JPH0765194B2 - Colored surface article and manufacturing method thereof - Google Patents
Colored surface article and manufacturing method thereofInfo
- Publication number
- JPH0765194B2 JPH0765194B2 JP2144547A JP14454790A JPH0765194B2 JP H0765194 B2 JPH0765194 B2 JP H0765194B2 JP 2144547 A JP2144547 A JP 2144547A JP 14454790 A JP14454790 A JP 14454790A JP H0765194 B2 JPH0765194 B2 JP H0765194B2
- Authority
- JP
- Japan
- Prior art keywords
- coating
- base material
- film
- temporary
- article
- 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 - Lifetime
Links
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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
- C23C18/1612—Process or apparatus coating on selected surface areas by direct patterning through irradiation means
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
- C23C18/1608—Process or apparatus coating on selected surface areas by direct patterning from pretreatment step, i.e. selective pre-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemically Coating (AREA)
- Electroplating Methods And Accessories (AREA)
- Physical Vapour Deposition (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- ing And Chemical Polishing (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、基材の少なくとも一面に色彩及び／又は色調
の異なる被膜を形成してなる有色表面物品及びその製造
方法に関し、具体的には、装飾品、スポーツ用品、工具
又は各種部品に装飾用又は表示用の有色表面物品及びそ
の製造方法に関する。Description: TECHNICAL FIELD The present invention relates to a colored surface article in which a coating having different colors and / or different color tones is formed on at least one surface of a substrate, and a method for producing the same, and specifically, The present invention relates to a colored surface article for decoration or display on a decorative article, a sports article, a tool or various parts, and a manufacturing method thereof.
（従来の技術） 従来から、ステンレス鋼、超硬合金、サーメットなどの
基材の表面を鏡面研磨することが、時計ケース、バン
ド、文字板などの装飾部分に用いられている。しかし、
この方法によっては、基材そのものの色彩に頼るために
単調となり、装飾的価値は制約される。また、これにエ
ッチングなどの手段によって刻印・刻字しても、鮮明な
ものが得られない。(Prior Art) Conventionally, mirror polishing of the surface of a base material such as stainless steel, cemented carbide, or cermet has been used for a decorative portion such as a watch case, a band, and a dial. But,
Some methods are monotonous because they rely on the color of the substrate itself, limiting the decorative value. In addition, even if this is engraved or inscribed by means such as etching, a clear one cannot be obtained.
この問題を解決するために、基材の表面に化学蒸着（CV
D）法や物理蒸着（PVD）法のようなドライプレーティン
グ法；又は陽極酸化処理、電解メッキ、無電解メッキな
どのウェットプレーティング法により、金色、銀色、黒
色などを組み合わせた複数の色相を呈する被膜を形成し
てなる装飾部品に関する提案が、多数なされている。こ
れらの多色装飾部品に関する代表的な提案は、特開昭58
−100682号公報、特開昭61−157673号公報及び特開昭64
−75659号公報に開示されている。To solve this problem, chemical vapor deposition (CV
D) method or dry plating method such as physical vapor deposition (PVD) method; or wet plating method such as anodizing, electrolytic plating, electroless plating, etc., to present multiple hues combining gold, silver, black, etc. Many proposals have been made regarding decorative parts formed by coating. A representative proposal for these multicolor decorative parts is disclosed in Japanese Patent Laid-Open No.
-100682, JP 61-157673 and JP 64
-75659.
（発明が解決しようとする課題） 上述の装飾部品の多色化に関する提案のうち、特開昭58
−100682号公報には、低炭素オーステナイト系ステンレ
ス鋼の表面にAl2O3とTiO2からなる容射材料を0.1〜1mm
の厚みに容射した後、ラッピング加工によって鏡面状態
にし、残りのステンレス部分に金メッキ又はTiNコーテ
ィングする時計用外装部品の製造方法が開示されてい
る。しかし、この方法による時計用外装部品は、容射の
際の加熱及び冷却によりステンレス鋼と容射被膜との間
に歪を生じ、容射被膜面に微小クラックが入って美的効
果が低下することと、マスキングと容射によっては細い
線模様を形成できないために模様の形状に制約があるこ
と、さらに金メッキの場合には金の被膜が容易に剥離す
るという問題がある。(Problems to be Solved by the Invention) Among the above-mentioned proposals regarding multicoloring of decorative parts, JP-A-58-58
No. 100682 discloses that a surface of low carbon austenitic stainless steel is coated with a spray material of Al 2 O 3 and TiO 2 in an amount of 0.1 to 1 mm.
The method of manufacturing the exterior component for a timepiece is disclosed in which the outer surface of the timepiece is exposed to the same thickness, and then the surface is mirror-finished by lapping, and the remaining stainless portion is gold-plated or TiN-coated. However, the exterior parts for timepieces produced by this method may cause distortion between the stainless steel and the spray coating due to heating and cooling during spraying, resulting in microcracks on the spray coating surface and reducing aesthetic effects. However, there is a problem that the shape of the pattern is limited because a thin line pattern cannot be formed by masking and radiation, and that the gold coating easily peels off in the case of gold plating.
