JP3334577B2 - Ornament parts, ornaments, electronics and watches - Google Patents

Ornament parts, ornaments, electronics and watches

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Publication number
JP3334577B2
JP3334577B2 JP27630597A JP27630597A JP3334577B2 JP 3334577 B2 JP3334577 B2 JP 3334577B2 JP 27630597 A JP27630597 A JP 27630597A JP 27630597 A JP27630597 A JP 27630597A JP 3334577 B2 JP3334577 B2 JP 3334577B2
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JP
Japan
Prior art keywords
layer
decorative
passivation film
component according
coating layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP27630597A
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Japanese (ja)
Other versions
JPH11106951A (en
Inventor
亙 塚本
清博 今井
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Seiko Epson Corp
Original Assignee
Seiko Epson Corp
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Filing date
Publication date
Application filed by Seiko Epson Corp filed Critical Seiko Epson Corp
Priority to JP27630597A priority Critical patent/JP3334577B2/en
Publication of JPH11106951A publication Critical patent/JPH11106951A/en
Application granted granted Critical
Publication of JP3334577B2 publication Critical patent/JP3334577B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明が属する技術分野】本発明は装飾品用部品、およ
びこれを備えた装飾品、電子機器および時計に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative part, and a decorative part, an electronic device and a timepiece provided with the part.

【０００２】[0002]

【従来の技術】従来、時計用外装部品表面に耐食性、耐
衝撃性（耐応力割れ性）、耐摩耗性等を向上させ、ま
た、素地表面に白銀色の色調を施すために白色系Ｐｄ−
Ｎｉ合金メッキが行われていた。しかし、このメッキ層
が皮膚に直接触れるとメッキ層から溶出するＮｉによ
り、皮膚カブレ等を引き起こす金属アレルギーが問題と
なっていた。2. Description of the Related Art Conventionally, a white Pd-based material has been used to improve corrosion resistance, impact resistance (stress cracking resistance), abrasion resistance and the like on the surface of watch exterior parts, and to impart a silver-white color tone to the substrate surface.
Ni alloy plating was performed. However, when the plating layer comes into direct contact with skin, Ni elutes from the plating layer, causing a problem of metal allergy causing skin rash and the like.

【０００３】そこで、Ｐｄ−Ｎｉ合金メッキ層に代わ
り、Ｎｉを含有しないＰｄを主成分とする白色系メッキ
層を設けることが試みられている。このようなＰｄメッ
キ層を設けることにより金属アレルギーの問題は解消さ
れるが、外気に放置しておくとメッキ層中のＰｄが大気
中のＳ、Ｏ、Ｃ等を経時的に吸着し、該Ｐｄメッキ層表
面に黒褐色系の変質層を形成する。したがって、Ｐｄメ
ッキ層を設けた時計用外装部品を腕時計等に用いた場
合、腕時計の外装部分が店頭に陳列されている間に変色
し、商品価値が損なわれてしまうという問題があった。Therefore, an attempt has been made to provide a white plating layer mainly containing Pd containing no Ni instead of the Pd-Ni alloy plating layer. By providing such a Pd plating layer, the problem of metal allergy can be solved, but if left in the open air, Pd in the plating layer adsorbs S, O, C, etc. in the air with the passage of time. A black-brown deteriorated layer is formed on the surface of the Pd plating layer. Therefore, when a watch exterior component provided with a Pd plating layer is used for a wristwatch or the like, there has been a problem that the exterior portion of the wristwatch is discolored while being displayed at a store and the commercial value is impaired.

【０００４】このような変質層の形成等の問題は、最表
層が純Ｐｄメッキ層である場合に特に顕著に現れてい
た。[0004] Such a problem as the formation of an altered layer has been particularly prominent when the outermost layer is a pure Pd plating layer.

【０００５】[0005]

【発明が解決しようとする課題】本発明の目的は、耐変
色性、耐食性等に優れる装飾品用部品、およびこれを備
えた装飾品、電子機器および時計を提供することにあ
る。SUMMARY OF THE INVENTION An object of the present invention is to provide a decorative component having excellent discoloration resistance, corrosion resistance, and the like, and a decorative component, an electronic device, and a timepiece provided with the component.

【０００６】[0006]

【課題を解決するための手段】このような目的は、下記
（１）〜（２１）の本発明により達成される。This and other objects are achieved by the present invention which is defined below as (1) to (21).

【０００７】（１） 素地上に少なくとも１層からなる
下地層と、ＰｄまたはＰｄ系合金からなる被覆層が設け
られ、該被覆層表面に不動態被膜が形成されていること
を特徴とする装飾品用部品。[0007] (1) A decoration characterized in that at least one underlayer and a coating layer made of Pd or a Pd-based alloy are provided on a substrate, and a passivation film is formed on the surface of the coating layer. Goods parts.

【０００８】（２） 前記不動態被膜は酸化剤溶液に浸
漬することにより形成される上記（（１）に記載の装飾
品用部品。(2) The decorative article according to (1), wherein the passivation film is formed by immersing the film in an oxidizing agent solution.

【０００９】（３） 前記酸化剤溶液はクロム酸塩溶液
である上記（２）に記載の装飾品用部品。(3) The decorative component according to (2), wherein the oxidizing agent solution is a chromate solution.

【００１０】（４） 前記溶液は重クロム酸塩の水溶液
である上記（３）に記載の装飾品用部品。(4) The decorative component according to the above (3), wherein the solution is an aqueous solution of dichromate.

【００１１】（５） 前記重クロム酸塩の水溶液は重ク
ロム酸塩を３〜７wt％含有する上記（４）に記載の装飾
品用部品。(5) The decorative component according to the above (4), wherein the aqueous solution of bichromate contains 3 to 7% by weight of dichromate.

【００１２】（６） 前記酸化剤溶液への浸漬時間が１
５〜６０秒である上記（２）ないし（５）のいずれかに
記載の装飾品用部品。(6) The immersion time in the oxidizing agent solution is 1
The decorative article component according to any one of the above (2) to (5), which has a duration of 5 to 60 seconds.

【００１３】（７） 前記被覆層は純Ｐｄ層である上記
（１）ないし（６）のいずれかに記載の装飾品用部品。(7) The decorative component according to any one of (1) to (6), wherein the coating layer is a pure Pd layer.

【００１４】（８） 前記被覆層はメッキ層である上記
（１）ないし（７）のいずれかに記載の装飾品用部品。(8) The decorative component according to any one of (1) to (7), wherein the coating layer is a plating layer.

【００１５】（９） 前記メッキ層は亜硝酸系パラジウ
ム溶液を用いて設けられたものである上記（８）に記載
の装飾品用部品。(9) The decorative component according to the above (8), wherein the plating layer is provided using a nitrous acid-based palladium solution.

【００１６】（10） 前記被覆層の厚さが０．３〜１１
μｍであることを特徴とする上記（（１）ないし（９）
のいずれかに記載の装飾品用部品。(10) The coating layer has a thickness of 0.3 to 11
(1) to (9), wherein
A decorative part according to any one of the above.

【００１７】（11） 前記被覆層上にＡｕまたはＮｉ不
含有Ａｕ系合金からなる層が設けられた上記（１）ない
し（10）のいずれかに記載の装飾品用部品。(11) The decorative component according to any one of (1) to (10), wherein a layer made of Au or a Ni-free Au-based alloy is provided on the coating layer.

【００１８】（12） 前記ＡｕまたはＮｉ不含有Ａｕ系
合金からなる層の厚さは０．５〜１０μｍである上記
（11）に記載の装飾品用部品。(12) The decorative component according to the above (11), wherein the layer made of the Au or Ni-free Au-based alloy has a thickness of 0.5 to 10 μm.

【００１９】（13） 前記ＡｕまたはＮｉ不含有Ａｕ系
合金からなる層に前記不動態被膜が形成された上記（1
1）または（12）に記載の装飾品用部品。(13) The above (1) wherein the passivation film is formed on the layer made of the Au or Ni-free Au-based alloy.
A decorative part according to (1) or (12).

【００２０】（14） 前記不動態被膜は、該不動態被膜
の有無による前記装飾品用部品の表面の色差が１．８以
下である上記（１）ないし（13）のいずれかに記載の装
飾品用部品。(14) The decoration according to any one of (1) to (13), wherein the passivation film has a color difference of 1.8 or less on the surface of the ornamental component depending on the presence or absence of the passivation film. Goods parts.

【００２１】（15） 前記不動態被膜は、該不動態被膜
の有無による前記装飾品用部品の表面の色差が１．０以
下である上記（１）ないし（14）のいずれかに記載の装
飾品用部品。(15) The decoration according to any one of the above (1) to (14), wherein the passivation film has a color difference of 1.0 or less on the surface of the decorative article component depending on the presence or absence of the passivation film. Goods parts.

