JPH02217460A - Outer ornament parts for watch - Google Patents
Outer ornament parts for watchInfo
- Publication number
- JPH02217460A JPH02217460A JP3973089A JP3973089A JPH02217460A JP H02217460 A JPH02217460 A JP H02217460A JP 3973089 A JP3973089 A JP 3973089A JP 3973089 A JP3973089 A JP 3973089A JP H02217460 A JPH02217460 A JP H02217460A
- Authority
- JP
- Japan
- Prior art keywords
- film
- color
- coating
- compounds
- 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.)
- Granted
Links
- 238000000576 coating method Methods 0.000 claims abstract description 44
- 239000011248 coating agent Substances 0.000 claims abstract description 39
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 20
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 19
- 238000007733 ion plating Methods 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 230000000873 masking effect Effects 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000003086 colorant Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 238000005530 etching Methods 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 238000010030 laminating Methods 0.000 claims abstract description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 3
- 238000005868 electrolysis reaction Methods 0.000 abstract description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000010931 gold Substances 0.000 abstract description 3
- 229910052737 gold Inorganic materials 0.000 abstract description 3
- 239000010936 titanium Substances 0.000 description 52
- 239000007789 gas Substances 0.000 description 17
- 239000011651 chromium Substances 0.000 description 16
- 239000000758 substrate Substances 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 230000002950 deficient Effects 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 6
- 239000000956 alloy Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 235000019646 color tone Nutrition 0.000 description 5
- 238000009500 colour coating Methods 0.000 description 4
- 238000010849 ion bombardment Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 241001441724 Tetraodontidae Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はイオンプレイティング法を用いて被膜を形成し
た時計用外装部品に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an exterior part for a timepiece in which a film is formed using an ion plating method.
［発明の概要］
本発明は時計用外装部品ににおいて、Ｔｉ又はＴｉ合金
素材表面にイオンプレーティング法により、下地層とし
てＣｒａｍ、仕上層としてＴｉ。[Summary of the Invention] The present invention relates to an exterior part for a watch, in which Cram is applied as a base layer and Ti is applied as a finishing layer on the surface of a Ti or Ti alloy material by an ion plating method.
Ｃ，Ｎの化合物を主成分とする金色・黒灰色系。A golden/blackish-gray color whose main components are C and N compounds.
Ｔｉ、Ｃ，Ｏの化合物を主成分とする黒茶色系。A blackish-brown color whose main components are Ti, C, and O compounds.
又は、Ｔｉ、Ｏの化合物を主騰分とする青色系の内の一
種のＴｉ系硬質被膜を被覆・積層して仕上げ、更には該
被膜を部分的にマスキングした１食にＴｉ系硬質被膜お
よびＣｒ被膜を化学的にエツチング除去、次いでマスキ
ング被膜を除去して素材色とＴｉ系硬質被膜色の二色に
仕上げかことによリ、Ｔｉ又はＴｉ合金の軽量、高耐食
性を生かし、更には硬質で、耐擦傷性、耐摩耗性に優れ
且、色調バラエティ−に富んだＴｉ系カラー被膜又は素
材色とＴｉ系硬質被膜色の二色に仕上げた時計用外装部
品を提供するものである。Alternatively, a Ti-based hard coating, which is a type of blue-based Ti-based hard coating mainly containing Ti and O compounds, is coated and laminated, and the coating is partially masked, and a Ti-based hard coating and a Ti-based hard coating are applied. By chemically etching the Cr film and then removing the masking film to finish in two colors: the material color and the Ti-based hard film color, we can take advantage of the light weight and high corrosion resistance of Ti or Ti alloys, and also create a hard coating. The present invention provides an exterior part for a watch that has excellent scratch resistance and abrasion resistance, and is finished in a Ti-based color coating with a rich variety of colors or in two colors: the material color and the Ti-based hard coating color.
