JPS6079608A - Transparent thin film with protecting film - Google Patents
Transparent thin film with protecting filmInfo
- Publication number
- JPS6079608A JPS6079608A JP18892683A JP18892683A JPS6079608A JP S6079608 A JPS6079608 A JP S6079608A JP 18892683 A JP18892683 A JP 18892683A JP 18892683 A JP18892683 A JP 18892683A JP S6079608 A JPS6079608 A JP S6079608A
- Authority
- JP
- Japan
- Prior art keywords
- film
- transparent conductive
- conductive thin
- thin film
- protective film
- 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.)
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Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】 〔技術分野〕 本発明は保護膜付き透明導電性薄ｌｌ臭に関する。[Detailed description of the invention] 〔Technical field〕 The present invention relates to a transparent conductive thin film with a protective film.
本発明の保護膜付き透明導電性薄膜は、液晶表示用の透
明電極、防曇ガラスの発熱体、赤外線を遮断する選択透
過膜等に好適である。The transparent conductive thin film with a protective film of the present invention is suitable for transparent electrodes for liquid crystal displays, heating elements for antifogging glass, selective transmission films that block infrared rays, and the like.
ｔ’ｒｏ膜〔インジウムオキサイド（Ｉｎ２０゜）と二
酸化錫（Ｓ ｎ、ｏ ２ ）の固溶体〕等からなる透明
導電性Ｍ賎は、例えば、真空蒸着法、スパッタリング、
イオンブレーティング等の真空成膜法あるいはスプレー
法等により、ガラス等の基板上に形成され、種々の用途
に供されている。The transparent conductive M film made of t'ro film [solid solution of indium oxide (In20°) and tin dioxide (S n, o 2 )] etc. can be produced by, for example, vacuum evaporation, sputtering,
It is formed on a substrate such as glass by a vacuum film forming method such as ion blasting or a spray method, and is used for various purposes.
ところで、従来は、この透明導電性薄膜は主にディスプ
レイ関係、光学系など比較的静的な環境下で用いられる
ことが多く、それゆえ透明導電性薄膜の耐久性が要求さ
れることは少ながった。しかるに、近年では、透明導電
性薄等の優れた特性に注目され、車両、航空機、建築等
において動的な用い方をされはじめ、物理的、化学的に
胞しい環境下に晒されるようになった。このため、透明
導電性薄膜の耐久性を上げる必要が生じ、種々の保護方
法が講じちれている。By the way, in the past, transparent conductive thin films were often used in relatively static environments, such as in displays and optical systems, and therefore durability of transparent conductive thin films was rarely required. It was. However, in recent years, they have attracted attention for their excellent properties such as transparent conductive thin films, and they have begun to be used dynamically in vehicles, aircraft, architecture, etc., and are exposed to physically and chemically harsh environments. Ta. For this reason, it has become necessary to increase the durability of transparent conductive thin films, and various protection methods have been taken.
かかる透明導電性薄膜の保護方法として、従来は、第１
図に示す如く、合わせガラス１内に透明導電性薄膜２を
ポリビニルブチラール中間膜３と共に挟持したり、第２
図に示す如く、プラスチックカバー４で覆ったり、また
第３図に示す如く、アクリルやウレタン等の樹脂５をコ
ーティングしたり、あるいは二酸化珪素（Ｓｉｎ、）を
蒸着すル等の方法が採られている。Conventionally, as a method for protecting such a transparent conductive thin film, the first
As shown in the figure, a transparent conductive thin film 2 is sandwiched within a laminated glass 1 together with a polyvinyl butyral interlayer film 3, and a second
As shown in the figure, methods such as covering with a plastic cover 4, coating with a resin 5 such as acrylic or urethane, or vapor depositing silicon dioxide (Sin) as shown in Figure 3 are adopted. There is.