【００２２】（16） 前記下地層はＣｕ、Ｎｉ不含有Ｃ
ｕ系合金、Ａｕ、Ｎｉ不含有Ａｕ系合金、Ｐｄ、Ｎｉ不
含有Ｐｄ系合金からなる群より選ばれた少なくとも１つ
から構成される層を有する上記（１）ないし（15）のい
ずれかに記載の装飾品用部品。(16) The underlayer is made of Cu containing no Cu or Ni.
Any of the above (1) to (15) having a layer composed of at least one selected from the group consisting of a u-based alloy, Au, a Ni-free Au-based alloy, Pd, and a Ni-free Pd-based alloy. Parts for decorative goods as described.

【００２３】（17） 前記下地層の厚さが０．５〜３０
μｍである上記（１）ないし（16）のいずれかに記載の
装飾品用部品。(17) The underlayer has a thickness of 0.5 to 30.
The decorative component according to any one of the above (1) to (16), which has a size of μm.

【００２４】（18） 前記装飾品用部品は時計用外装部
品である上記（１）ないし（17）のいずれかに記載の装
飾品用部品。(18) The decorative part according to any one of the above (1) to (17), wherein the decorative part is a watch exterior part.

【００２５】（19） 上記（１）ないし（18）のいずれ
かに記載の装飾品用部品を備えることを特徴とする装飾
品。(19) A decorative article comprising the decorative part according to any one of the above (1) to (18).

【００２６】（20） 上記（１）ないし（18）のいずれ
かに記載の装飾品用部品を備えることを特徴とする電子
機器。(20) An electronic device comprising the decorative component according to any one of (1) to (18).

【００２７】（21） 上記（18）に記載の時計用外装部
品を備えることを特徴とする時計。(21) A timepiece comprising the timepiece exterior part according to (18).

【００２８】[0028]

【発明の実施の形態】以下、本発明の装飾品用部品の実
施例について図を参照しながら説明する。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of a decorative part according to an embodiment of the present invention.

【００２９】図１は、本発明の装飾品用部品の一例を示
す時計用外装部品１の部分断面図である。FIG. 1 is a partial cross-sectional view of a watch exterior part 1 showing an example of a decorative part according to the present invention.

【００３０】図１に示すように、本発明の時計用外装部
品１は、該部品を構成する素地４と、素地４の上に少な
くとも１層からなる下地層３と、下地層３の上にＰｄま
たはＮｉ不含有Ｐｄ系合金からなる被覆層９とを有し、
該被覆層９の表面に不動態被膜２が形成されている。As shown in FIG. 1, a watch exterior part 1 according to the present invention comprises a base 4 constituting the part, a base layer 3 comprising at least one layer on the base 4, and a base layer 3 on the base layer 3. A coating layer 9 made of a Pd or Ni-free Pd-based alloy,
The passivation film 2 is formed on the surface of the coating layer 9.

【００３１】素地４の構成材料は、時計用外装部品１を
成形する基礎となるものであって、外的影響に対する耐
久性、加工容易性等の観点から適宜選択される。The constituent material of the base 4 is a basis for forming the timepiece exterior part 1 and is appropriately selected from the viewpoint of durability against external influences, workability, and the like.

【００３２】例えば、時計用外装部品１が腕時計のよう
な携帯時計の場合、耐食性、強度および切削・研磨等の
加工性の良さと、製造コストとの観点から選択され、例
えば、ステンレス鋼、黄銅、洋白等の銅系合金、チタ
ン、金、銀、白金等の貴金属等またはこれらの貴金属を
含む合金等の金属材料、Ａｌ2 Ｏ3 系、ＳｉＯ2 系、Ｚ
ｒＯ2 系セラミックス等のセラミックス材料、またはＡ
ＢＳ樹脂（アクリロニトリル・ブタジエン・スチレ
ン）、ＦＲＰ（繊維強化プラスチック）等の樹脂材料が
用いられる。これらの金属材料、セラミックス材料、樹
脂材料は、部品の全部を構成するものには限られず、他
の材料との組合せにより部品の一部分を構成するもので
あってもよい。For example, when the watch exterior part 1 is a portable watch such as a wristwatch, it is selected from the viewpoints of corrosion resistance, strength, workability such as cutting and polishing, and manufacturing cost. , Nickel-based alloys such as copper alloys, titanium, gold, silver, platinum and other noble metals or metal materials such as alloys containing these noble metals, Al 2 O 3 -based, SiO 2 -based, Z
Ceramic materials such as rO 2 ceramics or A
Resin materials such as BS resin (acrylonitrile / butadiene / styrene) and FRP (fiber reinforced plastic) are used. These metal materials, ceramic materials, and resin materials are not limited to those constituting the entire part, but may be those constituting a part of the part in combination with other materials.

【００３３】素地４の製造方法は特に限定されず、例え
ば、プレス加工、切削加工、鍛造加工、鋳造加工、粉末
冶金焼結、金属粉末射出成形（ＭＩＭ）、ロストワック
ス法等が挙げられる。The method for producing the substrate 4 is not particularly limited, and examples thereof include pressing, cutting, forging, casting, powder metallurgy sintering, metal powder injection molding (MIM), and a lost wax method.

【００３４】また、素地４の表面は表面仕上加工が施さ
れていることが好ましく、必要に応じて、例えば鏡面研
磨加工、すじ目加工、ホーニング加工、マーキング加工
等による表面仕上げが挙げられ、これらを２種以上組合
せた表面仕上げが施されていてもよい。The surface of the substrate 4 is preferably subjected to a surface finishing process. If necessary, a surface finish such as a mirror polishing process, a streaking process, a honing process, a marking process, or the like may be used. May be applied to the surface finish.

【００３５】素地４上には、種々の目的により少なくと
も１層からなる下地層３が設けられている。下地層３を
設けることにより耐食性を確保することができる。例え
ば、素地４の表面にピンホールがあった場合、そこへ水
や気体が侵入し素地４が侵されて錆び、ひび割れ等が発
生するのを防ぐ役割を果たす。さらに、素地４にバリ、
肌荒れ等の欠陥があった場合、後述の被覆層９がバリ部
分で薄くなり、耐食性が不十分となるおそれがある。し
たがって、このような素地４の表面の欠陥をカバーする
ことを目的として設けられるものである。On the substrate 4, an underlayer 3 composed of at least one layer is provided for various purposes. By providing the underlayer 3, corrosion resistance can be ensured. For example, if there is a pinhole on the surface of the substrate 4, it plays a role in preventing water and gas from entering into the substrate 4, and thereby preventing the substrate 4 from being rusted and cracked. Furthermore, the base 4 has burr,
When there is a defect such as rough skin, a coating layer 9 described later becomes thin at a burr portion, and the corrosion resistance may be insufficient. Therefore, it is provided for the purpose of covering such a defect on the surface of the substrate 4.

【００３６】さらに、被覆層９に対し密着性のよい層を
下地層３の最表面に設けることにより、下地層３と被覆
層９との密着性を向上させることも可能である。Further, by providing a layer having good adhesion to the coating layer 9 on the outermost surface of the underlayer 3, the adhesion between the underlayer 3 and the coating layer 9 can be improved.

【００３７】下地層３は少なくとも１層から構成され、
Ｃｕ、Ｎｉ不含有Ｃｕ系合金、Ａｕ、Ｎｉ不含有Ａｕ系
合金、Ｐｄ、Ｎｉ不含有Ｐｄ系合金からなる群より選択
された少なくとも一種から構成される層を有することが
好ましい。このような構成とすることにより、上記の効
果がより一層向上する。また、Ｎｉを含有しない下地層
を設けることにより、金属アレルギー等の問題を回避す
ることができる。The underlayer 3 is composed of at least one layer.
It is preferable to have a layer made of at least one selected from the group consisting of Cu, Ni-free Cu-based alloy, Au, Ni-free Au-based alloy, Pd, and Ni-free Pd-based alloy. With such a configuration, the above effect is further improved. Further, by providing an underlayer containing no Ni, it is possible to avoid problems such as metal allergy.

【００３８】なお、ここで「Ｎｉ不含有」とは、各種合
金中にＮｉが全く含まれていないか、あるいは、金属ア
レルギー等の観点から無視できる程度の極微量しか含ま
れていないことを意味する。Here, "Ni-free" means that various alloys contain no Ni or only negligible traces from the viewpoint of metal allergy and the like. I do.

【００３９】本実施例の場合、素地４に接触している側
から、Ｃｕ st.層５（ st.＝ストライクメッキ：０．１
μm 以下の薄いメッキ層を意味する）、Ｃｕ層６、Ｃｕ
−Ｓｎ合金層７、Ａｕ st.またはＰｄ st.層８とから構
成されている。なお、ストライクメッキは異種層間の密
着性向上のため設けられる層である。In the case of this embodiment, the Cu st. Layer 5 (st. = Strike plating: 0.1
μm or less), Cu layer 6, Cu layer
-Sn alloy layer 7, Au st. Or Pd st. Layer 8. The strike plating is a layer provided for improving the adhesion between different kinds of layers.