［従来の技術］
従来のＴｉ又はＴｉ合金基板表面へのイオンプレイティ
ング法によるＴｉ系カラー被膜形成は、基板表面に直接
被覆する方法が一般的である。又、Ｔｉ又はＴｉ合金素
材とＴｉ系カラー被膜による二色仕上げは、素材表面を
部分的に耐熱性マスキング剤でマスキングした後にＴｉ
系カラー被膜を被覆し、マスキング被膜を溶解除去する
方法が一般的である。[Prior Art] The conventional method for forming a Ti-based color film on the surface of a Ti or Ti alloy substrate by ion plating is to directly coat the surface of the substrate. In addition, two-color finishing using Ti or Ti alloy material and Ti-based color coating is possible after partially masking the surface of the material with a heat-resistant masking agent.
A common method is to apply a color film and dissolve and remove the masking film.
［発明が解決しようとする課題］
しかし時計用外装部品は外観や色調品質は特に厳しく管
理され、イオンプレイティング加工に於いては色調限度
外不良や色ムラ不良等による不良率が３〜５％は発生し
てしまうため、これらの不良基板を救済する方法として
、従来の方法では、Ｔｉ系カラー被膜をフッ酸と硝酸の
混液により剥離除去するのが一般的であるがＴｉ又はＴ
ｉ合金基板表面に直接Ｔｉ系カラー被膜を被覆している
ため基板表面も同時にエツチングされてしまい、高付加
価値のついた基板を廃却するか又は、長時間をかけて再
研磨を施さないと救済が不可能であり、納期面、コスト
面で問題が発生していた。又二色仕上げにおいては、素
材表面を部分的に耐熱性マスキング剤でマスキングした
後にＴｉ系カラー被膜を被覆する際、マスキング被膜よ
りガスが発生し、色ムラ不良等が多発してしまう。又仕
上がり外観上素材色の面積が大きいデザインの１勿では
マスキング塗布に長時間を要し、納期面、コ、スト面で
問題が発生していた。本発明はこのような問題点を解決
するもので、その目的とするところは、イオンプレイテ
ィング加工に於ける不良品を基板表面がエツチングされ
ることな（Ｔｉ系カラー被膜をフッ酸と硝酸の混液によ
り剥離除去し、直ちに再イオンプレイティング加工を可
能とし、更には、二色仕上げ方法としてＴｉ系カラー被
膜を表面全体に被覆した陵に部分的にマスキングしＴｉ
系カラー被膜をフッ酸とｌｉｉ！１酸の混液により剥離
除去、次いでＣｒ被膜を剥離除去することにより不良品
の救済および不良率の大幅減少を図り、納期短縮、コス
トダウンにより軽量、高耐食性、硬質で、耐擦イｉ性、
耐摩耗性に優れ且、色調バラエティ−に富んだＴｉ系カ
ラー被膜又は素材色とＴｉ系硬質被膜色の二色に仕上げ
た時計用外装部品を安価で安定的に提供するところにあ
る。[Problem to be solved by the invention] However, the appearance and color quality of exterior parts for watches are particularly strictly controlled, and in ion plating processing, the defect rate due to defects outside the color tone limit, color unevenness, etc. is 3 to 5%. The conventional method for repairing these defective substrates is to peel off and remove the Ti-based color film using a mixture of hydrofluoric acid and nitric acid.
Since the Ti-based color film is directly coated on the i-alloy substrate surface, the substrate surface is also etched at the same time, and the high value-added substrate must be discarded or re-polished over a long period of time. Remedies were not possible, and problems had arisen in terms of delivery time and costs. In addition, in two-color finishing, when a Ti-based color film is applied after partially masking the surface of the material with a heat-resistant masking agent, gas is generated from the masking film, resulting in frequent defects such as color unevenness. In addition, in the case of a design with a large area of material color in terms of finished appearance, it takes a long time to apply masking, which causes problems in terms of delivery time, cost, and cost. The present invention is intended to solve these problems, and its purpose is to prevent defective products from being etched on the substrate surface during ion plating processing. It is possible to peel off and remove with a mixed solution and immediately perform re-ion plating processing.Furthermore, as a two-color finishing method, Ti
Color coating with hydrofluoric acid! By stripping and removing the Cr coating with a mixed solution of 1 acid, and then stripping and removing the Cr coating, we are able to rescue defective products and significantly reduce the defective rate.This results in shorter delivery times and lower costs, resulting in lightweight, high corrosion resistance, hardness, and scratch resistance.
