JP3027316B2 - Laminated film - Google Patents
Laminated filmInfo
- Publication number
- JP3027316B2 JP3027316B2 JP7102850A JP10285095A JP3027316B2 JP 3027316 B2 JP3027316 B2 JP 3027316B2 JP 7102850 A JP7102850 A JP 7102850A JP 10285095 A JP10285095 A JP 10285095A JP 3027316 B2 JP3027316 B2 JP 3027316B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- gas barrier
- layer
- transparent conductive
- barrier 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.)
- Expired - Fee Related
Links
Landscapes
- Liquid Crystal (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、フィルム液晶表示装置
に用いられる透明導電性フィルムに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent conductive film used for a film liquid crystal display.
【０００２】[0002]
【従来の技術】透明導電性フィルムとしては、ポリエス
テルフィルム等の透明高分子フィルム表面に酸化インジ
ウム、酸化錫、あるいは錫、インジウム合金の酸化膜等
の半導体膜や金、銀、パラジウムあるいはそれらの合金
等の金属膜、半導体膜と金属膜を組み合わせて形成され
たもの等が知られている。一方、ガスバリヤー層として
は、高分子フィルム上の少なくとも片面にＡｌ2Ｏ3又は
ＳｉＯ2 等を蒸着したもの、あるいは、高分子フィルム
上に塩化ビニリデン系ポリマーやビニルアルコール系ポ
リマーなど相対的にガスバリヤー性のあるポリマーのコ
ーティング層を設けたものが知られている。高分子フィ
ルム液晶表示装置には、ガスバリヤー性、透明導電性を
合わせ持つフィルムが必要である。しかし、これらの機
能を有する各層をくみあわせ透明性、ガスバリアー性を
付与し、液晶表示装置材料として必要な耐久性のすべて
が十分な透明導電性フィルムは、いまだ工業的には生産
されていない。2. Description of the Related Art As a transparent conductive film, a transparent polymer film such as a polyester film or the like, a semiconductor film such as indium oxide, tin oxide, or an oxide film of tin or indium alloy, gold, silver, palladium or an alloy thereof is used. And the like, and those formed by combining a semiconductor film and a metal film. On the other hand, the gas barrier layer is formed by depositing Al 2 O 3 or SiO 2 on at least one surface of the polymer film, or a gas barrier layer such as vinylidene chloride polymer or vinyl alcohol polymer on the polymer film. One provided with a coating layer of a polymer having a barrier property is known. A polymer film liquid crystal display device requires a film having both gas barrier properties and transparent conductivity. However, a transparent conductive film that combines these layers having these functions to impart transparency and gas barrier properties and has sufficient durability as a liquid crystal display device material has not yet been industrially produced. .
【０００３】[0003]
【発明が解決しようとする課題】本発明は、かかる現状
に鑑みなされたもので、透明性、ガスバリヤー性、耐久
性の優れた透明で導電性を有するフィルムを提供するこ
とにある。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a transparent and conductive film having excellent transparency, gas barrier properties and durability.
【０００４】[0004]
【課題を解決するための手段】上述の目的は、下記の本
発明により達成される。即ち本発明は、高分子フィルム
の片面に、Ａｌ2Ｏ3及びＳｉＯｘ（１．５＜ｘ≦２．
０）を順次積層したガスバリヤー層、シランカップリン
グ剤を含むエポキシアクリレート紫外線硬化樹脂のコー
ティング層並びに透明導電層を順次積層してなることを
特徴とする積層フィルムであり、高分子フィルムの両面
に、Ａｌ2Ｏ3及びＳｉＯｘ（１．５＜ｘ≦２．０）を順
次積層したガスバリヤー層、シランカップリング剤を含
むエポキシアクリレート紫外線硬化樹脂のコーティング
層並びに透明導電層を順次積層してなることを特徴とす
る積層フィルムであり、高分子フィルムの両面に、Ａｌ
2Ｏ3及びＳｉＯｘ（１．５＜ｘ≦２．０）を順次積層し
たガスバリヤー層並びにシランカップリング剤を含むエ
ポキシアクリレート紫外線硬化樹脂のコーティング層を
順次積層し、更に片面のみに透明導電層を積層してなる
ことを特徴とする積層フィルムである。The above-mentioned object is achieved by the present invention described below. That is, according to the present invention, Al 2 O 3 and SiOx (1.5 <x ≦ 2.