また特開昭61−157673号公報には、基材の表面にイオン
プレーティング処理により硬質色層を形成した後、この
硬質色層の任意の部分をマスキングし、次いでイオンプ
レーティング処理によって該硬質色層とは異なった色の
層を形成する多色硬質膜の製造方法が開示されている。
しかし、この方法によって得られる多色硬質膜物品は、
微細な模様を形成するのが困難であるうえ、AuやPtなど
の貴金属を形成しても、容易に剥離して実用化できない
という問題がある。Further, in JP-A-61-157673, a hard color layer is formed on the surface of a substrate by an ion plating treatment, then an arbitrary portion of the hard color layer is masked, and then the hard color layer is treated by an ion plating treatment. A method for producing a multicolor hard film that forms a layer having a color different from that of the color layer is disclosed.
However, the multicolor rigid film article obtained by this method is
There is a problem that it is difficult to form a fine pattern, and even if a precious metal such as Au or Pt is formed, it is easily peeled off and cannot be put to practical use.
さらに、特開昭64−75659号公報には、下地金属の表面
にイオンプレーティングによって有色被膜を形成した
後、レーザー加工により被膜の一部を除去し、金属を露
出させる金属表面の多色化法が開示されている。しか
し、この方法によって得られる多色物品は、被膜の材質
が制限されること、とくにAuやPtなどの貴金属の被膜を
形成する場合、貴金属の使用量が多くなり高価になるこ
と、貴金属による繊細な図案や模様の形成が困難である
こと、及び密着性が悪く、容易に剥離して実用化できな
いという問題がある。Further, in Japanese Patent Laid-Open No. 64-75659, a colored film is formed on the surface of a base metal by ion plating, and then a part of the film is removed by laser processing to expose the metal, thereby making the metal surface multicolored. The law is disclosed. However, the multicolored products obtained by this method are limited in the material of the coating, especially when forming a coating of a noble metal such as Au or Pt, the amount of precious metal used increases and the cost becomes high. There is a problem that it is difficult to form various designs and patterns, and the adhesiveness is poor, so that it is easily peeled off and cannot be put to practical use.
本発明は、上述のような問題点を解決したもので、基本
的には、基材の少なくとも一面にAuやPtのような貴金属
ないしCu系金属の被膜を密着性よく被覆してなる貴金属
色ないしCu系金属色によって繊細な模様や文字・記号を
構成することを可能にするとともに、被膜の密着力を高
めた実用性のある有色表面物品及びその製造方法の提供
を目的とするものである。The present invention has solved the above-mentioned problems, basically, a noble metal color obtained by coating a film of a noble metal such as Au or Pt or a Cu-based metal with good adhesion on at least one surface of the substrate. It is intended to provide a practical colored surface article and a manufacturing method thereof, which enables delicate patterns and characters / symbols to be formed by a Cu-based metal color, and which improves the adhesion of the coating. .
（課題が解決するための手段） 本発明は、基材の少なくとも一面の特定部分に被膜を形
成してなる物品において、 該被膜がCu、Ag、Au、Pt、Ir、Os、Pd、Rh、Ru及びこれ
らを含有する合金の少なくとも１種の単層膜もしくは複
層膜からなり；かつ該被膜は該基材の表面に設けられ、
幅0.1μ〜2mmの凹部状線の熱溶融面上に形成されてなる ことを特徴とする有色表面物品である。(Means for Solving the Problems) The present invention provides an article in which a coating is formed on a specific portion of at least one surface of a substrate, wherein the coating is Cu, Ag, Au, Pt, Ir, Os, Pd, Rh, A single layer film or a multilayer film of at least one kind of Ru and an alloy containing them; and the coating film is provided on the surface of the substrate,
A colored surface article formed on a heat-melting surface of a concave line having a width of 0.1 μm to 2 mm.
該有色表面物品は、下記（ａ）、（ｂ）、（ｃ）、
（ｄ）及び（ｅ）工程を経て、表面に設けられた凹部状
線の熱溶融面上に被膜を形成することによって製造する
ことができる。The colored surface article has the following (a), (b), (c),
Through the steps (d) and (e), it can be manufactured by forming a coating film on the heat-melting surface of the concave wire provided on the surface.
（ａ）基材の表面に後述の被膜に対して親和性の低い物
質からなる仮設被膜を形成する工程； （ｂ）該仮設被膜の表面にレーザー照射を行って、該仮
設被膜及びその部位の基材の表面を溶融及び除去し、該
基材の表面に凹部状線の熱溶融面を形成する工程； （ｃ）Cu、Ag、Au、Pt、Ir、Os、Pd、Rh、Ru及びこれら
を含有する合金の少なくとも１種の単層膜もしくは複層
膜からなる被膜を形成する工程； （ｄ）該仮設被膜面状に残存する被膜を除去する工程；
及び （ｅ）該仮設被膜を除去する工程。(A) a step of forming a temporary coating made of a substance having a low affinity for the coating described later on the surface of the base material; (b) irradiating the surface of the temporary coating with a laser to remove the temporary coating and its portion. A step of melting and removing the surface of the base material and forming a heat-melting surface of the concave line on the surface of the base material; (c) Cu, Ag, Au, Pt, Ir, Os, Pd, Rh, Ru and these. Forming a film composed of at least one single-layer film or multi-layer film of an alloy containing: (d) removing the film remaining on the surface of the temporary film;
And (e) a step of removing the temporary coating.