It is an object of the present invention to stably provide at low cost an exterior part for a watch which has excellent abrasion resistance and is finished in a Ti-based color coating with a rich variety of colors or in two colors: the material color and the Ti-based hard coating color.
［課題を解決するための手段］
上記問題点を解決するために本発明の時計用外装部品は
、
（１）Ｔｉ又はＴｉ合金を用いた時計用外装部品の表面
に、イオンプレーティング法により、下地層としてＣｒ
被膜、仕上層としてＴｉ系硬質被膜を被覆・積層して仕
上げ、更には該被膜を部分的にマスキングした浚にＴｉ
系硬質被膜およびＣｒ被膜を化学的にエツチング除去、
次いでヤスキング被膜を除去して素材色とＴｉ系硬質被
膜色の二色に仕上げ、
（２）下地層としてのＣｒ被膜厚みが、０，２〜５．０
μｍであり、仕上層としてＴｉ系硬質被膜が、Ｔｉ、Ｃ
，Ｎの化合物を主成分とする金色・黒灰色系、Ｔｉ、Ｃ
，Ｏの化合物を主成分とする黒茶色系、又は、Ｔｉ、Ｏ
の化合物を主成分とする青色系の内の一種であり、被膜
厚みが０．２〜２．０μｍであることを特徴とする。[Means for Solving the Problems] In order to solve the above-mentioned problems, the watch exterior part of the present invention has the following features: (1) The surface of the watch exterior part using Ti or a Ti alloy is coated by an ion plating method. Cr as the base layer
Finishing is done by coating and laminating a Ti-based hard film as a coating and finishing layer, and furthermore, Ti
Chemically removes hard coatings and Cr coatings,
Next, the Yasking film was removed and finished in two colors: the material color and the Ti-based hard film color. (2) The thickness of the Cr film as the base layer was 0.2 to 5.0.
μm, and a Ti-based hard coating is used as a finishing layer of Ti, C
, N, gold/blackish-gray color mainly composed of compounds of Ti, C
, O, or Ti, O.
It is a type of blue color whose main component is a compound of the following, and is characterized by a coating thickness of 0.2 to 2.0 μm.
［作用］
本発明の上記構成によれば、Ｔ１又はＴｉ合金を用いた
時計用外装部品の表面にイオンブレーテ、フグ法により
、下地層としてＣｒ被膜を被覆したことにより、仕上層
としてのＴｉ系硬質被膜イオンプレイティング加工に於
ける不良品の救済および二色仕上げにおけるＴｉ系硬質
被膜の部分剥離に用いるフッ酸とｌｕ’ｆ酸の混液によ
るエツチング処理をＴｉ又はＴｉ合金素地を荒らすこと
なく可能となる。再イオンプレイティング加工に於いて
はＣｒＭＦＪはまったくエツチングされないためそのま
ま使用可能である。又二色仕上げにおけるＴｉ系硬質被
膜の部分刊Ｉｆｆ ！こ於いても上記同様にＣｒ被膜は
まったくエツチングされない。しかし、Ｔ１又はＴｉ合
金素地を露出させなければならないために、Ｃｒ ＊
ＩＧｔを剥離する必要がある。Ｃｒ被膜は燐酸・炭酸ナ
トリウム等の水溶液中で陽極電解することにより素地を
荒らすことなく簡単に剥離除去が可能である。Ｔｉ又は
Ｔｉ合金素地上のＣｒ被膜厚みは、生産性、およびエツ
チング保護性、密着性より０．２μｍ〜１．５μｍが畏
適であるが、５μｍまで広げても問題ない。[Function] According to the above structure of the present invention, the surface of the watch exterior part made of T1 or Ti alloy is coated with a Cr film as a base layer by the ion brate method or the blowfish method, thereby forming a Ti-based hard layer as a finishing layer. Enables etching treatment using a mixed solution of hydrofluoric acid and lu'f acid, which is used to rescue defective products in film ion plating processing and to partially peel off Ti-based hard films in two-color finishing, without damaging the Ti or Ti alloy substrate. Become. In the re-ion plating process, CrMFJ is not etched at all, so it can be used as is. Also, a partial publication of Ti-based hard coatings in two-color finishing If! In this case as well, the Cr film is not etched at all. However, since the T1 or Ti alloy matrix must be exposed, Cr*
It is necessary to peel off the IGt. The Cr coating can be easily peeled off and removed without damaging the substrate by anodic electrolysis in an aqueous solution of phosphoric acid, sodium carbonate, or the like. The thickness of the Cr coating on the Ti or Ti alloy substrate is preferably 0.2 μm to 1.5 μm from the viewpoint of productivity, etching protection, and adhesion, but there is no problem in increasing the thickness to 5 μm.