0) is a laminated film characterized by sequentially laminating a gas barrier layer, a coating layer of an epoxy acrylate ultraviolet curable resin containing a silane coupling agent, and a transparent conductive layer, which are sequentially laminated. , Al 2 O 3 and SiO x (1.5 <x ≦ 2.0) in order, a gas barrier layer, a coating layer of an epoxy acrylate ultraviolet curable resin containing a silane coupling agent, and a transparent conductive layer. A laminated film characterized in that Al film is formed on both sides of the polymer film.
A gas barrier layer in which 2 O 3 and SiOx (1.5 <x ≦ 2.0) are sequentially laminated, and a coating layer of an epoxy acrylate ultraviolet curing resin containing a silane coupling agent are sequentially laminated, and a transparent conductive layer is formed only on one surface. Are laminated to form a laminated film.
【０００５】本発明で用いる透明の高分子フィルムとし
てはポリエステルフィルム、ポリエーテルイミドフィル
ム、ポリアリレートフィルム、ポリエーテルサルフォン
フルム等があげられる。本発明で用いられる透明な高分
子フィルムの全光線等か率は少なくとも４０％以上、好
ましくは８０％以上が望ましい。本発明に用い透明な高
分子フィルムはガスバリヤー層導電層の形成に先立ち各
層及び透明な高分子フィルムの密着力を高めるために脱
ガス処理、コロナ放電処理、火炎処理等の表面処理やア
クリル系エポキシ系の公知のアンカーコートが施されて
いてもよい。[0005] Examples of the transparent polymer film used in the present invention include a polyester film, a polyetherimide film, a polyarylate film, and a polyether sulfone film. It is desired that the transparent polymer film used in the present invention has a total light ray ratio of at least 40% or more, and preferably 80% or more. The transparent polymer film used in the present invention is a gas barrier layer. Prior to the formation of the conductive layer, a surface treatment such as degassing treatment, corona discharge treatment, flame treatment, etc., and an acrylic resin are used to enhance the adhesion between each layer and the transparent polymer film. A known epoxy-based anchor coat may be applied.
【０００６】本発明でいうガスバリヤー層は、Ａｌ2Ｏ3
とＳｉＯｘ（１．５＜ｘ≦２．０）で示すことができ
る。該ガスバリヤー層は公知のＥＢ蒸着により順次形成
することができる。Ａｌ2Ｏ3層は５０Å以下では連続構
造を保つことができず１０００Å以上では着色が生じ好
ましくなく、８０〜３００Åが望ましい。ＳｉＯｘ
（１．５＜ｘ≦２．０）層は１００Å以下では連続構造
を保つことができず、良好なガスバリヤー性を得られな
く、１０００Å以上では、着色によるの透明性の低下、
ガスバリヤー層の内部応力起因するクラックの発生によ
るガスバリヤー性の低下が起こり好ましくない。さらに
言えば、ガスバリヤー性を高めるためには、ガスバリヤ
ー層の厚みが内部応力に起因するクラックが発生しない
４００Å程度が好ましい。ＳｉＯｘ（１．５＜ｘ≦２．
０）はＡｌ2Ｏ3を高分子フィルムに形成するとＳｉＯｘ
（１．５＜ｘ≦２．０）膜を形成したときに比べ同膜厚
での表面凹凸が半分以下になることに着目して鋭意検討
した結果、高分子フィルム上にＡｌ2Ｏ3膜を形成した表
面にＳｉＯｘ（１．５＜ｘ≦２．０）膜を形成すると高
分子フィルムにＳｉＯｘ（１．５＜ｘ≦２．０）膜を直
接形成したときに比較してＳｉＯｘ（１．５＜ｘ≦２．
０）膜を同じにしたとき表面の凹凸が半分になることを
みいだした。即ち、ＳｉＯｘ（１．５＜ｘ≦２．０）が
Ａｌ2Ｏ3膜に沿って堆積するためＳｉＯｘ（１．５＜ｘ
≦２．０）が表面の平滑な膜を形成した結果緻密な構造
となりガスバリヤー性が向上させるに至った。In the present invention, the gas barrier layer is made of Al 2 O 3
And SiOx (1.5 <x ≦ 2.0). The gas barrier layer can be sequentially formed by known EB deposition. The Al 2 O 3 layer cannot maintain a continuous structure at a temperature of 50 ° or less, and is not preferably colored at a temperature of 1000 ° or more. SiOx
(1.5 <x ≦ 2.0) When the layer is less than 100 °, a continuous structure cannot be maintained, and a good gas barrier property cannot be obtained.