本発明に用いられる基材は、本発明の物品の使用目的に
適したものであれば何でもよく、特に限定されないが、
例えばニッケル、ステンレス鋼、高速度鋼、Cr−Al−Ni
合金、黄銅、青銅などの金属材料；ガラス、セラミック
ス、人工サファイアなどの無機材料及びサーメット、超
硬合金のような無機材料と金属の複合体が例示される。
これらの中で、被膜との色彩及び／又は色調の対照によ
って美観を呈することから、特にステンレス鋼、サーメ
ット及び超硬合金が好ましい。用途的には、装飾品、工
具、銘板などの材料に適したものが好ましい。The substrate used in the present invention may be any one suitable for the purpose of use of the article of the present invention, and is not particularly limited,
For example, nickel, stainless steel, high speed steel, Cr-Al-Ni
Examples thereof include metal materials such as alloys, brass and bronze; inorganic materials such as glass, ceramics and artificial sapphire, and composites of inorganic materials and metals such as cermet and cemented carbide.
Among these, stainless steel, cermet and cemented carbide are particularly preferable because they show an aesthetic appearance by contrasting the color and / or color tone with the coating. In terms of applications, those suitable for materials such as ornaments, tools and name plates are preferable.
この基材の表面に局部的に設ける凹部状線の熱溶融面と
は、所望する装飾又は表示のための図案もしくは図形に
より異なるもので、具体的には、幅が少なくとも0.1μ
ｍ〜2mmであり、深さが少なくとも0.50μｍであること
が好ましい。特に美麗な線形を創製するためには、幅が
少なくとも0.5μｍ、深さが少なくとも１μｍからなる
ことがより好ましい。この凹部状線の形状は、基材の断
面からの形状が例えば底面の段付形状、円形状、角形状
又はＶ字形状があり、この内、美麗な線形の創製と被膜
の基材への密着強さを高めるために、特に段付形状が好
ましく、この段付形状としては、１段付形状から凹部状
線の幅によっては複数段付形状からなるものである。こ
の凹部状線の深さは、被膜の基材への密着強さ及び被膜
の使用量の関係から、基材の表面の面粗さにより生ずる
最小値（基材の表面凹凸の最大深さ）を基準とし、この
基準から少なくとも0.5μｍ深いことが好ましく、基準
から少なくとも１μｍ深いことがより好ましく、基準か
ら３〜100μｍ深いことが特に好ましい。この凹部状線
は、基材が熱によって溶融及び除去されて、熱溶融面を
形成して生じたものである。The heat-melting surface of the concave line locally provided on the surface of the base material is different depending on the design or graphic for the desired decoration or display, and specifically, the width is at least 0.1 μm.
It is preferably m to 2 mm and the depth is at least 0.50 μm. In order to create a particularly beautiful line, it is more preferable that the width is at least 0.5 μm and the depth is at least 1 μm. The shape of the concave line may be, for example, a stepped shape of the bottom surface, a circular shape, a square shape, or a V shape from the cross section of the base material. In order to increase the adhesion strength, a stepped shape is particularly preferable, and the stepped shape may be one stepped shape or a plurality of stepped shapes depending on the width of the concave line. The depth of this concave line is the minimum value (maximum depth of the surface irregularities of the base material) caused by the surface roughness of the base material from the relationship between the adhesion strength of the coating to the base material and the amount of the coating used. Is preferably at least 0.5 μm deeper than this standard, more preferably at least 1 μm deeper than the standard, and particularly preferably 3 to 100 μm deeper than the standard. The concave line is formed by melting and removing the base material by heat to form a hot-melt surface.
本発明において、被膜を構成する物質として用いられる
ものは、Cu、Ag、Au、Pt、Ir、Os、Pd、Rh、Ru及びPtで
ある。また、これらの金属を主成分とする合金もまた用
いることができる。そのような合金の例としては、Au−
Ag合金、Au−Ni合金、Au−Ni−In合金、Au−Cu合金、Au
−Cu−Cd合金、Pt−Rh合金、Cu−Zn合金、Cu−Su合金な
どが挙げられる。In the present invention, Cu, Ag, Au, Pt, Ir, Os, Pd, Rh, Ru and Pt are used as the material constituting the coating film. Further, alloys containing these metals as main components can also be used. Examples of such alloys include Au-
Ag alloy, Au-Ni alloy, Au-Ni-In alloy, Au-Cu alloy, Au
-Cu-Cd alloy, Pt-Rh alloy, Cu-Zn alloy, Cu-Su alloy etc. are mentioned.
これらのうち、とくに美観と堅牢度から、Cu、Ag、Au、
Pt及びこれらを含む合金の中の少なくとも１種を用いる
ことが望ましい。またとくにAuやPt及びこれらを含む合
金は、本発明の方法を用いるときに、はじめて基材の上
に強固に密着させることができるので好ましい。Of these, Cu, Ag, Au,
It is desirable to use at least one of Pt and alloys containing them. Further, Au, Pt and alloys containing them are particularly preferable because they can be firmly adhered to the substrate for the first time when the method of the present invention is used.