次に、イオンプレイティング法によるＴｉ系硬質被膜の
金色・黒灰色系は、Ｔｉ又はＴｉ合金を蒸発源として窒
素系ガスおよび炭化水素系ガスを反応性ガスとして生成
されるＴｉとＮとＣ元素との化合物が適用できうる。黒
茶色系は、Ｔｉ又はＴｉ合金を蒸発源として炭化水素系
ガスおよび酸素ガスを反応性ガスとして生成されるＴ１
とＣとＣ元素との化合物が適用できうる。青色系は、Ｔ
ｉ又はＴｉ合金を蒸発源として酸素ガスを反応性ガスと
して生成されるＴｉとＯｙｃ素との化合物が適用できう
る。いずれも硬質被膜の厚みは、生産性、機能性より０
．５μｍ〜１．０μｍが是適であるが０．２μｍ〜２．
０μｍの範囲に広げてもＨｖｌＯＯＯ以上と硬いため耐
摩耗性、耐擦傷性の効果は何ら変わらない。以下本発明
について実施例に基すいて説明する。Next, the golden/blackish-gray color of the Ti-based hard coating produced by the ion plating method is produced by using Ti, N, and C elements using Ti or a Ti alloy as an evaporation source and nitrogen-based gas and hydrocarbon-based gas as reactive gases. Compounds with can be applied. The black-brown type is T1, which is produced using Ti or Ti alloy as an evaporation source and hydrocarbon gas and oxygen gas as reactive gases.
A compound of C and C element can be applied. Blue color is T
A compound of Ti and Oyc produced using Oyc or Ti alloy as an evaporation source and oxygen gas as a reactive gas can be applied. In both cases, the thickness of the hard coating is 0 due to productivity and functionality.
．． 5 μm to 1.0 μm is suitable, but 0.2 μm to 2.0 μm.
Even if the thickness is expanded to a range of 0 μm, the hardness is greater than HvlOOOO, so there is no change in the effects of wear resistance and scratch resistance. The present invention will be explained below based on examples.
［実施例１コ
第１図は本発明の時計用外装部品の断面図であり、図に
基ずいて説明する。[Example 1] FIG. 1 is a sectional view of an exterior part for a timepiece according to the present invention, and explanation will be given based on the figure.
純Ｔ１により形成された時計ケース１をイオンプレイテ
ィング装置中でアルゴンガスを導入し、０．０２ｔｏｒ
ｒ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ない時計ケース基板表
面のクリーニングを行なった。次にアルゴンガスを排出
し真空室内をｌＸｌ０−’ｔｏｒｒに戻した陵、電子ビ
ーム加熱により金属クロムを蒸発させ、基板電圧を−０
゜Ｉ Ｋ ｖ印加しプラズマを発生させ、イオン化した
金属クロム２を基板に生成させた。次いでイオンプレイ
ティング装置より一旦取り出し外観、色調等′Ｖｆ１認
後、再度イオンプレイティング装置中でアルゴンガスを
用いて前述と同様にイオンボンバードメントを行ない時
計ケース基板表面のクリーニングを行なった。その後、
純Ｔｉを０．２μｍイオンプレイティングし反応性ガス
としてＮ２ガスを導入しＴｉＮ層を０．２μｍ形成した
。更に、Ｃ，Ｈ，ガスを導入しＮ２ガスと Ｃ２Ｈ，を
２対１の割合で９ｘｌＯ−’ｔｏｒｒ迄導入して最終的
に仕上層としてＴｉ、Ｎ、Ｃを主成分とする金色層３を
０．５μｍ ｆｆｆ層した。又、上記処理による色調不
良品については、フッ酸と硝酸の混液によ、り金色層を
剥離除去した俺、再度上記方法により金色層を積層し救
ｉ斉した。The watch case 1 made of pure T1 was heated to 0.02 torr by introducing argon gas into the ion plating device.