しかしながら、上記合わせガラス内に透明導電性薄股を
形成したものは、熱効率等の性能上問題があり、またプ
ラスチックカバーを被せたものは、見栄えが良くなく意
匠性に問題がある。この点、透明導電性薄膜上に直接保
護膜を形成したものが望ましい。しかしながら、従来の
如く、透明導電性薄膜に樹脂や二酸化珪素を被覆したも
のは、耐摩耗性、耐擦過性、密着性が十分でばないとい
う問題があった。However, the laminated glass in which transparent conductive thin strips are formed has performance problems such as thermal efficiency, and the glass covered with a plastic cover does not look good and has problems in terms of design. In this respect, it is desirable to form a protective film directly on the transparent conductive thin film. However, conventional transparent conductive thin films coated with resin or silicon dioxide have the problem of insufficient abrasion resistance, scratch resistance, and adhesion.
このため、透明導電性薄膜との密着性が高く、かつ強固
な保護膜が要望されている。Therefore, there is a demand for a strong protective film that has high adhesion to the transparent conductive thin film.
本発明は、上記従来技術の問題を解決するためになされ
たもので、厳しい環境下での使用に十分耐えうる、耐久
性に優れた保護膜付き透明導電性薄膜を提供することを
目的とする。The present invention has been made in order to solve the above-mentioned problems of the prior art, and aims to provide a highly durable transparent conductive thin film with a protective film that can withstand use under harsh environments. .
〔発明の構成〕
かかる目的は、本発明によれば、透明導電性薄膜の表面
に、酸化ジルコニウム（ＺｒＯ□）、酸化アルミニウム
（Ａ６＋Ｏ＋）のうぢ、いずれか一方からなる保護膜を
形成したごとを特徴とする保護膜（；Ｊき透明導電性薄
膜によって達成される。[Structure of the Invention] According to the present invention, this object is achieved by forming a protective film made of either zirconium oxide (ZrO□) or aluminum oxide (A6+O+) on the surface of a transparent conductive thin film. This is achieved by a transparent conductive thin film with a protective film (;J).
酸化ジルコニウムおよび酸化アルミニウムは、透明導電
性薄膜としてのビｒｏ股との密着性がよく、かつ酸化ジ
ルコニウム、酸化アルミニウム自体が耐摩耗性、耐擦過
性に優れているため、本考案の保護膜付き透明導電性薄
膜の面ｊ天性が向」二する。Zirconium oxide and aluminum oxide have good adhesion to the biro crotch as a transparent conductive thin film, and zirconium oxide and aluminum oxide themselves have excellent wear resistance and scratch resistance, so the protective film of the present invention can be used. The nature of the surface of the transparent conductive thin film is favorable.
以上より、本発明の保護膜付き透明導電性薄膜は、以下
の効果を奏する。As described above, the transparent conductive thin film with a protective film of the present invention has the following effects.
（イ）透明導電性薄膜の耐久性が大幅に向上する。(a) The durability of the transparent conductive thin film is greatly improved.
従って、厳しい環境下での使用も可能となり、適用範囲
が大幅に拡大する。Therefore, it can be used in harsh environments, and the range of application is greatly expanded.
（ロ）真空成膜法により、透明導電性薄膜と同様に保護
膜の成形が可能なため、作業性が良い。(b) The vacuum film forming method allows the formation of a protective film in the same way as a transparent conductive thin film, so workability is good.
次に、本発明の詳細な説明する。 Next, the present invention will be explained in detail.
（第１実施例）
本考案の保護膜イ１き透明導電性薄膜の耐摩耗性試験を
、従来のものと比較のうえ行った。(First Example) The abrasion resistance test of the transparent conductive thin film having the protective film No. 1 of the present invention was conducted in comparison with that of the conventional one.
−辺１００龍、厚さ５龍で中心に直径６Ｉ１ｍの孔のあ
いたガラスを、トリクレンと純水で十分に洗浄した後、
乾燥し、透明導電性薄膜としてのＩＴＯと各種保護映利
料をスパフタリングして、Ａ、Ｂ、Ｃ，Ｄの４種の試験
片を作製した。この４種の試験片のうち、ＡとＢは従来
例を示し、ＣとＤは本発明の例を示す。かかる４種の試
験片の構成は次の通りである。-After thoroughly cleaning a glass with a hole of 6I1m in diameter and a side of 100mm and a thickness of 5mm in the center with Triclean and pure water,
After drying, ITO as a transparent conductive thin film and various protective materials were sputtered to prepare four types of test pieces A, B, C, and D. Among these four types of test pieces, A and B show the conventional example, and C and D show the example of the present invention. The configurations of these four types of test pieces are as follows.