これらの１種を単層膜として用いてもよく、また被膜の
形成を複数回行うことによって、相互に、また基材とも
色彩及び／又は色調の異なる複数個の被膜を形成しても
よい。この場合、一部の被膜は、Tiなどの金属をドライ
プレーティングで形成してもよい。One of these may be used as a monolayer film, or a plurality of coatings having different colors and / or tones may be formed by mutually forming the coating a plurality of times. In this case, some coatings may be formed by dry plating a metal such as Ti.
被膜の厚さはとくに限定されないが、好ましくは0.01〜
20μｍ、さらに好ましくは0.1〜５μｍの厚さである。
あまり厚くなると材料が無駄であるばかりか、後述のよ
うに仮設被膜の上に形成された部分を除去するときに、
境界部分の切断に外力を多く必要とする。特に基材面よ
りも低い状態で被膜が形成されていることが好ましい。The thickness of the coating is not particularly limited, but preferably 0.01 to
The thickness is 20 μm, more preferably 0.1 to 5 μm.
Not only is the material useless if it becomes too thick, but when removing the portion formed on the temporary coating as described below,
A lot of external force is required to cut the boundary. Particularly, it is preferable that the coating film is formed in a state lower than the surface of the base material.
本発明の有色表面物品は、次のようにして製造される。The colored surface article of the present invention is manufactured as follows.
（ａ）仮設被膜の形成 まず、基材の多色化したい表面に仮設被膜を形成する。
必要に応じて、該表面に研磨、ラッピング、洗浄などの
前処理を施しても差支えない。(A) Formation of Temporary Coating First, a temporary coating is formed on the surface of the base material to be multicolored.
If necessary, the surface may be subjected to pretreatment such as polishing, lapping, and washing.
仮設被膜は、本発明の被膜を形成した後に、処理その他
の方法によって除去される。したがって仮設被膜の材質
は、被膜形成能があり、かつ除去しやすい、本発明の被
膜に用いられる以外の金属又は合金から選ばれ、特にそ
れらとの間に親和性が少なくて、仮設被膜の上に形成し
た被膜を剥離しやすいものが選ばれる。すなわち、Ti、
Zr、Cr、Ti−Zr合金、Ti−Al合金、Ti−Ni合金、Ti−Ｖ
合金などが好ましい。ただし、実際に基材に用いられた
ものとは別の金属又は合金が用いられる。また基材との
密着性が乏しい場合には、別の下地層、たとえばNiなど
の層を設ける。The temporary coating is removed by treatment or other methods after forming the coating of the present invention. Therefore, the material of the temporary coating is selected from the metals or alloys other than those used in the coating of the present invention, which have the ability to form a coating and are easy to remove. A material that easily peels off the coating film formed on is selected. That is, Ti,
Zr, Cr, Ti-Zr alloy, Ti-Al alloy, Ti-Ni alloy, Ti-V
Alloys and the like are preferable. However, a metal or alloy different from the one actually used for the substrate is used. If the adhesion to the substrate is poor, another underlayer, such as a layer of Ni, is provided.
仮設被膜を形成する方法としては、その材質に応じて、
陽極酸化、電解メッキ、無電解メッキ、イオンプレーテ
ィング、真空蒸着、電子ビーム蒸着、容射、スパッタリ
ング、CVDなど、任意の方法を用いることができる。被
膜形成は物品の表面全部に行ってもよく、物品の形状や
目的に応じて、一部、たとえば多色表面の形成が必要な
部分についてのみ行ってもよい。As a method of forming a temporary coating, depending on the material,
Any method such as anodic oxidation, electrolytic plating, electroless plating, ion plating, vacuum deposition, electron beam deposition, spraying, sputtering, and CVD can be used. The film formation may be performed on the entire surface of the article, or may be performed only on a part, for example, a portion where a multicolored surface is required, depending on the shape and purpose of the article.
仮設被膜の厚さは目的によって任意に選択しうるが、好
ましくは10μｍ以下、より好ましくは１μｍ以下、さら
に好ましくは0.1〜0.5μｍである。The thickness of the temporary coating can be arbitrarily selected depending on the purpose, but it is preferably 10 μm or less, more preferably 1 μm or less, still more preferably 0.1 to 0.5 μm.
（ｂ）レーザー処理 このようにして仮設被膜を形成したのち、レーザー処理
によって該被膜を局部的に除去するとともに、該部位の
基材を、少なくとも0.5μｍの深さまで溶融除去する。
すなわち、該被膜を施した面より、模様、パターン、文
字、記号など、後に被膜を被着したい部位にのみレーザ
ー光を照射して、その部位の仮設被膜と表面付近の基材
を溶融除去し、基材を露出させる。(B) Laser treatment After the temporary coating is formed in this manner, the coating is locally removed by laser treatment, and the base material at the site is melted and removed to a depth of at least 0.5 μm.
