag, In, Pd-Co, Pd-Ag, Sn-Cu, S
n-Zn, Ag-Sn, Pb-Sn, Cu-Sn-Zn
A decorative member, characterized in that one or more undercoating layers of plating are covered and a Ti compound or Cr compound coating is formed on the surface.
Co、Au−Pd、Au−Sn、Au−Pd−Cu、A
u−Pd−In、Au−Co−In、Au−Ag−C
u、Au−Ag、Au−Cu、Auメッキの内の一種ま
たは二種以上の金色メッキ層を被覆積層し、該金色メッ
キ層上に Ti化合物またはCr化合物被膜が全面また
は部分選択的に形成されていることを特徴とする装飾部
材。2. The Au-plated layer on the undercoat plating layer according to claim 1.
Co, Au-Pd, Au-Sn, Au-Pd-Cu, A
u-Pd-In, Au-Co-In, Au-Ag-C
u, Au-Ag, Au-Cu, Au plating of one or more of Au plating is laminated, and a Ti compound or Cr compound coating is selectively or entirely formed on the gold plating layer. A decorative member characterized by being.
Co、Pd、Pt、Rh、Ru、CRメッキの内の一種
または二種以上の白色メッキ層を被覆積層し、該白色メ
ッキ層上に Ti化合物またはCr化合物被膜が全面ま
たは部分選択的に形成されていることを特徴とする装飾
部材。3. Pd-on the base plating layer according to claim 1.
A white plating layer of one or more of Co, Pd, Pt, Rh, Ru, and CR plating is coated and laminated, and a Ti compound or Cr compound coating is formed on the entire or a partial selective surface of the white plating layer. A decorative member characterized by being.
o、Pd、Pt、Rh、Ru、CRメッキの内の一種ま
たは二種以上の白色メッキ層を部分選択的に被覆積層
し、該金色メッキ層または該白色メッキ層上に Ti化
合物またはCr化合物被膜が部分選択的に形成されてい
ることを特徴とする装飾部材。4. The Pd-C on the gold plating layer according to claim 2.
O, Pd, Pt, Rh, Ru, CR one or more kinds of white plating layers are partially selectively coated and laminated, and a Ti compound or Cr compound coating is formed on the gold plating layer or the white plating layer. The decorative member is characterized by being partially selectively formed.
Co、Au−Pd、Au−Sn、Au−Pd−Cu、A
u−Pd−In、Au−Co−In、Au−Ag−C
u、Au−Ag、Au−Cu、Auメッキの内の一種ま
たは二種以上の金色メッキ層を被覆積層し、該白色メッ
キ層上または該金色メッキ層上に Ti化合物またはC
r化合物被膜が全面または部分選択的に形成されている
ことを特徴とする装飾部材。5. The Au-plated layer on the white plated layer according to claim 3.
Co, Au-Pd, Au-Sn, Au-Pd-Cu, A
u-Pd-In, Au-Co-In, Au-Ag-C
u, Au-Ag, Au-Cu, Au plating, one or more kinds of gold-plated layers are laminated by coating, and a Ti compound or C is formed on the white-plated layer or the gold-plated layer.
An ornamental member characterized in that an r compound coating is formed on the entire surface or in a partial selective manner.
項2記載の金色メッキ層上または請求項3記載の白色メ
ッキ層上に、Ti化合物またはCr化合物被膜の中から
選ばれた色調の異なる二種以上の被膜を積層し、少なく
とも該化合物被膜の最上層を部分選択的に積層し、多色
に仕上げたことを特徴とする装飾部材。6. A color tone selected from a Ti compound or Cr compound coating on the undercoat plating layer according to claim 1, the gold plating layer according to claim 2, or the white plating layer according to claim 3. A decorative member, characterized in that two or more different kinds of coatings are laminated, and at least the uppermost layer of the compound coating is partially and selectively laminated to give a multicolor finish.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP23634091A JP2921204B2 (en) | 1991-09-17 | 1991-09-17 | Decorative material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP23634091A JP2921204B2 (en) | 1991-09-17 | 1991-09-17 | Decorative material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0570990A true JPH0570990A (en) | 1993-03-23 |
JP2921204B2 JP2921204B2 (en) | 1999-07-19 |
Family
ID=16999364
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP23634091A Expired - Fee Related JP2921204B2 (en) | 1991-09-17 | 1991-09-17 | Decorative material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2921204B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997020970A1 (en) * | 1995-08-23 | 1997-06-12 | Citizen Watch Co., Ltd. | Ornamental member |
JP2002161393A (en) * | 2000-11-22 | 2002-06-04 | Bikutoria:Kk | Method for plating noble metal having corrosion resistance and noble metal plate accessories |
WO2006079278A1 (en) * | 2005-01-25 | 2006-08-03 | Roring Industries (Xiamen), Ltd. | Decorative laminate, plating solution and plating method for forming the decorative layer, and products use this decorative layer |
-
1991
- 1991-09-17 JP JP23634091A patent/JP2921204B2/en not_active Expired - Fee Related
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997020970A1 (en) * | 1995-08-23 | 1997-06-12 | Citizen Watch Co., Ltd. | Ornamental member |
US5972526A (en) * | 1995-12-07 | 1999-10-26 | Citizen Watch Co., Ltd. | Decorative member |
JP2002161393A (en) * | 2000-11-22 | 2002-06-04 | Bikutoria:Kk | Method for plating noble metal having corrosion resistance and noble metal plate accessories |
WO2006079278A1 (en) * | 2005-01-25 | 2006-08-03 | Roring Industries (Xiamen), Ltd. | Decorative laminate, plating solution and plating method for forming the decorative layer, and products use this decorative layer |
Also Published As
Publication number | Publication date |
---|---|
JP2921204B2 (en) | 1999-07-19 |
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