JPH0442470B2 - - Google Patents
Info
- Publication number
- JPH0442470B2 JPH0442470B2 JP58180394A JP18039483A JPH0442470B2 JP H0442470 B2 JPH0442470 B2 JP H0442470B2 JP 58180394 A JP58180394 A JP 58180394A JP 18039483 A JP18039483 A JP 18039483A JP H0442470 B2 JPH0442470 B2 JP H0442470B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- purple
- titanium carbonitride
- reaction gas
- reddish
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/36—Carbonitrides
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (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)
- Chemical Vapour Deposition (AREA)
Description
〔発明の技術分野〕
本発明は赤紫色又は銅色の表面光沢を有し、し
かもその表面が平滑面である装飾品に関する。
〔発明の技術的背景とその問題点〕
従来から、式：TiCxN1-x（式中、ｘは炭素原子
の混入率を表わす）で示される炭窒化チタンは、
ｘ＝0.3付近で独特の赤紫色の色調を呈するので
注目されている。そして、超硬合金工具などの基
材の表面に化学蒸着法（CVD法）を適用して上
記炭窒化チタンをコーテイングする方法が知られ
ている。
しかしながら、CVD法で得られた炭窒化チタ
ンの薄膜は、その表面がガサツぽく平滑ではない
ので装飾品としては不適当で、しかも、薄膜形成
時に適用する温度が約1000℃と高温であるため、
基材としてはこの温度に耐え得るものしか用いる
ことができず、処理できる基材が限定されざるを
得なかつた。
〔発明の目的〕
本発明は、赤紫色又は銅色の色調を有し、かつ
平滑な光沢表面を備えた装飾品の提供を目的とす
る。
〔発明の概要〕
本発明の装飾品は、表面が炭窒化チタン
（TiCN）薄膜で被覆されていることを特徴とす
る。
本発明の装飾品において、基材の表面を被覆す
るTiCN被膜は、反応ガス中の炭素の原子数を
ｎ、反応ガス中の窒素の原子数をn′としたとき、
ｎ，n′が１％≦ｎ／（ｎ＋n′）≦12％の関係を満
足するプラズマ化学蒸着法によつて形成された炭
窒化チタン薄膜で被覆されており、その表面が
JIS Ｚ 8105−2068で規定する（CIE1976）Ｌ
＊，ａ＊，ｂ＊色空間において、Ｌ＊，ａ＊，ｂ
＊はそれぞれ、60％≦Ｌ＊≦100％，２≦ａ＊≦
15，２≦ｂ＊≦28の関係を満足するような色調を
有しているものである。
この色調のとき、TiCN薄膜は赤紫色又は銅色
の光沢をもつて輝いている。ここで、Ｌ＊が小さ
すぎると、薄膜表面の明度が低くなつて光沢が不
満足となり、また100％のときはキラキラしすぎ
て表面の色相、彩度が不明確に知覚されるように
なる。したがつて、Ｌ＊は60％以上100％未満が
好ましく、更に好ましくは、70％≦Ｌ＊≦90％で
ある。
また、ａ＊及びｂ＊がそれぞれ大きくなりすぎ
ると、薄膜表面の色相はそれぞれ赤色、黄色が強
くなり、逆にａ＊，ｂ＊がそれぞれ小さくなりす
ぎると、表面の色調は白色に近くなり、目的とす
る色調の赤紫色又は銅色が得られ難くなる。した
がつてａ＊については２≦ａ＊≦15，ｂ＊につい
ては２≦ｂ＊≦28が好ましい。更に好ましくは、
ａ＊については５≦ａ＊≦12，ｂ＊については７
≦ｂ＊≦20である。
本発明にかかるTiCN薄膜は、模式図として例
示した以下の処理装置を用いることによりプラズ
マ化学蒸着法（PCVD法）で形成することができ
る。
図で、１は反応室で、室内にはヒータ用電源２
に接続したヒータ３、その上には放電用直流電源
４に接続した負電極５、負電極５と対向して正電
極６が配置されている。負電極５は表面処理すべ
き基体７の支持台の機能も兼ねている。
反応室１には、原料である反応ガスの供給系
（図示した右側の系）が連結されていて、ここか
ら、所定の流量で各原料が導入される。反応ガス
は水素（H2）と四塩化チタン（TiCl4）と炭素水
素と窒素（N2）の４種類の混合ガスである。図
で、８はN2の供給ボンベ、９は炭化水素の供給
ボンベである。用いる炭化水素としては、メタ
ン、エタン、プロパン、エチレン、アセチレン、
プロピレンなどが好適で、炭素数の少ない炭化水
素は取り扱い上好ましい。
１０はTiCl4のバブラー恒温槽で、ここに収納
されているTiCl4は水素ボンベ１１から送入され
るH2でバブリングされ、該恒温槽の温度に相当
する蒸気圧のTiCl4がH2ととも反応室１内に導入
される。このとき、槽１０の温度はTiCl4の供給
量との関係から決められるが、通常20〜80℃の範
囲のある温度に管理される。
また、アルゴンボンベ１２は、基体７の表面に
TiCN薄膜を形成する先立つて該基体表面を清浄