Ａ試験片：１ＴＯ（６０（１０人）十
三酸化珪素（３０００人）
Ｂ試験片：ＩＴＯ（６０００人）＋
弗化マグネシウム（３０００人）
Ｃ試験片：１ＴＯ（６０００人）＋
酸化ジルコニウム（３０００人）
Ｄ試験片：１ＴＯ（６０００人）＋
酸化アルミニウム（３０００人）
この４種の試験片をテーバ型摩耗試験機にかけてくもり
度（ヘーズ値）を調べた。ここで、テーバ型摩耗試験機
は、研＠わ）入りゴムホイールを試料面で回転し、摩耗
さ・Ｕることにより、試験後の試料の重量減少あるいは
くもり度を調べる機械である。試験は、摩耗ホイール（
Ｃ３−１０Ｆ）を用い・荷重５００ｇで１ｏ００１ｉａ
１転さ−Ｕ、くもり度の増加をヘーズメータによりＪ、
す定した。A test piece: 1TO (60 (10 people)) trisilicon oxide (3000 people) B test piece: ITO (6000 people) + magnesium fluoride (3000 people) C test piece: 1TO (6000 people) + zirconium oxide (3000 people) Test piece D: 1TO (6000 people) + Aluminum oxide (3000 people) These four types of test pieces were run on a Taber type abrasion tester to check the degree of haze (haze value).Here, the Taber type abrasion tester was This is a machine that examines the weight loss or degree of cloudiness of a sample after testing by rotating a rubber wheel with a grinding wheel on the surface of the sample and causing wear and tear. The test was carried out on worn wheels (
C3-10F) using 1o001ia with a load of 500g
1 - U, the increase in cloudiness is measured by a haze meter,
It has been decided.
この結果、従来例を示すＡ試験片と１３試験片は、それ
ぞれ保護膜である二酸化珪素と弗化マグネシウムが完全
に剥離したのに対し、本考案の例を示ずＣ試験片とＤ試
験片には、剥離は全く見られず、ヘーズ値ばそれぞれ０
．８％、１．１％であった。このヘーズ値は、自動車用
安全ガラスのＪＩＳ規格で決められている２、０％以内
という条件を十分満足するものである。因に、ガラス自
体のヘーズ値は０．８％であり、本発明の保護膜イ１き
透明導電性薄膜は、ガラスなみの耐摩耗性をイｊするこ
とが確かめられた。As a result, the protective films of silicon dioxide and magnesium fluoride were completely peeled off in Test Pieces A and Test Piece 13, which are conventional examples, whereas Test Pieces C and D, which do not show examples of the present invention, were completely peeled off. No peeling was observed at all, and the haze value was 0.
．． They were 8% and 1.1%. This haze value fully satisfies the condition of being within 2.0% as determined by the JIS standard for automobile safety glass. Incidentally, the haze value of the glass itself is 0.8%, and it was confirmed that the transparent conductive thin film with the protective film of the present invention has wear resistance equivalent to that of glass.
（第２実施例）
本発明の保護膜付き透明導電性薄膜の耐薬品性と耐熱、
耐水性を調べた。(Second Example) Chemical resistance and heat resistance of the transparent conductive thin film with a protective film of the present invention,
We investigated water resistance.
一辺５０鰭、厚さ５１ＩＮのガラスに、第１実施例と同
様にして、Ｅ試験片とＦ試験片を作製した。An E test piece and an F test piece were prepared on glass having 50 fins on each side and a thickness of 51 IN in the same manner as in the first example.
ここで、Ｅ試験片はＣ試験片と、またＦ試験片ばＤ試験
片と実質的に同じである。この両試験片を複数作製し、
以下の試験を行った。Here, the E test piece is substantially the same as the C test piece, and the F test piece and the D test piece. A plurality of these test pieces were prepared,
The following tests were conducted.
（ａ）０．ＩＮのＮ ａ ＯＨ溶液に、室温で２４０時
間浸漬した。この結果、ＩＴＯ膜のみの場合は、約１０
時間後に白濁を生じたが、本発明のＥ試験片とＦ試験片
の場合は、なんら変化が認められなかった。(a) 0. It was immersed in a NaOH solution of IN for 240 hours at room temperature. As a result, in the case of only ITO film, approximately 10
Although clouding occurred after a period of time, no change was observed in the case of the E test piece and F test piece of the present invention.