【００４０】下地層３の厚さは特に限定されないが、合
計で０．５〜３０μm が好ましく、１．０〜１０μm が
特に好ましい。下地層３が０．５μm 未満である場合、
耐食性が確保されにくく、また３０μm を超えると下地
層３自身にクラックが発生するおそれがあり、したがっ
て耐食性を確保できないおそれがある。The thickness of the underlayer 3 is not particularly limited, but is preferably 0.5 to 30 μm in total, and particularly preferably 1.0 to 10 μm. When the underlayer 3 is less than 0.5 μm,
Corrosion resistance is hardly ensured, and if it exceeds 30 μm, cracks may occur in the underlayer 3 itself, so that corrosion resistance may not be ensured.

【００４１】下地層３を構成する各層の厚さは上記の合
計膜厚の範囲内であれば、いかなる厚さであってもよ
く、また成膜方法についても特に限定されず、例えば、
通常の湿式メッキ法や、蒸着法、スパッタリング、イオ
ンプレーティング等の乾式メッキ法等のいかなる方法に
よるものであってもよいが、同一成膜法で連続的に積層
することが好ましい。The thickness of each layer constituting the underlayer 3 may be any thickness as long as it is within the range of the above total film thickness, and the film forming method is not particularly limited.
Although any method such as a usual wet plating method, a dry plating method such as an evaporation method, a sputtering method, and an ion plating method may be used, it is preferable to continuously laminate by the same film forming method.

【００４２】なお、上記の下地層３の構成は一例であっ
て、下地層の層構成や形成方法等はいかなるものであっ
てもよい。The configuration of the underlayer 3 described above is an example, and the underlayer may have any layer configuration, formation method, or the like.

【００４３】下地層３の上には主としてＰｄからなる被
覆層９が設けられている。これにより、時計用外装部品
１の耐食性、耐摩耗性、耐変色品質が向上する。また、
被覆層９は白銀色を呈しているため、高級感を付与する
ことができる。On the underlayer 3, a coating layer 9 mainly made of Pd is provided. Thereby, the corrosion resistance, wear resistance, and discoloration resistance quality of the timepiece exterior component 1 are improved. Also,
Since the coating layer 9 has a silvery white color, it can give a sense of quality.

【００４４】被覆層９はＰｄまたはＮｉ不含有Ｐｄ系合
金からなる層であって、特に純Ｐｄ層であることが好ま
しい。純Ｐｄ層は美しい白銀色を呈するため商品価値を
向上させることができる。また、Ｎｉを含有しないため
金属アレルギー等の問題を引き起こすおそれがない。さ
らに、素地４にＮｉを含有する材料が使用され、あるい
はＮｉを含有する下地層が設けられている場合であって
も、そのような材料や下地層からのＮｉの溶出を阻止す
ることができる。この意味で純Ｐｄ層による被覆層９は
溶出金属バリア層としても機能し得る。The coating layer 9 is a layer made of a Pd-based alloy containing no Pd or Ni, and is particularly preferably a pure Pd layer. Since the pure Pd layer presents a beautiful white silver color, its commercial value can be improved. Further, since it does not contain Ni, there is no possibility of causing problems such as metal allergy. Furthermore, even when a material containing Ni is used for the substrate 4 or an underlayer containing Ni is provided, the elution of Ni from such a material or the underlayer can be prevented. . In this sense, the coating layer 9 made of a pure Pd layer can also function as an eluting metal barrier layer.

【００４５】ここで、「純Ｐｄ層」とは、被覆層中にＰ
ｄを９９．９wt％以上を含有する層を意味する。Ｐｄの
含有量が９９．９％未満の場合、被覆層９にクラックが
発生しやすくなるおそれがある。純Ｐｄ層中には、０．
１wt％未満の他の成分、他の元素が含まれていてもよ
い。例えば、他の成分としては光沢剤等が挙げられ、他
の元素としては例えばＡｌ、Ａｕ、Ｆｅ、Ｔｉ、Ｃｒ、
Ｃｕ、Ｐｔ、Ｓｎ、Ｖ、Ｉｎ等が挙げられる。Here, the “pure Pd layer” means that P
d means a layer containing 99.9% by weight or more. When the content of Pd is less than 99.9%, cracks may easily occur in the coating layer 9. In the pure Pd layer, 0.
Other components less than 1 wt% and other elements may be contained. For example, other components include a brightener and the like, and other elements include, for example, Al, Au, Fe, Ti, Cr,
Cu, Pt, Sn, V, In and the like can be mentioned.

【００４６】このような被覆層９はメッキ層であること
が好ましい。これにより密着性、耐摩耗性等に優れた被
膜を形成することができる。また、時計用外装部品１の
形状、大きさを問わず被覆層９を設けることができ、層
の厚さの調整も容易である。Such a coating layer 9 is preferably a plating layer. This makes it possible to form a film having excellent adhesion, abrasion resistance and the like. In addition, the covering layer 9 can be provided regardless of the shape and size of the timepiece exterior component 1, and the thickness of the layer can be easily adjusted.

【００４７】本発明で用い得るメッキ方法としては特に
限定されず、例えば、電解メッキや無電解メッキ等の湿
式メッキ法や、蒸着法、スパッタリング、イオンプレー
ティング等の乾式メッキ法等が挙げられる。The plating method usable in the present invention is not particularly limited, and examples thereof include a wet plating method such as electrolytic plating and electroless plating, and a dry plating method such as vapor deposition, sputtering, and ion plating.

【００４８】純Ｐｄ層がメッキにより設けられる場合、
メッキ液としては特に限定されず、例えば亜硝酸系パラ
ジウムメッキ液や塩化パラジウム系メッキ液等が挙げら
れるが、亜硝酸系パラジウムメッキ液が好ましい。これ
により、耐応力割れ品質のより良好なメッキ層を容易に
形成することができる。When a pure Pd layer is provided by plating,
The plating solution is not particularly limited and includes, for example, a nitrite-based palladium plating solution, a palladium chloride-based plating solution, and the like, and a nitrite-based palladium plating solution is preferable. As a result, a plating layer having better stress cracking resistance can be easily formed.

【００４９】被覆層９の厚さは０．３〜１１μｍが好ま
しく、１．０〜５．０μｍがより好ましい。被覆層９の
厚さが０．３μｍ未満であると耐食性等の向上を図るこ
とが困難である場合がある。一方、１１μｍを超えると
耐クラック性が低下するおそれがあり、さらには製造コ
ストが増大することとなる。The thickness of the coating layer 9 is preferably from 0.3 to 11 μm, more preferably from 1.0 to 5.0 μm. If the thickness of the coating layer 9 is less than 0.3 μm, it may be difficult to improve corrosion resistance and the like. On the other hand, if it exceeds 11 μm, the crack resistance may decrease, and the production cost will further increase.

【００５０】該被覆層９の表面には不動態被膜２が形成
されている。これにより、耐食性、耐変色性等が向上す
る。The passivation film 2 is formed on the surface of the coating layer 9. Thereby, corrosion resistance, discoloration resistance, and the like are improved.

【００５１】不動態被膜２の形成方法は特に限定されな
いが、例えば酸化剤溶液に浸漬することが好ましい。酸
化剤により金属表面が酸化され、薄く強固な金属酸化物
膜による不動態被膜が形成される。この不動態被膜２が
保護層として機能し、耐変色性、耐食性を向上させるこ
とができる。The method for forming the passivation film 2 is not particularly limited, but is preferably immersed in, for example, an oxidizing agent solution. The metal surface is oxidized by the oxidizing agent, and a passive film formed of a thin and strong metal oxide film is formed. The passivation film 2 functions as a protective layer, and can improve discoloration resistance and corrosion resistance.

【００５２】酸化剤溶液は特に限定されず、例えばクロ
ム酸塩溶液であることが好ましい。クロム酸塩は強力な
酸化作用を有しており、上記金属酸化物被膜を容易に形
成することができる。クロム酸塩には、クロム（IV）酸
塩、クロム（Ｖ）酸塩、クロム（VI）酸塩、重クロム
（VI）酸塩等が挙げられるが、重クロム（VI）酸塩が特
に好ましい。重クロム酸塩の酸性水溶液は強力な酸化作
用を有するため、金属の酸化を促進し不動態被膜２をよ
り容易に形成することができる。The oxidizing agent solution is not particularly limited, and is preferably, for example, a chromate solution. Chromate has a strong oxidizing effect, and can easily form the above-mentioned metal oxide film. Chromates include chromate (IV), chromate (V), chromate (VI), bichromate (VI), and the like, with dichromate (VI) being particularly preferred. . Since the acidic aqueous solution of the dichromate has a strong oxidizing action, the oxidation of the metal is promoted and the passivation film 2 can be more easily formed.