化するためのアルゴン（Ar）スパツタ用である。
１３は反応室１内を所定のガス圧に調節するた
めの真空ポンプ、１４は真空ポンプの油逆流防
止、TiCN薄膜形成時に副生する塩化物を捕捉す
るためのトラツプであり、これら全体で排気系が
構成されている。
図の装置を用いて、まず、供給系からArガス
を適当量導入しながら真空ポンプ１３で排気し反
応室１内を約0.05TorrのAr雰囲気に圧力調節し
基体７の表面を電流密度約0.5mA／cm3でスパツタ
して清浄化する。
その後、反応ガス供給系を切替え反応ガスを反
応室１内に導入しながら排気し反応ガスの全体圧
力を所定の値に調節しながら、ヒータ３で基体７
を加熱して両電極５，６間に電圧印加し反応室１
内にグロー放電を発生させる。
室内のガス圧が0.05Torr未満の場合にはグロ
ー放電が発生せず、また5Torrを超えるとグロー
放電が安定しないばかりでなくアーク放電が発生
し始める。好ましくは0.5〜2Torrである。
基体の加熱温度は100〜1000℃、好ましくは300
〜700℃、最も好ましくは500℃である。
また、放電時、基体の単位面積当りに流す電流
の電流密度は0.01〜1mA／cm2、好ましくは0.05〜
0.5mA／cm2である。
装置を運転するに当り必要な他のパラメータ、
例えば放電維持電圧、反応ガスの流量などは、反
応室の大きさや基体の表面積が変動すると、上記
した３つの条件の変動に対応して変化させなけれ
ばならないので一義的には決められない。
本発明にかかるTiCN薄膜の形成時における重
要な問題は、上記した反応ガス中で、炭素の原子
数と窒素の原子数を所定の割合で制御することで
ある。
すなわち、反応ガス中の炭素原子数をｎ、同じ
く窒素原子数をn′としたとき、ｎ，n′を１％≦
ｎ／ｎ＋n′≦12％となるように炭化水素とN2の係給
量を制御することである。
この比が小さすぎると、薄膜表面の色調は金色
が強くなる傾向が生じ、また大きすぎると、白色
光に近づく傾向が顕著になつていき、本発明が目
的とする色調が得にくくなる。したがつて、
ｎ／ｎ＋n′は１％から12％が好ましく、２〜６％で
あることが更に好ましい。
また、このTiCN薄膜が実用的な硬度を得るた
めには、その膜厚が0.1μm以上であることが好ま
しい。
なお、表面処理を施す基材としては、上記した
薄膜形成時に適用される温度に耐え得るものであ
ればいかなるものであつてもよい。例えば、金
属、セラミツク（含ガラス）等があるが、基材が
金属であれば導電性があり、TiCNが付着しやす
く、一方基材がセラミツクであると、基材が硬い
為、圧痕ができにくい装飾品を提供できる。
〔発明の実施例〕
実施例 １〜６
図に示した装置を用い、かつ表示した条件で
Ni基硬質合金ブロツクおよび時計側の鏡面仕上
げした表面にTiCN薄膜を形成した。この薄膜に
つき、その硬度をマイクロヴイツカース計で測定
し、また膜厚は薄膜をシヤドウイングしそのとき
形成された段差を表面粗さ計で測定した。更に、
各薄膜表面の色調は、JIS Ｚ 8105−2014で規定
する標準の光Ｃを用いてJIS Ｚ 8105−1013で規
定する分光反射率を求め、この値を（CIE1976）
Ｌ＊，ａ＊，ｂ＊色空間に変換して定量化した。
また、色調については肉眼観察も行なつた。以上
の結果を一括して表に示した。
[Technical Field of the Invention] The present invention relates to a decorative article having a reddish-purple or copper-colored surface gloss and a smooth surface. [Technical background of the invention and its problems] Conventionally, titanium carbonitride represented by the formula: TiC x N 1-x (in the formula, x represents the mixing rate of carbon atoms),
It is attracting attention because it exhibits a unique reddish-purple color tone around x=0.3. A method is known in which the surface of a base material such as a cemented carbide tool is coated with the titanium carbonitride by chemical vapor deposition (CVD). However, the thin film of titanium carbonitride obtained by the CVD method has a rough and uneven surface, making it unsuitable for use as a decorative item.Moreover, the temperature applied when forming the thin film is as high as approximately 1000°C.