（ｂ）２８％のアンモニアン容ン夜に、室温で２４０時
冊浸漬した。この結果、ＩＴＯ膜のみの場合は、約１５
時間後に白濁を生じたが、本発明のＥ試験片とＦ試験片
の場合は、なんら変化が認められなかった。(b) Soaked in 28% ammonia overnight at room temperature for 240 hours. As a result, in the case of only ITO film, approximately 15
Although clouding occurred after a period of time, no change was observed in the case of the E test piece and F test piece of the present invention.
（Ｃ）沸騰水中に２時間浸漬した。この結果、ＩＴＯ膜
のみの場合は変色を生じたが、本発明のＥ試験片とＦ試
験片の場合は、なんら変化が認められなかった。(C) Immersed in boiling water for 2 hours. As a result, discoloration occurred in the case of only the ITO film, but no change was observed in the case of the E test piece and F test piece of the present invention.
以上より、本発明の保護膜付き透明導電性薄膜は、耐薬
品性および耐熱、耐水性に優れていることが荀［１忍さ
れた。From the above, it was confirmed that the transparent conductive thin film with a protective film of the present invention has excellent chemical resistance, heat resistance, and water resistance.
（第３実施例）
第４Ｍに示す保護膜イ」き透明導電性）°・Ｖ膜を作製
した。第４図は本発明の第３実施例に係る保護膜イζＪ
き透明導電性薄膜の概要を示ず概略構成図である。(Third Example) A transparent conductive (transparent conductive) V film with a protective film shown in No. 4M was prepared. FIG. 4 shows a protective film ζJ according to a third embodiment of the present invention.
FIG. 2 is a schematic configuration diagram without showing the outline of a transparent conductive thin film.
一辺５０龍、厚さ５關の透明ガラスｌに、スパッタリン
グにより、１１゛０膜２を約１０ （１００人形成した
。このときのシート抵抗ば；３．８Ω／口であった。次
いで、保護膜として酸化ジルコニウムＩＷ６を、スパッ
クリングにより５０００人の股Ｆ’−に形成した。更に
、この酸化ジルコニウムｌ１％ ６の上に、スパッタリ
ングにより反射防止脈とし゛Ｃ二酸化珪素膜７を約９０
０人形成した。この二酸化珪素膜７の膜厚ｄは、反射さ
せたくない可視光線の中心波長を５２０鰭と設定し、ｎ
ｄ−λ／４に、ｎ＝１．４５（二酸化珪素の屈折率）、
λ−５２０鰭を代入してめた。Approximately 10 (100 people) formed an 11゛0 film 2 by sputtering on a transparent glass plate with a side of 50 mm and a thickness of 5 mm.The sheet resistance at this time was 3.8 Ω/hole. A film of zirconium oxide IW6 was formed on the crotch F'- of 5,000 people by spackling.Furthermore, on this zirconium oxide l1%6, a film of about 90% of silicon dioxide 7 was deposited as an antireflection layer by sputtering.
0 people formed. The film thickness d of this silicon dioxide film 7 is determined by setting the center wavelength of visible light that is not desired to be reflected as 520 fins, and n
d-λ/4, n=1.45 (refractive index of silicon dioxide),
I substituted the λ-520 fin.
この結果得られた保護膜付きふ明導電性薄膜は、二酸化
珪素膜を設りない場合には、可視光線の反射率がガラス
の反射も含め一ζ２５％であったのに対し、１５％に低
減した。The resulting transparent conductive thin film with a protective film had a reflectance of visible light of 15%, which was 25% including the reflection of glass, when no silicon dioxide film was provided. Reduced.
また、第１実施例と同様に、テーバ型摩耗試験機にかけ
たところ、ガラスと同程度の傷付きしか受けず、くもり
度を示ずヘーズ値の増加は僅かに１．５％であった。Further, when it was subjected to a Taber type abrasion tester in the same way as in the first example, it was only scratched to the same extent as glass, showed no cloudiness, and the haze value increased by only 1.5%.