【００５３】この不動態被膜２は、該不動態被膜２の有
無による前記装飾品用部品の表面の色差が１．８以下で
あることが好ましく、１．０以下であることが特に好ま
しい。色差が１．８を超える場合、前記被覆層９や後述
するＡｕまたはＮｉ不含有Ａｕ系合金からなる層１０の
表面の色調、光沢等が変化してしまう可能性があり、肉
眼でもその差が判る場合がある。ただし、色差１．０〜
１．８程度のものであっても特に高品質が要求される特
殊品を除き、部品として使用しても何ら問題を生じるも
のではない。The color difference of the surface of the decorative component according to the presence or absence of the passivation film 2 is preferably 1.8 or less, particularly preferably 1.0 or less. When the color difference exceeds 1.8, there is a possibility that the color tone, gloss, and the like of the surface of the coating layer 9 and a layer 10 made of Au or a Ni-free Au-based alloy described later may change, and the difference is visible even to the naked eye. You may understand. However, color difference 1.0 ~
Even if it is about 1.8, it does not cause any problem even if it is used as a part, except for special products requiring particularly high quality.

【００５４】上記のような不動態被膜２の形成は、例え
ば重クロム酸塩の濃度および浸漬時間等により制御する
ことができる。具体的には、重クロム酸塩の水溶液は重
クロム酸塩を３〜７wt％含有することが好ましく、４〜
６wt％がより好ましい。重クロム酸塩の含有量が３wt％
未満であると不動態被膜２の形成が不十分となる場合が
あり、一方、７wt％を超えると上述の色差が１．０を超
える場合がある。The formation of the passivation film 2 as described above can be controlled by, for example, the concentration of dichromate and the immersion time. Specifically, the aqueous solution of dichromate preferably contains 3 to 7% by weight of dichromate,
6 wt% is more preferred. Bichromate content is 3wt%
If it is less than 7, the formation of the passivation film 2 may be insufficient. On the other hand, if it exceeds 7 wt%, the above-mentioned color difference may exceed 1.0.

【００５５】また、酸化剤溶液への浸漬時間は特に限定
されないが、１５〜６０秒であることが好ましい。浸漬
時間が短か過ぎると不動態被膜２の形成が不十分となる
場合があり、一方、６０秒を超えると、特に酸化剤濃度
が高い浸漬液を使用する場合には、表面の色差が１．０
を超え、メッキ等による表面仕上げの際の色調、光沢等
が変わるおそれがある。The immersion time in the oxidizing agent solution is not particularly limited, but is preferably 15 to 60 seconds. If the immersion time is too short, the formation of the passivation film 2 may be insufficient. On the other hand, if the immersion time is longer than 60 seconds, the color difference on the surface may be one, especially when using an immersion liquid having a high oxidizing agent concentration. .0
And the color tone, gloss, etc., at the time of surface finishing by plating or the like may change.

【００５６】図２は、装飾品用部品の第２の実施例を示
す時計用外装部品１の部分断面図である。図に示すよう
に、上記被覆層９上にＡｕまたはＮｉ不含有Ａｕ系合金
からなる層１０（以下、単に「Ａｕ層１０」という）が
設けられている。Ａｕ層１０を設けることにより、黄金
色の色調を付与することができ、豪華さをだすことがで
きる。FIG. 2 is a partial sectional view of a timepiece exterior part 1 showing a second embodiment of a decorative part. As shown in the drawing, a layer 10 made of Au or a Ni-free Au-based alloy (hereinafter, simply referred to as “Au layer 10”) is provided on the coating layer 9. By providing the Au layer 10, a golden color tone can be provided, and luxury can be achieved.

【００５７】また、図に示すように、Ａｕ層１０は部分
的に設けることが好ましい。前記被覆層９の白銀色とＡ
ｕ層１０の黄金色との組合せにより、単一色調よりも高
級な質感や色調を得ることができ、審美感を増すことが
できる。As shown in the figure, it is preferable that the Au layer 10 is partially provided. The silver color of the coating layer 9 and A
By combining with the golden color of the u layer 10, it is possible to obtain a higher quality texture and color tone than a single color tone, and it is possible to increase the aesthetic feeling.

【００５８】なお、Ａｕ系合金とは例えばＡｕを約５０
wt％以上含有するような、Ａｕを主とする合金を意味す
る。ＡｕとともにＡｕ層１０を構成し得る元素として
は、例えば、Ｃｕ、Ａｇ、Ｚｎ、Ｐｄ、Ｆｅ、Ｉｎ、Ｔ
ｉ、Ｃｏ、Ｓｎ等が挙げられる。このような元素をＡｕ
に添加することにより、Ａｕの持つ本来のイエローゴー
ルドと呼ばれる色調から、赤味を帯びたレッドゴール
ド、ピンクゴールド等の色調の変化を出すこともでき
る。The Au-based alloy is, for example, about 50% Au.
Au-based alloy containing at least wt% is meant. Elements that can constitute the Au layer 10 together with Au include, for example, Cu, Ag, Zn, Pd, Fe, In, T
i, Co, Sn and the like. Such an element is referred to as Au
Can change the color tone of red gold, pink gold, etc., which is reddish, from the original color tone of yellow gold possessed by Au.

【００５９】Ａｕ層１０の厚さは０．５〜１０μｍが好
ましい。Ａｕ層１０が薄過ぎると耐摩耗性が不十分とな
るおそれがあり、一方、厚過ぎると上記効果の向上がみ
られないばかりでなく製造コストが大きくなる。The thickness of the Au layer 10 is preferably 0.5 to 10 μm. If the Au layer 10 is too thin, the abrasion resistance may be insufficient. On the other hand, if the Au layer 10 is too thick, the above effects are not improved, and the manufacturing cost is increased.

【００６０】このようなＡｕ層１０上に、前記と同様の
不動態被膜２が形成される。これにより、表面の耐食
性、耐変色性が向上する。A passivation film 2 similar to the above is formed on such an Au layer 10. Thereby, corrosion resistance and discoloration resistance of the surface are improved.

【００６１】上記本発明の装飾品用部品を用いて、図３
に示すような腕時計１Ａ（携帯時計）が組立てられる。
同図に示すように、本発明の腕時計１Ａは、胴（ケー
ス）２２と、裏蓋２３と、ベゼル（縁）２４と、ガラス
板２５とを備えている。ケース２２内には、図示しない
ムーブメント（例えば文字板、針付きのもの）が収納さ
れる。By using the decorative article part of the present invention, FIG.
A wristwatch 1A (portable watch) as shown in FIG.
As shown in the figure, a wristwatch 1A of the present invention includes a body (case) 22, a back cover 23, a bezel (edge) 24, and a glass plate 25. A movement (not shown) (for example, one with a dial and a needle) is stored in the case 22.

【００６２】胴２２には巻真パイプ２６が嵌入・固定さ
れ、この巻真パイプ２６内にはりゅうず２７の軸部２７
１が回転可能に挿入されている。A stem winding pipe 26 is fitted into and fixed to the body 22.
1 is rotatably inserted.

【００６３】胴２２、裏蓋２３、ベゼル２４、巻真パイ
プ２６は、それぞれ上述したような金属材料で構成され
ている。胴２２とベゼル２４とは、プラスチックパッキ
ン２８により固定され、ベゼル２４とガラス板２５とは
プラスチックパッキン２９により固定されている。The body 22, the back cover 23, the bezel 24, and the winding stem pipe 26 are each made of the above-described metal material. The body 22 and the bezel 24 are fixed by a plastic packing 28, and the bezel 24 and the glass plate 25 are fixed by a plastic packing 29.

【００６４】また、胴２２に対し裏蓋２３が嵌合（また
は螺合）されており、これらの接合部（シール部）５０
には、リング状のゴムパッキン（裏蓋パッキン）４０が
圧縮状態で介挿されている。この構成によりシール部５
０が液密に封止され、防水機能が得られる。The back cover 23 is fitted (or screwed) to the body 22, and these joints (seal portions) 50 are joined.
, A ring-shaped rubber packing (back cover packing) 40 is inserted in a compressed state. With this configuration, the sealing portion 5
0 is sealed in a liquid-tight manner to obtain a waterproof function.

【００６５】りゅうず２７の軸部２７１の途中の外周に
は溝２７２が形成され、この溝２７２内にはリング状の
ゴムパッキン（りゅうずパッキン）３０が嵌合されてい
る。ゴムパッキン３０は巻真パイプ２６の内周面に密着
し、該内周面と溝２７２の内面との間で圧縮される。こ
の構成により、りゅうず２７と巻真パイプ２６との間が
液密に封止され防水機能が得られる。なお、りゅうず２
７を回転操作したとき、ゴムパッキン３０は軸部２７１
と共に回転し、巻真パイプ２６の内周面に密着しながら
周方向に摺動する。A groove 272 is formed in the outer periphery of the crown 27 of the crown 27 in the middle thereof, and a ring-shaped rubber packing (crown packing) 30 is fitted in the groove 272. The rubber packing 30 is in close contact with the inner peripheral surface of the winding stem pipe 26 and is compressed between the inner peripheral surface and the inner surface of the groove 272. With this configuration, the space between the crown 27 and the winding stem pipe 26 is liquid-tightly sealed, and a waterproof function is obtained. In addition, crown 2
7 is rotated, the rubber packing 30 is moved to the shaft portion 271.
, And slides in the circumferential direction while closely contacting the inner peripheral surface of the winding stem pipe 26.