That is, from the surface on which the coating is applied, laser light is radiated only to a portion, such as a pattern, pattern, character, or symbol, where the coating is to be applied later, and the temporary coating at that portion and the base material near the surface are melted and removed. Exposing the substrate.
レーザーとしてはNe−He、アルゴン、CO2などの気体レ
ーザー；ルビー、YAG、ガラスなどの固体レーザー及びG
aAsなどの半導体レーザーなどが例示されるが、室温で
連続発振を容易に行いうること、低い照射エネルギー領
域における制御性良いことから、YAGレーザーが好まし
い。照射条件は仮設被膜の材質と厚さによって異なり、
照射エネルギーを制御しつつ、熱でその部位の基材の表
面が溶融して、熱溶融面となるように照射すればよい。Gas lasers such as Ne-He, Argon and CO 2 ; solid state lasers such as ruby, YAG and glass and G
A semiconductor laser such as aAs is exemplified, but a YAG laser is preferable because it can easily perform continuous oscillation at room temperature and has good controllability in a low irradiation energy region. Irradiation conditions vary depending on the material and thickness of the temporary coating,
Irradiation may be performed while controlling the irradiation energy so that the surface of the base material at that portion is melted by heat and becomes a heat melting surface.
このようなレーザー照射によって仮設被膜と表面付近の
基材を溶融除去する幅は、0.1μｍ〜2mmである （ｃ）被膜の形成 レーザー照射を行った表面を、水又は有機溶剤で洗浄し
た後、被膜を形成する。該被膜の形成は、陽極酸化、電
解メッキ、無電解メッキのような通常のウェットプレー
ティング法によって行うことができる。The width for melting and removing the temporary coating and the substrate in the vicinity of the surface by such laser irradiation is 0.1 μm to 2 mm. (C) Formation of the coating After washing the surface subjected to laser irradiation with water or an organic solvent, Form a film. The formation of the coating film can be performed by an ordinary wet plating method such as anodic oxidation, electrolytic plating, and electroless plating.
レーザー照射の工程において、レーザーによって生ずる
溝は仮設被膜を貫いて基材に達し、さらに基材の中にま
で少なくとも0.5μｍの深さに貫入している。したがっ
てその部位においては、被膜はその深さまで基材に貫入
して形成される。なお、被膜のうち熱溶融面に形成され
た被膜は基材の表面よりも低くなっていることが好まし
い。すなわち、この部位では、被膜は凹部状線の内部に
形成されることが好ましい。In the laser irradiation step, the grooves generated by the laser penetrate the temporary coating to reach the substrate and further penetrate into the substrate to a depth of at least 0.5 μm. Therefore, at that site, the coating penetrates the substrate to that depth. The coating formed on the heat melting surface of the coating is preferably lower than the surface of the base material. That is, at this portion, the coating is preferably formed inside the concave line.
このレーザー照射とマスキング及び被膜の形成を複数回
行い、かつそのつど被膜に用いる材質を異なる色彩及び
／又は色調を呈するものに変更することによって、３色
以上の多色表面を形成することも可能である。It is also possible to form a multi-colored surface of three or more colors by performing this laser irradiation, masking and film formation multiple times, and changing the material used for the film each time to a different color and / or color tone. Is.
（ｄ）仮設被膜の上の被膜の除去 本発明者らが見出したところでは、このようにして形成
された被膜は、基材の上に形成された部分は基材への密
着性に優れ、基材に対して強固に接合されている。これ
に対して、仮設被膜の上に形成された被膜は仮設被膜に
対して剥離性を示す。(D) Removal of Coating on Temporary Coating The present inventors have found that the coating thus formed has excellent adhesiveness to the substrate in the portion formed on the substrate. It is firmly bonded to the base material. On the other hand, the coating formed on the temporary coating exhibits releasability with respect to the temporary coating.
したがって、本発明において被膜を形成した次の工程
は、水、アルコール、アセトン及びそれらの混合溶媒で
洗浄するか、クロスやレザーでこするなど、任意の方法
により、仮設被膜の上に形成されている部分の被膜を剥
離、除去することである。除去された被膜の材料は、回
収して再利用することができる。Therefore, in the next step of forming the coating film in the present invention, the film may be formed on the temporary coating film by any method such as washing with water, alcohol, acetone and a mixed solvent thereof, or rubbing with a cloth or a leather. This is to remove and remove the coating on the existing part. The removed coating material can be recovered and reused.
（ｅ）仮設被膜の除去 ついで、仮設被膜として用いられた金属又は合金を除去
する。除去は、仮設被膜の材質に応じて、また本発明の
被膜を冒さない条件を選んで、酸処理などの方法によっ
て行うことができる。(E) Removal of Temporary Coating Next, the metal or alloy used as the temporary coating is removed. The removal can be carried out by a method such as acid treatment, depending on the material of the temporary coating and by selecting the conditions that do not affect the coating of the present invention.