Only substrates that can withstand this temperature can be used, and the substrates that can be treated are limited. [Object of the Invention] The object of the present invention is to provide a decorative article having a reddish-purple or copper color tone and a smooth glossy surface. [Summary of the Invention] The decorative article of the present invention is characterized in that its surface is coated with a titanium carbonitride (TiCN) thin film. In the decorative article of the present invention, the TiCN film covering the surface of the base material has the following properties, where n is the number of carbon atoms in the reaction gas, and n' is the number of nitrogen atoms in the reaction gas.
It is coated with a titanium carbonitride thin film formed by plasma chemical vapor deposition in which n and n' satisfy the relationship of 1%≦n/(n+n')≦12%, and its surface is
Specified in JIS Z 8105-2068 (CIE1976)L
* , a * , b * In the color space, L * , a * , b
* respectively, 60%≦L * ≦100%, 2≦a * ≦
It has a color tone that satisfies the relationship: 15,2≦b * ≦28. At this color tone, the TiCN thin film shines with a reddish-purple or copper-colored luster. Here, if L * is too small, the brightness of the thin film surface will be low and the gloss will be unsatisfactory, and if it is 100%, it will be too sparkly and the hue and saturation of the surface will be perceived as unclear. Therefore, L * is preferably 60% or more and less than 100%, and more preferably 70%≦L * ≦90%. Furthermore, if a * and b * each become too large, the hue of the thin film surface becomes red and yellow, respectively, and conversely, if a * and b * each become too small, the surface tone becomes close to white, It becomes difficult to obtain the desired reddish-purple or copper color. Therefore, for a *, it is preferable that 2≦a * ≦15, and for b * , it is preferable that 2≦b * ≦28. More preferably,
5≦a * ≦12 for a * , 7 for b *
≦b * ≦20. The TiCN thin film according to the present invention can be formed by a plasma chemical vapor deposition method (PCVD method) by using the following processing apparatus illustrated as a schematic diagram. In the figure, 1 is the reaction chamber, and there is a heater power source 2 in the room.
A heater 3 is connected to a heater 3, a negative electrode 5 is connected to a discharge DC power source 4, and a positive electrode 6 is placed opposite the negative electrode 5. The negative electrode 5 also serves as a support for the substrate 7 to be surface treated. The reaction chamber 1 is connected to a supply system (system on the right side in the figure) for reactant gases, which are raw materials, from which each raw material is introduced at a predetermined flow rate. The reaction gas is a mixed gas of four types: hydrogen (H 2 ), titanium tetrachloride (TiCl 4 ), carbon-hydrogen, and nitrogen (N 2 ). In the figure, 8 is an N 2 supply cylinder, and 9 is a hydrocarbon supply cylinder. Hydrocarbons used include methane, ethane, propane, ethylene, acetylene,
Propylene and the like are preferred, and hydrocarbons with a small number of carbon atoms are preferred in terms of handling. 10 is a TiCl 4 bubbler constant temperature bath, and the TiCl 4 stored here is bubbled with H 2 sent from the hydrogen cylinder 11, and the TiCl 4 with a vapor pressure corresponding to the temperature of the constant temperature bath becomes H 2 . Both are introduced into the reaction chamber 1. At this time, the temperature of the tank 10 is determined based on the relationship with the amount of TiCl 4 supplied, but is usually controlled to a certain temperature in the range of 20 to 80°C. Further, the argon cylinder 12 is placed on the surface of the base 7.
