JPH06160914A - Display material and its production - Google Patents
Display material and its productionInfo
- Publication number
- JPH06160914A JPH06160914A JP4315195A JP31519592A JPH06160914A JP H06160914 A JPH06160914 A JP H06160914A JP 4315195 A JP4315195 A JP 4315195A JP 31519592 A JP31519592 A JP 31519592A JP H06160914 A JPH06160914 A JP H06160914A
- Authority
- JP
- Japan
- Prior art keywords
- tin film
- polarization
- color
- tin
- ion plating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、ＴｉＮセラミック被
膜の電解着色（エレクトロクロシズム）現象を活用した
表示材料及びその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a display material utilizing the electrolytic coloring phenomenon of a TiN ceramic coating and a method for producing the same.
【０００２】[0002]
【従来の技術】従来、金属製品の商品価値を高めるため
に、湿式めっきや塗装などの手段によって、その表面に
着色を施すことが行われ、さらに近年に至っては、金属
材料自体を発色させて、その外観のより一層の美麗化が
試行されている。特に最近では、大表面積を有する冷延
鋼板やステンレス鋼板等の商品価値を高めるため、蒸
着、スパッタリング及びイオンプレーティング等の乾式
めっき法を利用して鋼板表面に着色被膜を被成する試み
がなされている。例えば、表面上にＴｉＮ，Ｚｒ，Ｔａ
及びＮｂ等を被覆した鋼板に、陽極酸化処理を施して表
面に薄い酸化被膜を形成し、光の干渉作用によって発色
させるいわゆる発色処理を施すことによって、表面外観
のより一層の美麗化が図られている（例えば特開昭53−
119734号公報，特開昭56−153318号公報及び特公昭55-1
9319号公報等）。上記のように、鋼板自身（主としてス
テンレス鋼板が主に使用されている）又はＴｉＮ，Ｚ
ｒ，Ｔａ及びＮｂ等を被覆した鋼板を良好に発色させる
ためには、緻密で均一な酸化被膜を形成する必要がある
のは言うまでもなく、酸化被膜と鋼板との密着性が良好
で、耐食性にも優れていること、さらに均一な膜質の金
属被膜を被成することが重要であるとされている。2. Description of the Related Art Conventionally, in order to increase the commercial value of a metal product, its surface is colored by means such as wet plating or painting. In recent years, the metal material itself has been colored. , Further refinement of its appearance is being tried. In particular, in recent years, in order to enhance the commercial value of cold-rolled steel sheets and stainless steel sheets having a large surface area, attempts have been made to form a colored coating on the surface of the steel sheet using a dry plating method such as vapor deposition, sputtering and ion plating. ing. For example, TiN, Zr, Ta on the surface
A steel sheet coated with Nb, Nb, etc. is subjected to anodizing treatment to form a thin oxide film on the surface, and a so-called color development treatment that causes color development by the interference of light is performed to further improve the surface appearance. (For example, JP-A-53-
119734, JP 56-153318, and JP 55-1.
No. 9319). As mentioned above, the steel plate itself (mainly stainless steel plate is mainly used) or TiN, Z
Needless to say, it is necessary to form a dense and uniform oxide film in order to satisfactorily develop the color of the steel plate coated with r, Ta, Nb, etc., and the adhesion between the oxide film and the steel plate is good, and the corrosion resistance is high. It is said that it is important to be excellent and to form a metal film having a uniform film quality.
【０００３】これとは別に、発明者らは先に、特開平２
−118062号公報において、ＨＣＤ法を用いたイオンプレ
ーティング処理によって、低炭素鋼板又はステンレス鋼
板の表面にＴｉＮからなるセラミック被膜を被成したの
ち、該セラミック被膜の一部又は全面を陽極酸化処理に
より発色させることからなる発色セラミック被膜鋼板の
製造方法を開示した。Separately from this, the inventors have previously described in Japanese Patent Laid-Open No.
-118062, a ceramic coating made of TiN is formed on the surface of a low carbon steel sheet or a stainless steel sheet by ion plating treatment using HCD method, and then a part or the whole surface of the ceramic coating is anodized. Disclosed is a method for producing a color-developed ceramic-coated steel sheet comprising coloring.
【０００４】しかしながら上述した技術はいずれも、一
度発色処理を施した後は、色が変色したり、消えたりし
ないようにすることを重要視していたため、その用途に
は自ずから限界があった。この点、色調の変更が可能な
材料としては、従来わずかに、ＷＯ3 薄膜（透明）が知
られていて、水溶液中でカソード分極すると青色に変色
し、さらにアノード分極すると再び透明に戻る電解着色
（エレクトロクロミズム）現象が知られていた。しかし
ながら、このＷＯ3 薄膜は製造コストが高価につくだけ
でなく、工業的に安定して作成するにはまだ改良すべき
多くの問題が残されており、現在までのところ商品化さ
れるまでには至っていない。However, in all of the above-mentioned techniques, since it is important to prevent the color from discoloring or disappearing after the color-developing process is once performed, its use is naturally limited. In this respect, as a material whose color tone can be changed, a WO 3 thin film (transparent) has been known so far, and it undergoes cathodic polarization in an aqueous solution to change its color to blue. The phenomenon of (electrochromism) was known. However, this WO 3 thin film is not only expensive to manufacture, but also has many problems to be improved in order to produce it industrially stably. Until now, it has been commercialized. Has not arrived.