5 with a negative applied voltage of 0.5 Kv to the substrate and held at a pressure of r.
Ion bombardment was performed for a minute to clean the surface of the watch case substrate. Next, the argon gas was exhausted, the vacuum chamber was returned to l
゜IKv was applied to generate plasma, and ionized metal chromium 2 was generated on the substrate. Next, the watch case was removed from the ion plating apparatus, and after checking the appearance, color tone, etc., ion bombardment was performed again in the ion plating apparatus using argon gas in the same manner as described above to clean the surface of the watch case substrate. after that,
Pure Ti was ion plated to a thickness of 0.2 μm, and N2 gas was introduced as a reactive gas to form a TiN layer of 0.2 μm. Furthermore, C, H, and gases are introduced, and N2 gas and C2H are introduced at a ratio of 2:1 up to 9xlO-'torr, and finally a golden layer 3 mainly composed of Ti, N, and C is formed as a finishing layer. A 0.5 μm fff layer was formed. In addition, for products with poor color tone due to the above treatment, we removed the golden layer using a mixture of hydrofluoric acid and nitric acid, and then laminated the golden layer again using the above method.
上記方法により作成した金色硬質被膜からなる純Ｔｉ製
時計ケースは、被膜硬度がＨｖ１２００であった。品質
試験は、人工汗耐食試験！（４０“Ｃ×温温度９亢
０°Ｃ×湿度９０％ｘ４８Ｈ）、折り曲げ試９（１８０
・折り曲げ、熱シヨツク試験（３００°Ｃ×１０分加熱
→水中急冷、５回繰り返し）、耐摩耗試験（牛皮上にて
５００ｇ荷重を時計ケースにかけ、５ｃｍストロークに
て３万回擦りつける）、耐擦傷試験（ビニタイル上１ｍ
より２０回繰り返し落下する）を行ない上記試験結果は
すべて時計ケースとしての耐食性、密着性、耐摩耗性、
耐擦傷性を十分満足するものであった。The pure Ti watch case made of the golden hard coating produced by the above method had a coating hardness of Hv1200. The quality test is an artificial sweat corrosion resistance test! (40"C x temperature 9~0°C x humidity 90% x 48H), bending test 9 (180
・Bending, heat shock test (heating at 300°C for 10 minutes → quenching in water, repeated 5 times), abrasion test (applying a load of 500g to the watch case on cowhide and rubbing it 30,000 times with a 5cm stroke), Scratch test (1m on vinyl tile)
The above test results show that the watch case has excellent corrosion resistance, adhesion, abrasion resistance,
The scratch resistance was sufficiently satisfied.
［実施例２］
第２図は本発明の時計用外装部品の断面図であり、図に
基すいて説明する。[Example 2] FIG. 2 is a sectional view of an exterior part for a timepiece according to the present invention, and description will be given based on the figure.
Ｔｉ合金（８Ａ１−４Ｖ）により形成された時計ケース
４の表面に、実施例１と同様の方法によりイオンボンバ
ードメントの佳、金属クロム２を基板に生成させた。次
いでイオンプレイティング装置より一旦取り出し外観、
色調等確認後、再度イオンプレイティング装置中でアル
ゴンガスを用いて前述と同様にイオンボンバードメント
を行ない時計ケース基板表面のクリーニングを行なった
。Metal chromium 2, which is good for ion bombardment, was formed on the surface of the watch case 4 made of Ti alloy (8A1-4V) by the same method as in Example 1. Next, take it out from the ion plating device and see the appearance.
After confirming the color tone, etc., ion bombardment was performed again in the same manner as described above using argon gas in the ion plating apparatus to clean the surface of the watch case substrate.