【００６６】本発明の腕時計１Ａは、ベゼル２４、胴２
２、りゅうず２７、裏蓋２３等の時計用外装部品のう
ち、少なくとも１つ前述した不動態被膜２が設けられた
部品を備えるものである。The wristwatch 1A of the present invention has a bezel 24, a torso 2
2. Of the timepiece exterior parts such as the crown 27 and the back cover 23, at least one part provided with the above-mentioned passive film 2 is provided.

【００６７】本発明の装飾品用部品１を図示の各実施例
について説明したが、これらに限定されるものではな
い。装飾品用部品１を備える装飾品としては、時計の他
に例えば、指輪、ネックレス、ブレスレット、イヤリン
グ、ピアス、眼鏡フレーム、ライター、ネクタイピン、
カフスボタン、その他の各種アクセサリ等であってもよ
い。Although the decorative component 1 of the present invention has been described with reference to the illustrated embodiments, the present invention is not limited to these embodiments. Examples of the ornament provided with the accessory component 1 include, in addition to a clock, a ring, a necklace, a bracelet, an earring, an earring, an eyeglass frame, a lighter, a tie pin,
A cufflink or other various accessories may be used.

【００６８】また、本発明の装飾品用部品１を備え、少
なくとも一部に装飾的効果を発揮し得るように用いられ
た電子機器類も本発明の対象となる。このような電子機
器としては、例えば、電子時計、携帯電話機、ポケット
ベル、電卓、パーソナルコンピュータ、ワードプロセッ
サ、プリンタ、複写機、電子玩具、各種測定機器、液晶
表示素子（ＬＣＤ）等が挙げられる。Also, electronic equipment provided with the decorative article component 1 of the present invention and used so as to at least partially exhibit a decorative effect is also an object of the present invention. Examples of such electronic devices include electronic watches, mobile phones, pagers, calculators, personal computers, word processors, printers, copiers, electronic toys, various measuring devices, liquid crystal display devices (LCD), and the like.

【００６９】[0069]

【実施例】次に、本発明の具体的実施例について説明す
る。Next, specific examples of the present invention will be described.

【００７０】（実施例１） １．装飾品用部品の作製 次のようにして、装飾品用部品（携帯時計の胴）を作製
した。(Example 1) Production of Parts for Ornaments Parts for ornaments (body of a mobile watch) were produced as follows.

【００７１】部品の形成 まず、腕時計用の胴２２を黄銅（Ｂｓ）を用いて鋳造に
より作製した。この部品の材料表面に鏡面仕上げ加工を
施した。Forming of Parts First, a body 22 for a wristwatch was produced by casting using brass (Bs). The material surface of this part was mirror-finished.

【００７２】下地層３の形成 次に、胴２２に表面処理を施した。まず、材料表面（素
地）に層５〜層８の４層からなる下地層３を形成した。
下地層３を構成する各層の厚さ、形成方法は下記の通り
である。なお、胴２２の素地に最も近い側から層５、層
６・・・とする。Formation of Underlayer 3 Next, the body 22 was subjected to a surface treatment. First, an underlayer 3 composed of four layers, layer 5 to layer 8, was formed on the material surface (base).
The thickness of each layer constituting the underlayer 3 and the forming method are as follows. Note that layers 5, 6,... Are arranged from the side closest to the base of the body 22.

【００７３】層５ 被膜成分：Ｃｕ 被膜方法：電解メッキ（ストライクメッキ） 層の厚さ：０．１μｍ 層６ 被膜成分：Ｃｕ 被膜方法：電解メッキ 層の厚さ：３μｍ 層７ 被膜成分：Ｃｕ−Ｓｎ 被膜方法：電解メッキ 層の厚さ：３μｍ 層８ 被膜成分：Ａｕ 被膜方法：電解メッキ（ストライクメッキ） 層の厚さ：０．１μｍ 被覆層９の形成 下地層３の上に、純Ｐｄからなる被覆層９を電解メッキ
により設けた。Layer 5 Coating component: Cu Coating method: electrolytic plating (strike plating) Layer thickness: 0.1 μm Layer 6 Coating component: Cu coating method: electrolytic plating Layer thickness: 3 μm Layer 7 Coating component: Cu— Sn Coating method: electrolytic plating Layer thickness: 3 μm Layer 8 Coating component: Au Coating method: electrolytic plating (strike plating) Layer thickness: 0.1 μm Formation of coating layer 9 On base layer 3, pure Pd Was formed by electrolytic plating.

【００７４】メッキ条件、被覆層９の膜性状は次の通り
である。The plating conditions and the film properties of the coating layer 9 are as follows.

【００７５】 メッキ液：亜硝酸系パラジウムアミン溶液 メッキ液温度：４５〜５０℃ メッキ液ｐＨ：７〜７．５ 電流密度：１．２〜１．８（Ａ／dm2) メッキ時間：１３［分］ 膜厚：４μｍ 不動態被膜２の形成 上記の被覆層９を設けた後、後処理洗浄を行った。すな
わち、メッキが終了した胴２２を水洗しメッキ液を洗い
流した。その後アルカリ脱脂を行ない再び水洗した。次
に、酸で中和し、水洗して後処理洗浄を終了した。Plating solution: Nitrite-based palladium amine solution Plating solution temperature: 45 to 50 ° C. Plating solution pH: 7 to 7.5 Current density: 1.2 to 1.8 (A / dm 2 ) Plating time: 13 [ Min] Film thickness: 4 μm Formation of passivation film 2 After the above-mentioned coating layer 9 was provided, post-processing washing was performed. That is, the body 22 after the plating was washed with water to wash away the plating solution. Thereafter, alkali degreasing was performed, and washing was performed again with water. Next, the mixture was neutralized with an acid and washed with water to complete the post-treatment washing.

【００７６】これを重クロム酸ナトリウム水溶液に浸漬
し、不動態被膜２を形成した。浸漬液、浸漬条件は以下
の通りである。This was immersed in an aqueous solution of sodium dichromate to form a passivation film 2. The immersion liquid and immersion conditions are as follows.

【００７７】重クロム酸ナトリウム水溶液濃度：３wt％ 浸漬時間：１５秒 熱風乾燥 上記重クロム酸ナトリウム水溶液に浸漬した胴２２を引
き上げた後、純水で洗浄し、その後８０〜１００℃で５
〜２０分間熱風乾燥して本発明の時計用外装部品１を得
た。Sodium dichromate aqueous solution concentration: 3 wt% Immersion time: 15 seconds Hot air drying After the body 22 immersed in the above-mentioned sodium dichromate aqueous solution is pulled up, washed with pure water, and then washed at 80-100 ° C. for 5 seconds.
This was dried with hot air for about 20 minutes to obtain the timepiece exterior part 1 of the present invention.

【００７８】（実施例２〜２１）不動態被膜２の形成条
件（重クロム酸ナトリウム水溶液濃度、浸漬時間）を表
１に示す組合せとした以外は実施例１と同様にして、本
発明の時計用外装部品１を作製した。(Examples 2 to 21) The timepiece of the present invention was prepared in the same manner as in Example 1 except that the conditions for forming the passivation film 2 (concentration of the aqueous solution of sodium bichromate, immersion time) were set as shown in Table 1. The exterior component 1 for use was produced.

【００７９】（実施例２２〜４２）被覆層９の上に部分
的にＡｕ層１０を設け、各々不動態被膜２の形成条件
（重クロム酸水溶液濃度、浸漬時間）を表２に示す組合
せとした以外は実施例１と同様にして、本発明の時計用
外装部品１を作製した。(Examples 22 to 42) The Au layer 10 was partially provided on the coating layer 9, and the formation conditions (concentration of dichromic acid aqueous solution, immersion time) of the passivation film 2 were determined in accordance with the combinations shown in Table 2. A watch exterior component 1 of the present invention was produced in the same manner as in Example 1 except for the above.

【００８０】なお、Ａｕ層１０はＡｕ−Ｆｅ−Ｉｎ系合
金からなるメッキ層とした。The Au layer 10 was a plating layer made of an Au—Fe—In alloy.

【００８１】（比較例１）被覆層９の上に、不動態被膜
を形成しない以外は実施例１と同様にして時計用外装部
品を作製した。(Comparative Example 1) A watch external part was produced in the same manner as in Example 1 except that a passivation film was not formed on the coating layer 9.