【０００５】[0005]
【発明が解決しようとする課題】この発明は、プラズマ
を利用したイオンプレーティング法を用いて基板表面上
に被覆したＴｉＮ膜を、中性水溶液中でアノード分極し
た後、引き続きカソード分極すると、ＴｉＮ被膜が黄金
色から黒色へと変化し、再びアノード分極すると極めて
安定して黄金色に変化するという、新たに見出された電
解着色現象に基づいて完成されたものである。SUMMARY OF THE INVENTION According to the present invention, a TiN film coated on the surface of a substrate by using an ion plating method utilizing plasma is anodically polarized in a neutral aqueous solution and then cathodically polarized. It was completed based on the newly discovered electrolytic coloring phenomenon that the coating changes from golden color to black and changes extremely stably to golden color when anodic polarization is performed again.
【０００６】[0006]
【課題を解決するための手段】すなわちこの発明は、金
属基板の表面に、電位変化に応じて色調が可逆的に変化
するＴｉＮ被膜をそなえることを特徴とする表示材料で
ある。またこの発明は、金属基板表面上に、イオンプレ
ーティング法によってＴｉＮ被膜を被成したのち、中性
溶液中にてアノード分極及びカソード分極を交互に繰返
し行うことを特徴とする表示材料の製造方法である。That is, the present invention is a display material characterized in that a surface of a metal substrate is provided with a TiN film whose color tone reversibly changes in response to a change in potential. Further, the present invention is a method for producing a display material, characterized in that a TiN film is formed on the surface of a metal substrate by an ion plating method, and then anodic polarization and cathodic polarization are alternately repeated in a neutral solution. Is.
【０００７】この発明に従い得られたＴｉＮ膜は、アノ
ード分極とカソード分極を繰り返すことにより、黄金色
と黒色との変色が可逆的に生じ、しかもこの変色過程は
ＴｉＮ膜の電位変化に迅速に応答することから、表示材
料として極めて有用なものと言える。The TiN film obtained according to the present invention reversibly undergoes discoloration of golden color and black color by repeating anodic polarization and cathodic polarization, and this discoloration process responds rapidly to the potential change of the TiN film. Therefore, it can be said that it is extremely useful as a display material.
【０００８】以下、この発明を由来するに至った実験結
果について説明する。さて発明者らは、ＨＣＤ法による
イオンプレーティングを用いてステンレス鋼板（0.7 mm
×350 mm×350 mm）の表面に、約２μｍ厚のＴｉＮ被膜
を被成した。この時のイオンプレーティング条件は、Ｈ
ＣＤ電流：500 Ａ，ＨＣＤ電圧：40Ｖ，基板温度：250
℃、バイアス電圧：50Ｖである。ついでＴｉＮ被膜試料
を15mm×30mmの寸法に切断し、この試料をアセトンで超
音波洗浄し、シリコンシーランドで被覆したのち、中性
水溶液（pH 8.4のほう酸塩水溶液、液温：25℃, 窯で12
時間以上脱気）中でポテンシオシタットを用いて5.2 Ｖ
（ＳＨＥ）で２時間以上分極を続けた。その後、さらに
5.2Ｖ（ＳＨＥ）と−4.8 Ｖ（ＳＨＥ）の分極電位でア
ノード分極とカソード分極とを１秒間隔で繰り返したと
ころ、次第に、カソード分極の際には試料表面が黒色と
なり、一方アノード分極の際には元の黄金色に戻るよう
になった。引き続きこの操作を20回以上繰り返したとこ
ろ、黄金色と黒色との間の色調変化は、時定数１秒間以
内で迅速かつ可逆的に進行するようになった。The experimental results that led to the present invention will be described below. Now, the inventors of the present invention have used stainless steel plates (0.7 mm
The surface of (× 350 mm × 350 mm) was coated with a TiN film having a thickness of about 2 μm. The ion plating condition at this time is H
CD current: 500 A, HCD voltage: 40 V, substrate temperature: 250
C, bias voltage: 50V. Then, the TiN coated sample was cut into a size of 15 mm × 30 mm, ultrasonically washed with acetone and coated with silicon sea land, and then neutral aqueous solution (borate aqueous solution of pH 8.4, liquid temperature: 25 ° C., kiln). At 12
5.2 V with potentiostat in degassing for more than an hour
Polarization was continued for 2 hours or more by (SHE). Then further
When anodic polarization and cathodic polarization were repeated at an interval of 1 second with polarization potentials of 5.2 V (SHE) and -4.8 V (SHE), the sample surface gradually became black during cathodic polarization, while on the other hand during anodic polarization. Came back to the original golden color. When this operation was repeated 20 times or more, the color change between the golden color and the black color proceeded rapidly and reversibly within a time constant of 1 second.