（作用） 本発明によれば、基材と被膜によって、微細な模様、パ
ターン、文字及び／又は記号を含む多色表面を形成する
ことができる。レーザー照射によって被膜を形成したい
部位の仮設被膜を破壊するとともに、同じ部位の基材を
任意の深さまで溶融除去し、形成した被膜の基材への密
着性を高めることができる。(Operation) According to the present invention, the base material and the coating film can form a multicolored surface including fine patterns, patterns, characters and / or symbols. It is possible to destroy the temporary coating film at the site where the coating film is to be formed by laser irradiation, and melt and remove the base material at the same site to an arbitrary depth to improve the adhesion of the formed coating film to the base material.
（発明の効果） 本発明により、装飾性に富み、かつ堅牢な多色表面なら
びにそのような表面をもつ物品を容易に形成することが
できる。本発明で得られる有色表面は、その材質固有の
色調を保つとともに、微細な模様、パターン、文字又は
記号を表現することができる。(Effects of the Invention) According to the present invention, it is possible to easily form a decorative multicolored surface that is rich in decorativeness and an article having such a surface. The colored surface obtained by the present invention can maintain a color tone peculiar to the material and express a fine pattern, pattern, character or symbol.
したがって本発明は、時計ケース、バンド、文字盤、ネ
クタイピン、カフスボタン、ブローチ、ライター、メガ
ネなどの装飾品及びゴルフクラブなどのスポーツ用品に
おけるパターンの形成や文字などの表示、；切削工具や
耐摩工具などの工具における美的効果の向上；及び各種
製品やその銘板における製品名、商標、社標、品質など
の表示に用いて、きわめて有効である。Accordingly, the present invention is directed to the formation of patterns and the display of characters in ornaments such as watch cases, bands, dials, tie pins, cufflinks, broaches, lighters, and glasses, and sports equipment such as golf clubs; cutting tools and abrasion resistance. It is very effective for improving the aesthetic effect of tools such as tools; and for displaying product names, trademarks, company marks, quality, etc. on various products and their nameplates.
（実施例） 以下、本発明を実施例および比較例によって説明する。
実施例中に記した番号は、本発明の工程を説明する第１
図において用いた各部分の番号である。なお、本発明は
実施例によって限定されるものではない。(Examples) Hereinafter, the present invention will be described with reference to Examples and Comparative Examples.
The numbers given in the examples are the first to describe the steps of the present invention.
It is the number of each part used in the figure. The present invention is not limited to the examples.
実施例１ 表面の研磨及びラッピングによって鏡面化したSUS304か
らなる板状の基材１の、２色表面を形成したい面２に、
通常のホローカソード放電法（HCD法）によるイオンプ
レーティングを施して、仮設被膜として厚さ0.3μｍの
チタン被膜３を形成した。次いで、該被膜の上からYAG
レーザーをパルス幅2.0ms、パワー密度400kW/cm2で照射
走行させて、１本の幅が1mmの縞状にレーザー光を当
て、その部分の被膜及びその部位の基材の一部を溶融除
去するとともに、30μｍの深さからなる熱溶融面を形成
した。Example 1 On a surface 2 on which a two-color surface is to be formed, of a plate-shaped substrate 1 made of SUS304 that is mirror-finished by polishing and lapping the surface
Ion plating was performed by a normal hollow cathode discharge method (HCD method) to form a titanium coating 3 having a thickness of 0.3 μm as a temporary coating. Then, from the top of the film, YAG
The laser is irradiated with a pulse width of 2.0 ms and a power density of 400 kW / cm 2 , and the laser light is applied in stripes with a width of 1 mm to melt and remove the coating on that part and part of the base material on that part. At the same time, a hot-melt surface having a depth of 30 μm was formed.
このようにして得られた、面２の上に仮設被膜３がパタ
ーン状に残った面を、水及びアセトンによって洗浄した
後、シアン化金カリウムを用いて常法により金メッキを
行い、膜厚２μｍの金の被膜４を得た。この被膜４は、
さきにレーザー照射を行った部位では基材１に、それ以
外の部位では薄く３に接合していた。これを、水で洗浄
して４のうち３に接合している部分を剥離せしめて除去
し、洗浄及び乾燥を行った。さらに、３の上に一部残存
していた４を、クロスで抜きとり、除去した。The surface of the thus obtained surface 2 on which the temporary coating 3 was left in a pattern was washed with water and acetone, and then gold-plated with potassium gold cyanide by a conventional method to give a film thickness of 2 μm. Gold coating 4 was obtained. This coating 4 is
It was bonded to the base material 1 at the portion where the laser irradiation was previously performed and thinly bonded to the portion 3 at the other portions. This was washed with water to remove the portion bonded to 3 of 4 by peeling it off, and washed and dried. Further, 4 which was partially left on 3 was removed with a cloth.
ついで、フッ酸液に浸漬することによりチタン被膜を除
去し、金被膜を残した。ついで水及びアルコールによっ
て洗浄し、本発明の物品を得た。Then, the titanium coating was removed by immersing it in a hydrofluoric acid solution, leaving the gold coating. Then, it was washed with water and alcohol to obtain an article of the present invention.
以上の工程により、金属光沢と金色の２色表面を有する
本発明の物品を得た。Through the above steps, an article of the present invention having a two-color surface of metallic luster and gold was obtained.