その後、アルゴンガスを排出し真空室内を３×１０−’
Ｐａに戻した俺、改めて反応性ガスとして酸素を２×１
０””Ｐａまで導入し、基板電圧を０。After that, the argon gas was exhausted and the vacuum chamber was 3×10-'
I returned to Pa and used 2x1 oxygen as a reactive gas again.
The voltage was introduced to 0''Pa and the substrate voltage was set to 0.
３Ｋｖ印加し、プラズマを発生させ、金属チタンをボー
ド加熱で蒸発させ、仕上層としてＴｉと０の化合物であ
る肯系色の硬質被膜５を１．０μｍ積層した。次に、青
系色の硬質被１１５を残したい部分に市販の有機系レジ
ストを塗布してマスキン・グ被膜を形成した後、フッ酸
と硝酸の混液により青果色層を剥離除去した。次いで、
燐酸洛中において５ｖで陽極電解を行ないＣｒ被膜を剥
離除去した後、有機溶剤によりマスキング被膜を溶解除
去して素地色と青系色とからなる二色仕上げの時計ケー
スを作成した。この方法により作成したＴｉ合金（６Ａ
ｌ−４Ｖ）！２時計ケースは、青系色被膜硬度がＨｖ１
２００であった。品質試験は実施例１と同様に、耐食性
、密着性、耐摩耗性、耐擦傷性試験を行ない、品質試験
結果はすべて時計ケースとしての品質を十分満足するも
ので返った。3 Kv was applied to generate plasma, metal titanium was evaporated by board heating, and a positive color hard coating 5 made of a compound of Ti and 0 was laminated to a thickness of 1.0 μm as a finishing layer. Next, a commercially available organic resist was applied to the areas where the bluish hard coating 115 was to be left to form a masking film, and then the fruit and vegetable colored layer was peeled off using a mixture of hydrofluoric acid and nitric acid. Then,
Anodic electrolysis was carried out at 5V in a phosphoric acid solution to remove the Cr film, and then the masking film was dissolved and removed using an organic solvent to create a watch case with a two-color finish consisting of a base color and a bluish color. Ti alloy (6A
l-4V)! 2 The watch case has a blue coating hardness of Hv1.
It was 200. Similar to Example 1, the quality tests were conducted for corrosion resistance, adhesion, abrasion resistance, and scratch resistance, and all of the quality test results were sufficiently satisfactory for use as a watch case.
又、本発明の適用に当たっては時計用文字板、針、バン
ド等の時計用外装部品はもちろん、メガネフレーム、ラ
イター、ネクタイビン、装身具等の装飾部品すべてに適
用可能である。Furthermore, the present invention can be applied to all decorative parts such as eyeglass frames, lighters, tie bins, and accessories as well as exterior parts for watches such as watch dials, hands, and bands.
［発明の効果］
以上述べた如く本発明によれば、ＴｉまたはＴｉ合金に
より形成された時計用外装部品の表面にイオンプレーテ
ィングにより予め下地層としてＣｒ被膜を被覆したこと
により、Ｔｉ系硬質被膜仕上げおよびＴｉ又はＴｉ合金
素地色とＴｉ系硬質被膜の二色仕上げの不良品の救済お
よび不良率の大幅減少を図り、納期短縮、コストダウン
により軽量、高耐食性、硬質で、耐擦傷性、耐摩耗性に
優れ且、色調バラエティ−に富んだ時計用外装部品を安
価で安定的に提供することが可能となった。[Effects of the Invention] As described above, according to the present invention, a Ti-based hard coating is formed by coating the surface of a watch exterior part made of Ti or a Ti alloy with a Cr coating as a base layer by ion plating. Finishing and two-color finishing of Ti or Ti alloy base color and Ti-based hard coating will save defective products and significantly reduce the defective rate.By shortening delivery times and reducing costs, we have created lightweight, highly corrosion-resistant, hard, scratch-resistant, It has become possible to stably provide exterior parts for watches with excellent abrasion resistance and a wide variety of color tones at low cost.