This is for an argon (Ar) sputter to clean the substrate surface before forming a TiCN thin film. 13 is a vacuum pump for regulating the inside of the reaction chamber 1 to a predetermined gas pressure; 14 is a trap for preventing oil backflow of the vacuum pump; and a trap for capturing chloride by-produced during TiCN thin film formation; system is configured. Using the apparatus shown in the figure, first, while introducing an appropriate amount of Ar gas from the supply system, the vacuum pump 13 is used to evacuate the reaction chamber 1 to adjust the pressure in the reaction chamber 1 to an Ar atmosphere of about 0.05 Torr, and the surface of the substrate 7 is heated to a current density of about 0.5 Torr. Clean by sprinkling with mA/ cm3 . Thereafter, the reaction gas supply system is switched and the reaction gas is introduced into the reaction chamber 1 while being evacuated, and while the overall pressure of the reaction gas is adjusted to a predetermined value, the substrate 7 is
is heated and a voltage is applied between both electrodes 5 and 6 to open the reaction chamber 1.
Generates a glow discharge inside. If the gas pressure in the room is less than 0.05 Torr, no glow discharge will occur, and if it exceeds 5 Torr, not only will the glow discharge become unstable, but arc discharge will begin to occur. Preferably it is 0.5 to 2 Torr. The heating temperature of the substrate is 100-1000℃, preferably 300℃
~700°C, most preferably 500°C. Furthermore, during discharge, the current density of the current flowing per unit area of the base is 0.01 to 1 mA/cm 2 , preferably 0.05 to 1 mA/cm 2 .
It is 0.5mA/ cm2 . Other parameters necessary for operating the device,
For example, the discharge sustaining voltage, the flow rate of the reaction gas, etc. cannot be uniquely determined because they must be changed in response to changes in the above three conditions when the size of the reaction chamber or the surface area of the substrate changes. An important issue in forming the TiCN thin film according to the present invention is controlling the number of carbon atoms and the number of nitrogen atoms in the above-mentioned reaction gas at a predetermined ratio. That is, when the number of carbon atoms in the reaction gas is n and the number of nitrogen atoms is n', n and n' are 1%≦
The purpose is to control the amount of hydrocarbon and N 2 supplied so that n/n+n'≦12%. If this ratio is too small, the color tone of the thin film surface will tend to be more golden, and if it is too large, the color tone will tend to approach white light, making it difficult to obtain the color tone aimed at by the present invention. Therefore,
n/n+n' is preferably 1% to 12%, more preferably 2 to 6%. Further, in order for this TiCN thin film to have a practical hardness, it is preferable that the film thickness is 0.1 μm or more. The base material to be surface treated may be any material as long as it can withstand the temperature applied during the formation of the thin film described above. For example, there are metals, ceramics (including glass), etc. If the base material is metal, it is conductive and TiCN easily adheres to it, whereas if the base material is ceramic, the base material is hard and therefore indentations may occur. We can provide hard-to-wear ornaments. [Examples of the invention] Examples 1 to 6 Using the apparatus shown in the figure and under the conditions shown.
A TiCN thin film was formed on the Ni-based hard alloy block and the mirror-finished surface of the watch side. The hardness of this thin film was measured using a micro-Witzker's meter, and the film thickness was determined by shadowing the thin film and measuring the step formed at that time using a surface roughness meter. Furthermore,
The color tone of each thin film surface is determined by calculating the spectral reflectance specified by JIS Z 8105-1013 using the standard light C specified by JIS Z 8105-2014, and using this value as (CIE1976).
It was converted into L * , a * , b * color space and quantified.
In addition, the color tone was also observed with the naked eye. The above results are summarized in the table.