このように、ｌ ′ｒＯ膜と二酸化珪素膜の間に酸化ジ
ルコニウム股を介在さ・Ｕることにより、各層の密着強
度が増し、耐久性の向上が図れるとともに、反射防止機
能をも持たせることができた。In this way, by interposing the zirconium oxide layer between the l'rO film and the silicon dioxide film, the adhesion strength of each layer is increased, durability is improved, and it also has an anti-reflection function. was completed.
以上、本発明の特定の実施例について説明したが、本発
明は、この実施例に限定されるものではなく、特許請求
の範囲に記載の範囲内で種々の実Ｊｌｌ！ｉ態様が包含
されるものである。Although a specific embodiment of the present invention has been described above, the present invention is not limited to this embodiment, and can be applied to various embodiments within the scope of the claims. i aspect is included.
第１図〜第３図は、従来の透明導電性薄膜の保護方法を
示す機略構成図、
第４図は本発明の第３実施例に係る保護膜イ」き透明導
電性薄膜の概要を示す概略構成図である。
１−−−−ガラス
２−−−− Ｉ Ｔ Ｏ股（透明導電性薄膜）３−−−
−ポリビニルブチラール中間膜４−−−−−プラスチソ
クカハー
５−−−−４削脂（ウレタン等）
６−−−−−酸化ジルコニウム股（保護膜）７−、−−
二酸化珪素膜
出Ｊｆ（人 トヨタ自動車株入会社
第２図
第４図Figures 1 to 3 are schematic diagrams showing a conventional method for protecting a transparent conductive thin film, and Figure 4 shows an outline of a transparent conductive thin film with a protective film according to a third embodiment of the present invention. FIG. 1---Glass 2---ITO crotch (transparent conductive thin film) 3---
-Polyvinyl butyral interlayer film 4---Plastic coating 5---4 Grease removal (urethane, etc.) 6---Zirconium oxide crotch (protective film) 7-, ---
Silicon dioxide film Jf (person) Joined Toyota Motor Corporation Fig. 2 Fig. 4
Claims (1)
ｒＯ２）、酸化アルミニウム（Ａ ｌｔ ｒ Ｏｌ）の
うち、いずれか一方からなる保護膜を形成したことを特
徴とする保護膜付き透明導電性薄膜。(1) Zirconium oxide (Z
1. A transparent conductive thin film with a protective film, characterized in that a protective film made of either one of aluminum oxide (AltrOl) and aluminum oxide (AltrOl) is formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18892683A JPS6079608A (en) | 1983-10-07 | 1983-10-07 | Transparent thin film with protecting film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18892683A JPS6079608A (en) | 1983-10-07 | 1983-10-07 | Transparent thin film with protecting film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6079608A true JPS6079608A (en) | 1985-05-07 |
Family
ID=16232300
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18892683A Pending JPS6079608A (en) | 1983-10-07 | 1983-10-07 | Transparent thin film with protecting film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6079608A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017513542A (en) * | 2014-02-27 | 2017-06-01 | アライン テクノロジー， インコーポレイテッド | Thermal anti-fogging system and method |
| US11254608B2 (en) * | 2016-02-23 | 2022-02-22 | Saint-Gobain Glass France | Article comprising a protective top layer based on mixed oxide of zirconium and aluminum |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5136477A (en) * | 1974-09-20 | 1976-03-27 | Toray Industries | Arufua amino ipushiron kapurorakutamu no tanriho |
-
1983
- 1983-10-07 JP JP18892683A patent/JPS6079608A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5136477A (en) * | 1974-09-20 | 1976-03-27 | Toray Industries | Arufua amino ipushiron kapurorakutamu no tanriho |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017513542A (en) * | 2014-02-27 | 2017-06-01 | アライン テクノロジー， インコーポレイテッド | Thermal anti-fogging system and method |
| US10111581B2 (en) | 2014-02-27 | 2018-10-30 | Align Technology, Inc. | Thermal defogging system and method |
| US11134834B2 (en) | 2014-02-27 | 2021-10-05 | Alighn Technology, Inc. | Protective sleeve for intraoral scanner |
| US11254608B2 (en) * | 2016-02-23 | 2022-02-22 | Saint-Gobain Glass France | Article comprising a protective top layer based on mixed oxide of zirconium and aluminum |
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