【００８２】（比較例２）被覆層９の代わりにＰｄ−Ｎ
ｉメッキ層を設けることとした以外は比較例１と同様に
して時計用外装部品を作製した。(Comparative Example 2) Instead of the coating layer 9, Pd-N
A watch exterior component was produced in the same manner as in Comparative Example 1 except that the i-plated layer was provided.

【００８３】（比較例３）被覆層９の上にＡｕ層をメッ
キにより設けた以外は比較例１と同様にして時計用外装
部品を作製した。Comparative Example 3 An external part for a timepiece was produced in the same manner as in Comparative Example 1 except that an Au layer was provided on the coating layer 9 by plating.

【００８４】なお、Ａｕ層は実施例２２〜４２と同様の
Ａｕ−Ｆｅ−Ｉｎ系合金からなるメッキ層とした。The Au layer was a plating layer made of the same Au—Fe—In alloy as in Examples 22 to 42.

【００８５】（比較例４）被覆層（Ｐｄ−Ｎｉメッキ
層）の上にＡｕ層をメッキにより設けた以外は比較例２
と同様にして時計用外装部品を作製した。(Comparative Example 4) Comparative Example 2 except that an Au layer was provided on a coating layer (Pd-Ni plated layer) by plating.
In the same manner as in the above, a watch exterior part was produced.

【００８６】なお、Ａｕ層は比較例３の場合と同様とし
た。The Au layer was the same as in Comparative Example 3.

【００８７】２．色差測定 上記実施例１〜４２で作製した時計用外装部品１の不動
態被膜形成前後における表面色を測定し、両者の色差を
求めた。2. Color difference measurement The surface color of the watch exterior component 1 produced in Examples 1 to 42 before and after the formation of the passivation film was measured, and the color difference between the two was obtained.

【００８８】なお、実施例２２〜４２については、Ａｕ
層１０の色差を求めた。In Examples 22 to 42, Au was used.
The color difference of layer 10 was determined.

【００８９】色差測定はＪＩＳ Ｚ ８７３０に準拠
し、分光測色計ＣＭ−２０２２（ミノルタカメラ（株）
製）を用いて行った。The color difference was measured according to JIS Z 8730, using a spectrophotometer CM-2022 (Minolta Camera Co., Ltd.).
Manufactured by Toshiba Corporation.

【００９０】色差（ΔＥ* ab）は、下記式（１）により
計算される。The color difference (ΔE * ab) is calculated by the following equation (1).

【００９１】 ΔＥ* ab＝｛（ΔＬ* ）2 ＋（Δａ* ）3 ＋（Δｂ* ）2 ｝1/2 ・・・（１） なお、ΔＬ* 、Δａ* 、Δｂ* は、各々ＪＩＳ Ｚ ８
７２９に規定する表色系における２つの物体色の明度指
数Ｌ* 、クロマティクネス指数ａ* 、ｂ* の各々の差を
意味する。色差（ΔＥ* ab）が小さいほど、不動態被膜
による変化が小さいことを示す。ΔE * ab = ｛(ΔL * ) 2 + (Δa * ) 3 + (Δb * ) 2 ｝ 1/2 (1) Here, ΔL * , Δa * , and Δb * are JIS Z, respectively. 8
729 means the difference between the lightness index L * and the chromaticness indices a * and b * of the two object colors. The smaller the color difference (ΔE * ab), the smaller the change due to the passive film.

【００９２】結果を表１および表２に、また、不動態処
理条件と色差（ΔＥ* ab）との関係を図４および図５に
示す。The results are shown in Tables 1 and 2, and the relationship between the passivation conditions and the color difference (ΔE * ab) is shown in FIGS.

【００９３】[0093]

【表１】 [Table 1]

【００９４】[0094]

【表２】 [Table 2]

【００９５】これらの結果から、実施例１〜４２はいず
れの場合も表面に不動態被膜を形成することによって表
面の色調、光沢等の外観を損なうことはなかった。From these results, it was found that Examples 1-42 did not impair the appearance such as color tone and gloss of the surface by forming a passivation film on the surface in any case.

【００９６】特に、重クロム酸塩濃度が４〜６wt％の場
合には、色差（ΔＥ* ab）が１．０以下であり、極めて
良好な結果が得られた。In particular, when the dichromate concentration was 4 to 6 wt%, the color difference (ΔE * ab) was 1.0 or less, and extremely good results were obtained.

【００９７】３．耐変色性試験 上記実施例１〜４２および比較例１〜４で作製した各時
計用外装部品について、以下のような耐変色性試験を行
った。3. Discoloration Resistance Test The following discoloration resistance test was performed on each of the watch exterior parts produced in Examples 1 to 42 and Comparative Examples 1 to 4.

【００９８】(1) 耐変色性試験 Ａ．硫化アンモニウム曝気試験 実施例１〜４２、比較例１〜４で作製した各時計用外装
部品を硫化アンモニウム水溶液を入れた５リットルのデ
シケータに入れて密閉し、これを２５℃の恒温槽で１５
時間放置した。放置後、この時計用外装部品を取出し未
試験品と表面の色調を比較し、変色の程度を目視により
評価した。(1) Discoloration resistance test Ammonium sulfide aeration test Each of the watch exterior parts produced in Examples 1 to 42 and Comparative Examples 1 to 4 was put in a 5 liter desiccator containing an ammonium sulfide aqueous solution, and hermetically sealed.
Left for hours. After the standing, the watch exterior parts were taken out, and the color tone of the surface of the untested product was compared with that of the untested product, and the degree of discoloration was visually evaluated.

【００９９】なお、デシケータ内のアンモニウム水溶液
は、硫化アンモニウム（１級試薬）溶液４０ccを蒸留水
で希釈し、全量を１００ccとして用いた。The aqueous ammonium solution in the desiccator was prepared by diluting 40 cc of ammonium sulfide (primary reagent) solution with distilled water to make the total amount 100 cc.

【０１００】評価は次のように行った。The evaluation was performed as follows.

【０１０１】 ◎・・・変色が全くみられない ○・・・変色がみられない △・・・わずかな変色（褐色）あり △△・・わずかな変色（黒色）あり ×・・・変色（黒色）あり ××・・著しい変色（黒色）あり 結果を表１および表３に示す。◎: No discoloration observed ○: No discoloration observed △: Slight discoloration (brown) observed △△: Slight discoloration (black) observed ×: Discoloration ( XX: markedly discolored (black) The results are shown in Tables 1 and 3.

【０１０２】なお、実施例２２〜４２についてもＡｕ層
１０の耐変色性について評価を行ったが、いずれも良好
な結果が得られた。The discoloration resistance of the Au layer 10 was also evaluated for Examples 22 to 42, and good results were obtained in all cases.

【０１０３】Ｂ．人工汗曝気試験 実施例１〜４２、比較例１〜４で作製した各時計用外装
部品を人工汗１５０ccを入れた５リットルのデシケータ
に入れて密閉し、これを４０℃の恒温槽で２４時間放置
した。放置後、この時計用外装部品を取出し未試験品と
表面の色調を比較し、変色の程度を目視により評価し
た。B. Artificial sweat aeration test Each of the watch exterior parts produced in Examples 1 to 42 and Comparative Examples 1 to 4 was sealed in a 5-liter desiccator containing 150 cc of artificial sweat, and was sealed in a 40 ° C constant temperature bath for 24 hours. I left it. After the standing, the watch exterior parts were taken out, and the color tone of the surface of the untested product was compared with that of the untested product, and the degree of discoloration was visually evaluated.

【０１０４】人工汗の成分比は次のとおりである。The composition ratio of artificial sweat is as follows.

【０１０５】 塩化ナトリウム ９．９ｇ 硫化ナトリウム ０．８ｇ 尿素 １．７ｇ アンモニア水（１級試薬、濃度25％〜28％） ０．１８cc ショ糖（サッカロース） ０．２２ｇ 乳酸 １．１cc 蒸留水 １．０リットル 評価方法は、上記硫化アンモニウム曝気試験と同様とし
た。Sodium chloride 9.9 g Sodium sulfide 0.8 g Urea 1.7 g Aqueous ammonia (primary reagent, concentration 25% to 28%) 0.18 cc Sucrose (saccharose) 0.22 g Lactic acid 1.1 cc Distilled water 1. 0 liter The evaluation method was the same as the above ammonium sulfide aeration test.

【０１０６】結果を表３に示す。なお、実施例５および
実施例２６以外の他の実施例についても同様に良好な結
果が得られた。Table 3 shows the results. In addition, good results were similarly obtained in Examples other than Example 5 and Example 26.

【０１０７】[0107]

【表３】 [Table 3]

【０１０８】Ｃ．ＳＯx 曝気試験 実施例１〜４２、比較例１〜４で作製した各時計用外装
部品をＮａ2 ＳＯ3 の硫酸水溶液２５０ccとともに５リ
ットルのデシケータに入れて密閉し、これを２５℃で２
時間放置した。放置後、この時計用外装部品を取出し、
未試験品と表面の色調を比較し、変色の程度を目視によ
り評価した。C. SO x aeration test Each of the watch exterior parts produced in Examples 1 to 42 and Comparative Examples 1 to 4 was sealed in a 5 liter desiccator together with 250 cc of an aqueous solution of Na 2 SO 3 and sealed at 25 ° C. for 2 hours.
Left for hours. After leaving, take out the watch exterior parts,
The color tone of the untested product and the surface was compared, and the degree of discoloration was visually evaluated.