このようにして得られた２色表面を金属顕微鏡で調べた
ところ、被膜の厚さは15μｍであった。また、この表面
にセロハンテープを接着させ、これを強く引き剥して、
被膜が剥離するか否かを観察した。これを５回繰り返し
たところ、剥離は認められなかった。When the thus-obtained two-color surface was examined with a metallurgical microscope, the thickness of the coating was 15 μm. Also, attach cellophane tape to this surface, peel it off strongly,
It was observed whether the coating peeled off. When this was repeated 5 times, peeling was not observed.
実施例２ 実施例１と同様の基材を用いて、公知の電解メッキの方
法によって基材の表面に膜厚２μｍのNiメッキを行った
後、さらにNi被膜の表面に膜厚が２μｍになるようにCr
メッキを行った。次いで、被膜の表面からパルス幅1.7m
s、パワー密度600kW/cm2でレーザーを照射走行させて、
20μｍの深さの溝を形成し、その部分の被膜及び基材を
溶融除去して基材の表面に熱溶融面を作製した。次に、
実施例１と同様にして膜厚１μｍの金メッキ層を形成
し、洗浄、乾燥、クロスによる拭き取りを行った。Example 2 The same substrate as in Example 1 was used to perform Ni plating with a film thickness of 2 μm on the surface of the substrate by a known electrolytic plating method, and then the film thickness on the surface of the Ni coating became 2 μm. As Cr
It was plated. Then, pulse width 1.7m from the surface of the coating
s, laser irradiation with a power density of 600 kW / cm 2
A groove having a depth of 20 μm was formed, and the coating film and the base material at that portion were melted and removed to prepare a heat-melted surface on the surface of the base material. next,
In the same manner as in Example 1, a gold plating layer having a film thickness of 1 μm was formed, washed, dried, and wiped with a cloth.
その後、塩酸及び市販のNi被膜の剥離液でもってCr及び
Niの被膜を除去して、基材の表面に金被膜の形成されて
なる本発明品を得た。After that, with a stripper of hydrochloric acid and a commercially available Ni coating, Cr and
The Ni coating was removed to obtain a product of the present invention in which a gold coating was formed on the surface of the base material.
比較例 比較として、実施例１及び２と同様の基材を用いて、基
材の表面に膜厚が２μｍになるように金メッキを行って
比較例の物品を得た。Comparative Example For comparison, the same base material as in Examples 1 and 2 was used to perform gold plating on the surface of the base material so that the film thickness was 2 μm, to obtain a comparative example article.
こうして実施例１及び２と比較例で、それぞれ得た物品
について、金被膜と基材との密着強さを、ワイヤブラシ
状のもので引掻いて調べたところ、比較例の物品は１回
の試行で金が剥離したのに対し、実施例１及び２の物品
は３回行っても剥離せず、単に引掻き筋が入っている状
態であった。The adhesive strength between the gold coating and the base material of the articles obtained in Examples 1 and 2 and Comparative Example was examined by scratching with a wire brush. While the gold was peeled off in the trial, the articles of Examples 1 and 2 were not peeled off even after being carried out three times, and were in a state where only scratch lines were formed.
第１図は本発明の工程の一例を断面図で示したものであ
る。 １……基材 ２……多色表面を形成したい面 ３……仮設被膜 ４……被膜 （ ）内は工程順を示す。 （ａ）……仮設被膜形成 （ｂ）……レーザー照射 （ｃ）……被膜形成 （ｄ）……仮設被膜の上の被膜の除去 （ｅ）……仮設被膜の除去FIG. 1 is a sectional view showing an example of the process of the present invention. 1 ... Substrate 2 ... Surface on which multicolored surface is to be formed 3 ... Temporary coating 4 ... Film () shows the process order. (A) …… Formation of temporary coating (b) …… Laser irradiation (c) …… Formation of coating (d) …… Removal of coating on temporary coating (e) …… Removal of temporary coating
───────────────────────────────────────────────────── フロントページの続き (72)発明者 渋木 邦夫 神奈川県川崎市幸区塚越１丁目７番地 東 芝タンガロイ株式会社内 (72)発明者 渡辺 徳子 東京都葛飾区東立石２丁目19番１号 株式 会社大和鍍金工場内 (72)発明者 渡辺 昭啓 東京都葛飾区東立石２丁目19番１号 株式 会社大和鍍金工場内 (56)参考文献 特開 昭60−59073（ＪＰ，Ａ) 特開 平２−77586（ＪＰ，Ａ) 特開 昭60−33363（ＪＰ，Ａ) 特開 昭63−53267（ＪＰ，Ａ) 特開 昭63−1483（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Kunio Shibuki 1-7 Tsukakoshi, Sachi-ku, Kawasaki-shi, Kanagawa Higashi-Toshiba Tungaloy Co., Ltd. Daiwa Plating Co., Ltd. (72) Inventor Akihiro Watanabe 2-19-1 Higashi-Tateishi, Katsushika-ku, Tokyo Inside Daiwa Plating Co., Ltd. (56) Reference JP 60-59073 (JP, A) JP Japanese Patent Application Laid-Open No. 2-77586 (JP, A) JP 60-33363 (JP, A) JP 63-53267 (JP, A) JP 63-1483 (JP, A)
Claims (3)
形成してなる物品において、該被膜がCu、Ag、Au、Pt、
Ir、Os、Pd、Rh、Ru及びこれらを含有する合金の中の少
なくとも１種の単層膜もしくは複層膜からなり；かつ該
被膜は該基材の表面に設けられ、幅が0.1μｍ〜2mmの凹
部状線の熱溶融面上に形成されてなることを特徴とする
多色表面物品。1. An article comprising a base material and a coating formed on at least one specific surface of the base material, the coating comprising Cu, Ag, Au, Pt,
Consists of a single-layer film or a multi-layer film of at least one of Ir, Os, Pd, Rh, Ru and alloys containing them; and the coating is provided on the surface of the substrate and has a width of 0.1 μm to A multicolor surface article, which is formed on a heat-melting surface of a 2 mm concave line.