第１図、第２図は本発明による時計用外装部品の構成を
示す実施例の簡単な断面図である。
１・・・純Ｔｉ素材
２・・・Ｃｒ被膜
３・・・Ｔｉ系金色硬質被膜
４−−−Ｔｉ合金素材（６Ａｌ−４Ｖ）５・・・Ｔｉ系
青色系硬質被膜
以 上
−１系金色硬貢被膜
：ｒ被被
膜Ｔｉ素材
１系青色系硬買被膜
１合金素材（６Ａ１
−４ Ｖ ）
第２図FIGS. 1 and 2 are simple cross-sectional views of an embodiment showing the structure of an exterior part for a timepiece according to the present invention. 1...Pure Ti material 2...Cr coating 3...Ti-based golden hard coating 4---Ti alloy material (6Al-4V) 5...Ti-based blue hard coating or above -1 series gold color Hard coating: r coating Ti material 1-based blue hard coating 1 alloy material (6A1-4V) Fig. 2
Claims (2)
に、イオンプレーティング法により、下地層としてＣｒ
被膜、仕上層としてＴｉ系硬質被膜を被覆・積層して仕
上げ、更には該被膜を部分的にマスキングした後にＴｉ
系硬質被膜およびＣｒ被膜を化学的にエッチング除去、
次いでマスキング被膜を除去して素材色とＴｉ系硬質被
膜色の二色に仕上げたことを特徴とする時計用外装部品
。(1) Cr is applied as a base layer on the surface of a watch exterior part made of Ti or Ti alloy using an ion plating method.
The film is finished by coating and laminating a Ti-based hard film as a finishing layer, and after partially masking the film, a Ti-based hard film is applied.
Chemically etching away system hard coatings and Cr coatings,
The exterior part for a watch is characterized in that the masking film is then removed and finished in two colors: the material color and the Ti-based hard film color.
μｍであり、仕上層としてのＴｉ系硬質被膜が、Ｔｉ、
Ｃ、Ｎの化合物を主成分とする金色・黒灰色系、Ｔｉ、
Ｃ、Ｏの化合物を主成分とする黒茶色系、又は、Ｔｉ、
Ｏの化合物を主成分とする青色系の内の一種であり、被
膜厚みが０．２〜２．０μｍであることを特徴とする請
求項１記載の時計用外装部品。(2) The thickness of the Cr coating as the base layer is 0.2 to 5.0
μm, and the Ti-based hard coating as the finishing layer is made of Ti,
Golden/blackish-gray color mainly composed of C and N compounds, Ti,
Black-brown type mainly composed of C, O compounds, or Ti,
2. The exterior part for a timepiece according to claim 1, wherein the coating is a type of blue mainly composed of a compound of O and has a coating thickness of 0.2 to 2.0 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1039730A JP2985088B2 (en) | 1989-02-20 | 1989-02-20 | Manufacturing method of watch exterior parts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1039730A JP2985088B2 (en) | 1989-02-20 | 1989-02-20 | Manufacturing method of watch exterior parts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02217460A true JPH02217460A (en) | 1990-08-30 |
| JP2985088B2 JP2985088B2 (en) | 1999-11-29 |
Family
ID=12561091
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1039730A Expired - Fee Related JP2985088B2 (en) | 1989-02-20 | 1989-02-20 | Manufacturing method of watch exterior parts |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2985088B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04193967A (en) * | 1990-11-27 | 1992-07-14 | Kobe Steel Ltd | Surface treated metallic material and its manufacture |
| JP2003105561A (en) * | 2001-09-27 | 2003-04-09 | Seiko Instruments Inc | Decorative member |
| CN113445002A (en) * | 2020-03-25 | 2021-09-28 | 株式会社日本显示器 | Method for manufacturing vapor deposition mask |
-
1989
- 1989-02-20 JP JP1039730A patent/JP2985088B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04193967A (en) * | 1990-11-27 | 1992-07-14 | Kobe Steel Ltd | Surface treated metallic material and its manufacture |
| JP2003105561A (en) * | 2001-09-27 | 2003-04-09 | Seiko Instruments Inc | Decorative member |
| CN113445002A (en) * | 2020-03-25 | 2021-09-28 | 株式会社日本显示器 | Method for manufacturing vapor deposition mask |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2985088B2 (en) | 1999-11-29 |
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