【０１０９】なお、Ｎａ2 ＳＯ3 の硫酸水溶液は、無水
亜硫酸ナトリウム（Ｎａ2 ＳＯ3 ）２５ｇを１０％Ｈ2
ＳＯ4 （１級試薬）２５０ccに溶解したものを用いた。The aqueous solution of Na 2 SO 3 in sulfuric acid was prepared by adding 25 g of anhydrous sodium sulfite (Na 2 SO 3 ) to 10% H 2.
SO 4 (primary reagent) dissolved in 250 cc was used.

【０１１０】評価方法は、上記硫化アンモニウム曝気試
験と同様とした。The evaluation method was the same as the above-mentioned ammonium sulfide aeration test.

【０１１１】結果を表３に示す。なお、実施例５および
実施例２６以外の他の実施例についても同様に良好な結
果が得られた。Table 3 shows the results. In addition, good results were similarly obtained in Examples other than Example 5 and Example 26.

【０１１２】Ｄ．次亜塩素酸ナトリウム（ＮａＯＣｌ）
曝気試験 実施例１〜４２で、比較例１〜４で作製した各時計用外
装部品を１２％次亜塩素酸ナトリウム（１級試薬）５０
ccとともに５リットルのデシケータ内に入れて密閉し、
これを２５℃で１時間放置した。放置後、この時計用外
装部品を取出し、未試験品と表面の色調を比較し、変色
の程度を目視により評価した。D. Sodium hypochlorite (NaOCl)
Aeration test In Examples 1-42, each of the watch exterior parts produced in Comparative Examples 1-4 was subjected to 12% sodium hypochlorite (first-class reagent) 50%.
Put in a 5 liter desiccator with cc and seal,
This was left at 25 ° C. for 1 hour. After standing, the timepiece exterior part was taken out, the color tone of the untested product and the surface were compared, and the degree of discoloration was visually evaluated.

【０１１３】評価方法は、上記硫化アンモニウム曝気試
験と同様とした。The evaluation method was the same as the above-mentioned ammonium sulfide aeration test.

【０１１４】結果を表３に示す。なお、実施例５および
実施例２６以外の他の実施例についても同様に良好な結
果が得られた。Table 3 shows the results. In addition, good results were similarly obtained in Examples other than Example 5 and Example 26.

【０１１５】Ｅ．チオアセトアミド曝気試験 実施例１〜４２、比較例１〜４で作製した各時計用外装
部品を２５％チオアセトアミド溶液（特級試薬）２５０
ccとともに５リットルのデシケータ内に入れて密閉し、
これを２５℃で２４時間放置した。放置後、この時計用
外装部品を取り出し、未試験品と表面の色調を比較し、
変色の程度を目視により評価した。E. Thioacetamide aeration test 25% thioacetamide solution (special grade reagent) 250 for each watch exterior component produced in Examples 1-42 and Comparative Examples 1-4
Put in a 5 liter desiccator with cc and seal,
This was left at 25 ° C. for 24 hours. After standing, take out the watch exterior parts, compare the color of the surface with the untested product,
The degree of discoloration was visually evaluated.

【０１１６】評価方法は、上記硫化アンモニウム曝気試
験と同様とした。The evaluation method was the same as in the ammonium sulfide aeration test.

【０１１７】結果を表３に示す。なお、実施例５および
実施例２６以外の他の実施例についても同様に良好な結
果が得られた。Table 3 shows the results. In addition, good results were similarly obtained in Examples other than Example 5 and Example 26.

【０１１８】Ｆ．室内放置試験 実施例１〜４２、比較例１〜４で作製した各時計用外装
部品を一般的なオフィス環境下で５か月間放置後、未試
験品と表面の色調を比較し、変色の程度を目視により評
価した。F. Indoor leaving test Each of the watch exterior parts produced in Examples 1 to 42 and Comparative Examples 1 to 4 was left in a general office environment for 5 months, and then the color tone of the untested product and the surface was compared to determine the degree of discoloration. Was visually evaluated.

【０１１９】評価方法は、上記硫化アンモニウム曝気試
験と同様とした。The evaluation method was the same as the above-mentioned ammonium sulfide aeration test.

【０１２０】結果を表３に示す。なお、実施例５および
実施例２６以外の他の実施例についても同様に良好な結
果が得られた。Table 3 shows the results. In addition, good results were similarly obtained in Examples other than Example 5 and Example 26.

【０１２１】Ｇ．梱包箱内放置試験 実施例１〜４２、比較例１〜４で作製した各時計用外装
部品を腕時計完成品梱包用ダンボール箱内に収納し、一
般的なオフィス環境下で５か月間放置後、未試験品と表
面の色調を比較し、変色の程度を目視により評価した。G. Leaving test in packing box Each of the watch exterior parts produced in Examples 1 to 42 and Comparative Examples 1 to 4 was stored in a cardboard box for packing a finished wristwatch, and left for 5 months in a general office environment. The color tone of the untested product and the surface was compared, and the degree of discoloration was visually evaluated.

【０１２２】評価方法は、上記硫化アンモニウム曝気試
験と同様とした。The evaluation method was the same as the above-mentioned ammonium sulfide aeration test.

【０１２３】結果を表３に示す。なお、実施例５および
実施例２６以外の他の実施例についても同様に良好な結
果が得られた。Table 3 shows the results. In addition, good results were similarly obtained in Examples other than Example 5 and Example 26.

【０１２４】評価の結果、本発明の時計用外装部品はい
ずれの場合にも、あらゆる環境下において優れた耐変色
性を有していることがわかった。また、被覆層９（Ｐｄ
層）の上にＡｕ層１０が設けられた装飾品用部品につい
ても、Ｐｄ層、Ａｕ層ともに良好な耐変色性が得られ
た。As a result of the evaluation, it was found that the watch exterior parts of the present invention had excellent discoloration resistance under any environment in any case. The coating layer 9 (Pd
Also for the decorative article component in which the Au layer 10 was provided on the (layer), good color fastness was obtained for both the Pd layer and the Au layer.

【０１２５】特に、重クロム酸塩濃度が４〜６wt％、浸
漬時間が１５〜６０sec の範囲にある場合には、優れた
耐変色性を有するとともに、色差が１．０以下と低く、
不動態被膜処理前の表面の色調が良好に維持されること
が判った。In particular, when the dichromate concentration is in the range of 4 to 6 wt% and the immersion time is in the range of 15 to 60 sec, it has excellent discoloration resistance and a low color difference of 1.0 or less.
It was found that the color tone of the surface before the passivation film treatment was well maintained.

【０１２６】これに対し、比較例１〜４の時計用外装部
品は耐変色性に劣り、特に、比較例１および比較例３の
純Ｐｄによる被覆層は、硫化アンモニウム曝気試験、人
工汗曝気試験の結果、著しい変色が観察された。On the other hand, the watch exterior parts of Comparative Examples 1 to 4 were inferior in discoloration resistance. In particular, the coating layers made of pure Pd of Comparative Examples 1 and 3 showed ammonium sulfide aeration test and artificial sweat aeration test. As a result, significant discoloration was observed.

【０１２７】[0127]

【発明の効果】以上述べたように、本発明の装飾品用部
品、装飾品、電子機器および時計は、耐変色性等に優れ
ているため、経時的に表面の色調が劣化し外観が損なわ
れることがない。As described above, the decorative parts, decorative articles, electronic devices and watches of the present invention are excellent in discoloration resistance and the like, so that the surface tone deteriorates over time and the appearance is impaired. Never be.

【０１２８】さらに、本発明の不動態被膜は装飾品用部
品の表面の色調を変化させないで、表面保護層として機
能し、優れた外観品質を長く保つことができる。Further, the passivation film of the present invention functions as a surface protective layer without changing the color tone of the surface of the decorative component, and can maintain excellent appearance quality for a long time.

【０１２９】また、特にＡｕ層を設けた場合、審美感を
向上させつつその耐変色性を維持することができ、より
高品質のものとすることができる。またこれらの層を設
けることにより、デザイン的にもバリエーションが拡が
り、装飾品等としての商品価値を一層高めることができ
る。In particular, in the case where an Au layer is provided, it is possible to maintain the discoloration resistance while improving the aesthetic feeling, and to achieve higher quality. By providing these layers, variations in design can be widened, and the commercial value as a decorative product or the like can be further increased.

【図面の簡単な説明】[Brief description of the drawings]

【図１】本発明の装飾品用部品の第１の実施例を示す部
分断面図である。FIG. 1 is a partial sectional view showing a first embodiment of a decorative component according to the present invention.