【０００９】[0009]
【作用】このような電解着色法によるＴｉＮ被膜の黄金
色と黒色との可逆的色調変化は、この発明で初めて解明
されたものであるが、その色調変化のメカニズムは次の
とおりと考えられる。ＴｉＮ薄膜をアノード分極する
と、まず薄膜の表面層が次式(1) の反応によりＴｉＯ2
に変質する。The reversible color tone change between the golden color and the black color of the TiN film by the electrolytic coloring method was first clarified by the present invention, and the mechanism of the color tone change is considered as follows. When the TiN thin film is subjected to anodic polarization, first, the surface layer of the thin film reacts with TiO 2 by the reaction of the following equation (1).
Change to.
【数１】 ＴｉＮ＋２Ｈ2 Ｏ→ＴｉＯ2 ＋１／２Ｎ2 ＋４Ｈ+ ＋４ｅ ---(1) このＴｉＯ2 は透明であるため、下地ＴｉＮの黄金色は
アノード分極しても変化せず、従って被膜全体としては
黄金色を呈する。このようなアノード分極後、カソード
分極すると、溶液からＨ+ イオンが侵入し、ＴｉＯ2 を
ＴｉＯＯＨまで還元する。このＴｉＯＯＨは黒色を呈す
るので、被膜全体としては黒色となる。次にＴｉＮの表
面層に存在するＴｉＯＯＨを再びアノード分極すると、
ＴｉＯ2に戻り透明となるため、再びＴｉＮの黄金色が
鮮明に表れるようになる。[Formula 1] TiN + 2H 2 O → TiO 2 + 1 / 2N 2 + 4H + + 4e --- (1) Since this TiO 2 is transparent, the golden color of the underlying TiN does not change even if it is anode-polarized. Exhibits a golden color. When cathode polarization is performed after such anodic polarization, H + ions penetrate from the solution to reduce TiO 2 to TiOOH. Since this TiOOH exhibits a black color, the entire coating becomes a black color. Next, when TiOOH existing on the surface layer of TiN is anodic polarized again,
Since it returns to TiO 2 and becomes transparent, the golden color of TiN becomes visible again.
【００１０】次に、この発明の製造工程について述べ
る。金属基板としては、従来公知の金属板いずれもが適
合するが、とくに鋼帯、低炭素冷延鋼板及びステンレス
鋼板などはとりわけ有効である。次に、これらの金属基
板上に、必要に応じて洗浄した後、イオンプレーティン
グ法によってＴｉＮ被膜を被成する。このイオンプレー
ティング法によるＴｉＮ被膜の被成に際しては、従来公
知のＨＣＤ、アーク放電、マルティ・アーク及びＥＢ＋
ＲＦ法等いずれの方法を用いても良いが、イオン化率の
高く、平滑性、均一性及び密着性に優れたＴｉＮ被膜が
得易い方式を用いる方がより好ましい。Next, the manufacturing process of the present invention will be described. As the metal substrate, any conventionally known metal plate is suitable, but a steel strip, a low carbon cold-rolled steel plate, a stainless steel plate and the like are particularly effective. Next, a TiN coating film is formed on these metal substrates by an ion plating method after cleaning if necessary. When depositing a TiN film by this ion plating method, conventionally known HCD, arc discharge, multi arc and EB +
Although any method such as the RF method may be used, it is more preferable to use a method in which a TiN coating film having a high ionization rate and excellent smoothness, uniformity, and adhesion can be easily obtained.
【００１１】ついでＴｉＮ被膜表面を洗浄後、中性水溶
液中で、アノード分極とカソード分極とを交互に行う。
この中性水溶液としては、例えば、ほう酸水溶液など従
来公知のどのようなものを用いても良い。またこのとき
の分極電位は、アノード分極の場合は＋0.5 〜＋20Ｖ，
カソード分極の場合は−1.5 〜−10Ｖ程度とするのが好
ましい。さらにアノード分極とカソード分極との繰り返
し処理回数は、20回程度が好ましい。かくして得られた
ＴｉＮ被膜は、アノード分極とカソード分極の切り換え
により、0.01〜10秒間程度の短時間で迅速かつ可逆的に
変色するようになる。After cleaning the surface of the TiN film, anodic polarization and cathodic polarization are alternately performed in a neutral aqueous solution.