も0.5μｍの深さに形成されていることを特徴とする請
求項１記載の有色表面物品。2. The colored surface article according to claim 1, wherein the heat-melting surface is formed at a depth of at least 0.5 μm from the surface of the base material.
（ｅ）の工程を経て、基材の表面に設けられた凹部状線
の熱溶融面上に被膜を形成することを特徴とする有色表
面物品の製造方法。 （ａ）基材の表面に後述の被膜に対して親和性の低い物
質からなる仮設被膜を形成する工程； （ｂ）該仮設被膜の表面にレーザー照射を行って、該仮
設被膜及びその部位の基材の表面を溶融及び除去し、該
基材の表面に凹部状線の熱溶融面を形成する工程； （ｃ）Cu、Ag、Au、Pt、Ir、Os、Pd、Rh、Ru及びこれら
を含有する合金の中の少なくとも１種の単層膜もしくは
複層膜からなる被膜を形成する工程； （ｄ）該仮設被膜面上に残存する被膜を除去する工程；
及び （ｅ）該仮設被膜を除去する工程。3. A coating film is formed on the heat-melting surface of the concave line provided on the surface of the base material through the following steps (a), (b), (c), (d) and (e). A method for producing a colored surface article, comprising: (A) a step of forming a temporary coating made of a substance having a low affinity for the coating described later on the surface of the base material; (b) irradiating the surface of the temporary coating with a laser to remove the temporary coating and its portion. A step of melting and removing the surface of the base material and forming a heat-melting surface of the concave line on the surface of the base material; (c) Cu, Ag, Au, Pt, Ir, Os, Pd, Rh, Ru and these. Forming a film composed of at least one single-layer film or multi-layer film in the alloy containing Al; (d) removing the film remaining on the surface of the temporary film;
And (e) a step of removing the temporary coating.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2144547A JPH0765194B2 (en) | 1990-06-04 | 1990-06-04 | Colored surface article and manufacturing method thereof |
| DE69112277T DE69112277T2 (en) | 1990-05-31 | 1991-05-29 | Multi-colored product and method of making the same. |
| EP91108822A EP0459461B1 (en) | 1990-05-31 | 1991-05-29 | Multi-colored product and process for producing the same |
| KR1019910008935A KR960008013B1 (en) | 1990-05-31 | 1991-05-30 | Multi-colored product and process for producing the same |
| HK97101622A HK1000088A1 (en) | 1990-05-31 | 1997-07-31 | Multi-colored product and process for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2144547A JPH0765194B2 (en) | 1990-06-04 | 1990-06-04 | Colored surface article and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0441679A JPH0441679A (en) | 1992-02-12 |
| JPH0765194B2 true JPH0765194B2 (en) | 1995-07-12 |
Family
ID=15364835
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2144547A Expired - Lifetime JPH0765194B2 (en) | 1990-05-31 | 1990-06-04 | Colored surface article and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0765194B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH713250B1 (en) * | 2016-12-16 | 2021-01-29 | Rubattel Et Weyermann S A | A method of manufacturing a covering element, in particular a dial, timepiece or jewelry, in a non-conductive material and comprising metallized and / or colored engraved decorations. |
| EP3708384A1 (en) * | 2019-03-14 | 2020-09-16 | Omega SA | Trim element or dial of timepiece or piece of jewellery made of conductive material |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6033363A (en) * | 1983-08-02 | 1985-02-20 | Nippon Dento Kogyo Kk | Noble metal plating method |
| JPS6059073A (en) * | 1983-09-13 | 1985-04-05 | Seiko Instr & Electronics Ltd | Manufacture of external parts for watch |
| JPS631483A (en) * | 1986-06-19 | 1988-01-06 | Mitsubishi Electric Corp | Coloration of metal decorative panel |
| JPS6353267A (en) * | 1986-08-22 | 1988-03-07 | Nippon Dento Kogyo Kk | Plating method |
| JPS6475659A (en) * | 1987-09-18 | 1989-03-22 | Kowa Eng Kk | Multicoloration method for metallic surface |
| JPH0277586A (en) * | 1988-09-13 | 1990-03-16 | Seiko Epson Corp | External ornamental parts for timepiece |
-
1990
- 1990-06-04 JP JP2144547A patent/JPH0765194B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0441679A (en) | 1992-02-12 |
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