【図２】本発明の装飾品用部品の第２の実施例を示す部
分断面図である。FIG. 2 is a partial sectional view showing a second embodiment of the decorative article component of the present invention.

【図３】本発明の装飾品用部品を備える携帯時計の実施
例を示す部分断面図である。FIG. 3 is a partial cross-sectional view showing an embodiment of a portable timepiece provided with a decorative article component of the present invention.

【図４】不動態処理条件と表面の色差との関係を示す図
である。FIG. 4 is a diagram showing a relationship between passivation processing conditions and surface color differences.

【図５】不動態処理条件と表面の色差との関係を示す図
である。FIG. 5 is a diagram showing a relationship between passivation processing conditions and surface color differences.

【符号の説明】[Explanation of symbols]

１ 装飾品用部品（時計用外装部品） １Ａ 腕時計（携帯時計） ２ 不動態被膜 ３ 下地層 ４ 素地 ５ Ｃｕ st.層 ６ Ｃｕ層 ７ Ｃｕ−Ｓｎ層 ８ Ａｕ st.層 ９ 被覆層 １０ Ａｕ層 ２２ 胴 ２３ 裏蓋 ２４ ベゼル ２５ ガラス板 ２６ 巻真パイプ ２７ りゅうず ２７１ 軸部 ２７２ 溝 ２８ プラスチックパッキン ２９ プラスチックパッキン ３０ ゴムパッキン ４０ 裏蓋パッキン ５０ シール部 DESCRIPTION OF SYMBOLS 1 Decorative parts (exterior parts for watches) 1A Wrist watch (portable watch) 2 Passive film 3 Base layer 4 Base 5 Cu st. Layer 6 Cu layer 7 Cu-Sn layer 8 Au st. Layer 9 Coating layer 10 Au layer DESCRIPTION OF SYMBOLS 22 Body 23 Back cover 24 Bezel 25 Glass plate 26 Winding pipe 27 Crown 271 Shaft 272 Groove 28 Plastic packing 29 Plastic packing 30 Rubber packing 40 Back packing 50 Seal part

───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C23C 28/00 C23C 22/24 C25D 3/50 102 C25D 7/00 G04B 37/22 ──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. 7 , DB name) C23C 28/00 C23C 22/24 C25D 3/50 102 C25D 7/00 G04B 37/22

Claims (21)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】 素地上に少なくとも１層からなる下地層
と、ＰｄまたはＰｄ系合金からなる被覆層が設けられ、
該被覆層表面に不動態被膜が形成されていることを特徴
とする装飾品用部品。An underlayer comprising at least one layer and a coating layer comprising Pd or a Pd-based alloy are provided on a substrate,
A decorative article part, wherein a passivation film is formed on the surface of the coating layer. 【請求項２】 前記不動態被膜は酸化剤溶液に浸漬する
ことにより形成される請求項１に記載の装飾品用部品。2. The decorative component according to claim 1, wherein the passivation film is formed by dipping in a oxidizing agent solution. 【請求項３】 前記酸化剤溶液はクロム酸塩溶液である
請求項２に記載の装飾品用部品。3. The decorative part according to claim 2, wherein the oxidizing agent solution is a chromate solution. 【請求項４】 前記溶液は重クロム酸塩の水溶液である
請求項３に記載の装飾品用部品。4. The decorative component according to claim 3, wherein the solution is an aqueous solution of dichromate. 【請求項５】 前記重クロム酸塩の水溶液は重クロム酸
塩を３〜７wt％含有する請求項４に記載の装飾品用部
品。5. The decorative part according to claim 4, wherein the aqueous solution of dichromate contains 3 to 7% by weight of dichromate. 【請求項６】 前記酸化剤溶液への浸漬時間が１５〜６
０秒である請求項２ないし５のいずれかに記載の装飾品
用部品。6. The immersion time in the oxidizing agent solution is 15-6.
The decorative component according to any one of claims 2 to 5, wherein the time is 0 second. 【請求項７】 前記被覆層は純Ｐｄ層である請求項１な
いし６のいずれかに記載の装飾品用部品。7. The decorative component according to claim 1, wherein the coating layer is a pure Pd layer. 【請求項８】 前記被覆層はメッキ層である請求項１な
いし７のいずれかに記載の装飾品用部品。8. The decorative component according to claim 1, wherein the coating layer is a plating layer. 【請求項９】 前記メッキ層は亜硝酸系パラジウム溶液
を用いて設けられたものである請求項８に記載の装飾品
用部品。9. The decorative component according to claim 8, wherein the plating layer is provided using a nitrous acid-based palladium solution. 【請求項１０】 前記被覆層の厚さが０．３〜１１μｍ
であることを特徴とする請求項１ないし９のいずれかに
記載の装飾品用部品。10. The coating layer has a thickness of 0.3 to 11 μm.
The decorative component according to any one of claims 1 to 9, wherein: 【請求項１１】 前記被覆層上にＡｕまたはＮｉ不含有
Ａｕ系合金からなる層が設けられた請求項１ないし１０
のいずれかに記載の装飾品用部品。11. A layer made of Au or a Ni-free Au-based alloy is provided on the coating layer.
A decorative part according to any one of the above. 【請求項１２】 前記ＡｕまたはＮｉ不含有Ａｕ系合金
からなる層の厚さは０．５〜１０μｍである請求項１１
に記載の装飾品用部品。12. The layer made of Au or a Ni-free Au-based alloy has a thickness of 0.5 to 10 μm.
Parts for decorative goods described in. 【請求項１３】 前記ＡｕまたはＮｉ不含有Ａｕ系合金
からなる層に前記不動態被膜が形成された請求項１１ま
たは１２に記載の装飾品用部品。13. The decorative part according to claim 11, wherein the passivation film is formed on a layer made of the Au or Ni-free Au-based alloy. 【請求項１４】 前記不動態被膜は、該不動態被膜の有
無による前記装飾品用部品の表面の色差が１．８以下で
ある請求項１ないし１３のいずれかに記載の装飾品用部
品。14. The decorative component according to claim 1, wherein the passivation film has a surface color difference of 1.8 or less depending on the presence or absence of the passivation film. 【請求項１５】 前記不動態被膜は、該不動態被膜の有
無による前記装飾品用部品の表面の色差が１．０以下で
ある請求項１ないし１４のいずれかに記載の装飾品用部
品。15. The decorative part according to claim 1, wherein the passivation film has a color difference of 1.0 or less on the surface of the decorative part according to the presence or absence of the passivation film. 【請求項１６】 前記下地層はＣｕ、Ｎｉ不含有Ｃｕ系
合金、Ａｕ、Ｎｉ不含有Ａｕ系合金、Ｐｄ、Ｎｉ不含有
Ｐｄ系合金からなる群より選ばれた少なくとも１つから
構成される層を有する請求項１ないし１５のいずれかに
記載の装飾品用部品。16. The underlayer is a layer composed of at least one selected from the group consisting of Cu, Ni-free Cu-based alloy, Au, Ni-free Au-based alloy, Pd, and Ni-free Pd-based alloy. The decorative component according to any one of claims 1 to 15, comprising: 【請求項１７】 前記下地層の厚さが０．５〜３０μｍ
である請求項１ないし１６のいずれかに記載の装飾品用
部品。17. The thickness of the underlayer is 0.5 to 30 μm.
The decorative article component according to any one of claims 1 to 16, wherein 【請求項１８】 前記装飾品用部品は時計用外装部品で
ある請求項１ないし１７のいずれかに記載の装飾品用部
品。18. The decorative part according to claim 1, wherein the decorative part is a watch exterior part. 【請求項１９】 請求項１ないし１８のいずれかに記載
の装飾品用部品を備えることを特徴とする装飾品。19. A decorative article comprising the decorative article part according to claim 1. Description: 【請求項２０】 請求項１ないし１８のいずれかに記載
の装飾品用部品を備えることを特徴とする電子機器。20. An electronic device comprising the decorative component according to claim 1. Description: 【請求項２１】 請求項１８に記載の時計用外装部品を
備えることを特徴とする時計。21. A timepiece comprising the timepiece exterior part according to claim 18.
JP27630597A 1997-10-08 1997-10-08 Ornament parts, ornaments, electronics and watches Expired - Fee Related JP3334577B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP27630597A JP3334577B2 (en) 1997-10-08 1997-10-08 Ornament parts, ornaments, electronics and watches

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP27630597A JP3334577B2 (en) 1997-10-08 1997-10-08 Ornament parts, ornaments, electronics and watches

Publications (2)

Publication Number Publication Date
JPH11106951A JPH11106951A (en) 1999-04-20
JP3334577B2 true JP3334577B2 (en) 2002-10-15

Family

ID=17567610

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Link
JP (1) JP3334577B2 (en)

Also Published As

Publication number Publication date
JPH11106951A (en) 1999-04-20

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