As the neutral aqueous solution, any conventionally known aqueous solution such as boric acid aqueous solution may be used. The polarization potential at this time is +0.5 to +20 V in the case of anodic polarization,
In the case of cathodic polarization, it is preferably about -1.5 to -10V. Further, the number of times of repeating the anode polarization and the cathode polarization is preferably about 20 times. The TiN coating film thus obtained becomes rapidly and reversibly discolored in a short time of about 0.01 to 10 seconds by switching between anodic polarization and cathodic polarization.
【００１２】[0012]
【実施例】Ｃ：0.01wt％（以下単に％で示す）, Ｓｉ：
0.21％，Ｍｎ：0.6 ％，Ｐ：0.02％及びＣｒ：12.8％を
含有するステンレス鋼板（0.7 mm×350 mm×350 mm）
を、脱脂したのち、ＨＣＤ方式のイオンプレーティング
（加速電圧：40Ｖ，加速電流：500 ＶＡ, バイアス電
圧：50Ｖ，真空度：７×10-4Torr) により、厚み：1.5
μm のＴｉＮ被膜を被成した。 ついで、鋼板を15mm×
30mmの寸法に切断し、超音波洗浄を施した後、中性水溶
液中にて分極電位：5.0 Ｖ，−4.5 Ｖでアノード分極と
カソード分極を交互に施した。この時、カソード分極で
は表面が黒色となり、一方アノード分極では表面が黄金
色となった、この操作を20回以上繰り返したところ、色
調が迅速に変化するようになり、その後はアノード分極
電位を１Ｖまで下げ、カソード分極電位を−1.5 Ｖまで
上げても、変色は迅速かつ安定して進行するようになっ
た。[Example] C: 0.01 wt% (hereinafter, simply expressed as%), Si:
Stainless steel plate (0.7 mm × 350 mm × 350 mm) containing 0.21%, Mn: 0.6%, P: 0.02% and Cr: 12.8%
After degreasing, the thickness: 1.5 by HCD type ion plating (accelerating voltage: 40 V, accelerating current: 500 VA, bias voltage: 50 V, vacuum degree: 7 × 10 −4 Torr).
A μm TiN coating was applied. Then, the steel plate is 15 mm ×
After cutting to a size of 30 mm and ultrasonic cleaning, anodic polarization and cathodic polarization were alternately applied in a neutral aqueous solution at a polarization potential of 5.0 V and -4.5 V. At this time, the surface became black in cathodic polarization, while the surface became golden in anodic polarization. When this operation was repeated 20 times or more, the color tone changed rapidly, and then the anodic polarization potential was changed to 1 V. And the cathodic polarization potential was increased to -1.5 V, the discoloration proceeded rapidly and stably.
【００１３】[0013]
【発明の効果】かくしてこの発明によれば、分極電位の
切り換えによって、ＴｉＮ被膜の色調を迅速かつ安定し
て変化させることができ、特に表示材料としての用途に
おいて偉効を奏する。As described above, according to the present invention, the color tone of the TiN film can be changed quickly and stably by switching the polarization potential, which is particularly effective for use as a display material.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 渡辺 重世 北海道札幌市東区11条東１丁目９−30 コ ーポ真鍋308号 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shigeyo Watanabe 1-9-30, Article 11 East, Higashi-ku, Sapporo-shi, Hokkaido Copo Manabe 308
Claims (2)
調が可逆的に変化するＴｉＮ被膜をそなえることを特徴
とする表示材料。1. A display material comprising a surface of a metal substrate provided with a TiN coating film whose color tone reversibly changes in response to a change in potential.
グ法によってＴｉＮ被膜を被成したのち、中性溶液中に
てアノード分極及びカソード分極を交互に繰返し行うこ
とを特徴とする表示材料の製造方法。2. A method for producing a display material, comprising depositing a TiN film on the surface of a metal substrate by an ion plating method, and then alternately repeating anodic polarization and cathodic polarization in a neutral solution. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4315195A JP2995125B2 (en) | 1992-11-25 | 1992-11-25 | Display material and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4315195A JP2995125B2 (en) | 1992-11-25 | 1992-11-25 | Display material and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06160914A true JPH06160914A (en) | 1994-06-07 |
| JP2995125B2 JP2995125B2 (en) | 1999-12-27 |
Family
ID=18062560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4315195A Expired - Fee Related JP2995125B2 (en) | 1992-11-25 | 1992-11-25 | Display material and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2995125B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008203740A (en) * | 2007-02-22 | 2008-09-04 | Nissan Motor Co Ltd | Dimming element and dimming device |
-
1992
- 1992-11-25 JP JP4315195A patent/JP2995125B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008203740A (en) * | 2007-02-22 | 2008-09-04 | Nissan Motor Co Ltd | Dimming element and dimming device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2995125B2 (en) | 1999-12-27 |
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