【表】【table】
以上の説明で明らかなように、本発明の装飾品
は、その表面色調が独特の赤紫色又は銅色であ
り、しかもその表面はガサツぽくなく平滑な光沢
面である。更には、その製造は、従来のように高
温（約1000℃）ではなく500℃近辺の比較的低温
下で行なうことができるので、基材選択の自由度
を増すことができて有用である。
As is clear from the above description, the surface of the decorative article of the present invention is a unique reddish-purple or copper color, and the surface is smooth and glossy without any roughness. Furthermore, since the production can be carried out at a relatively low temperature of around 500° C., rather than at a high temperature (approximately 1000° C.) as in the conventional method, the degree of freedom in selecting the base material can be increased, which is useful.
図は、本発明の装飾品を製造する際に用いる装
置例の模式図である。
１……反応室、２……ヒータ用電源、３……ヒ
ータ、４……グロー放電用直流電源、５……負電
極兼支持台、６……正電極、７……基材、８……
窒素ガスボンベ、９……炭化水素ガスボンベ、１
０……四塩化チタンバブラー恒温槽、１１……水
素ガスボンベ、１２……アルゴンボンベ、１３…
…真空ポンプ、１４……トラツプ。
The figure is a schematic diagram of an example of an apparatus used in manufacturing the decorative article of the present invention. DESCRIPTION OF SYMBOLS 1... Reaction chamber, 2... Power source for heater, 3... Heater, 4... DC power source for glow discharge, 5... Negative electrode and support stand, 6... Positive electrode, 7... Base material, 8... …
Nitrogen gas cylinder, 9... Hydrocarbon gas cylinder, 1
0...Titanium tetrachloride bubbler constant temperature bath, 11...Hydrogen gas cylinder, 12...Argon cylinder, 13...
...Vacuum pump, 14...Trap.
Claims (1)
応ガス中の窒素の原子数をn′としたとき、ｎ，
n′が１％≦ｎ／（ｎ＋n′）≦12％の関係を満足す
るプラズマ化学蒸着法によつて形成された炭窒化
チタン薄膜で被覆されており、該炭窒化チタンが
JIS Ｚ 8105−2068で規定する（CIE1976）Ｌ
＊，ａ＊，ｂ＊色空間において、Ｌ＊，ａ＊，ｂ
＊はそれぞれ、60％≦Ｌ＊≦100％，２≦ａ＊≦
15，２≦ｂ＊≦28の関係を満足する色調を有して
ることを特徴とする赤紫色又は銅色装飾品。 ２ 該炭窒化チタンの厚みが0.1μm以上である特
許請求の範囲第１項に記載の赤紫色又は銅色装飾
品。[Claims] 1. The surface is n, where n is the number of carbon atoms in the reaction gas and n' is the number of nitrogen atoms in the reaction gas.
It is coated with a titanium carbonitride thin film formed by plasma chemical vapor deposition in which n′ satisfies the relationship of 1%≦n/(n+n′)≦12%, and the titanium carbonitride
Specified in JIS Z 8105-2068 (CIE1976)L
* , a * , b * In the color space, L * , a * , b
* respectively, 60%≦L * ≦100%, 2≦a * ≦
A reddish-purple or copper-colored ornament characterized by having a color tone that satisfies the relationship 15,2≦b * ≦28. 2. The reddish-purple or copper-colored ornament according to claim 1, wherein the titanium carbonitride has a thickness of 0.1 μm or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18039483A JPS6075578A (en) | 1983-09-30 | 1983-09-30 | Red purple or copper-colored ornamental article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18039483A JPS6075578A (en) | 1983-09-30 | 1983-09-30 | Red purple or copper-colored ornamental article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6075578A JPS6075578A (en) | 1985-04-27 |
| JPH0442470B2 true JPH0442470B2 (en) | 1992-07-13 |
Family
ID=16082465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18039483A Granted JPS6075578A (en) | 1983-09-30 | 1983-09-30 | Red purple or copper-colored ornamental article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6075578A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02203728A (en) * | 1989-02-03 | 1990-08-13 | Yoshikazu Furuta | Fishing hook and its production |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT350285B (en) * | 1974-08-07 | 1979-05-25 | Plansee Metallwerk | COVERED, METAL USE ITEMS |
-
1983
- 1983-09-30 JP JP18039483A patent/JPS6075578A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6075578A (en) | 1985-04-27 |
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