Undesirably, the gas barrier layer deteriorates due to the generation of cracks due to the internal stress of the gas barrier layer. Furthermore, in order to enhance the gas barrier property, the thickness of the gas barrier layer is preferably about 400 ° at which cracks due to internal stress do not occur. SiOx (1.5 <x ≦ 2.
0) SiOx when Al 2 O 3 is formed on a polymer film
(1.5 <x ≦ 2.0) As a result of intensive study focusing on the fact that the surface unevenness at the same film thickness is less than half compared with the case of forming the film, an Al 2 O 3 film was formed on the polymer film. When a SiOx (1.5 <x ≦ 2.0) film is formed on the surface on which the polymer is formed, the SiOx (1 <1.5 ≦ 2.0) film is directly formed on the polymer film. 0.5 <x ≦ 2.
0) It was found that when the film was made the same, the surface irregularities were reduced by half. That is, since SiOx (1.5 <x ≦ 2.0) is deposited along the Al 2 O 3 film, SiOx (1.5 <x
.Ltoreq.2.0) formed a film having a smooth surface, resulting in a dense structure and improved gas barrier properties.
【０００７】本発明に使用されるガスバリヤー層を覆う
コーティング層としては、上述のガスバリヤー層と透明
導層の双方に対して密着力が必要であり、エポキシアク
リレートプレポリマーにシランカップリング剤を添加し
たとき、達成されることをみいだした。シランカップリ
ング剤の添加量は、０．５〜１．０重量％が望ましい。
シランカップリング剤としては、例えば信越化学（株）
のＫＭＢ−５０３、ＫＭＢ−８０３，日本ユニカー
（株）のＡー１８７が用いられるが、特にエポキシ基、
アミノ基、メルカプトン基を有するものが好ましい。エ
ポキシアクリレートプレポリマーは、融点が、５０℃以
上のものが好ましく、昭和高分子株式会社のＶＲ−９０
があげられる。As a coating layer covering the gas barrier layer used in the present invention, it is necessary to have adhesion to both the above-mentioned gas barrier layer and the transparent conductive layer, and a silane coupling agent is added to the epoxy acrylate prepolymer. When added, it was found to be achieved. The addition amount of the silane coupling agent is desirably 0.5 to 1.0% by weight.
As the silane coupling agent, for example, Shin-Etsu Chemical Co., Ltd.
KMB-503, KMB-803 and A-187 of Nippon Unicar Co., Ltd. are used.
Those having an amino group or a mercapton group are preferred. The epoxy acrylate prepolymer preferably has a melting point of 50 ° C. or higher.
Is raised.
【０００８】即ち、該ガスバリヤー層は、該透明導電性
フィルムを用いてＬＣＤを作製する際に必要なＮａＯＨ
溶液浸せき処理、ＨＣｌ浸せき処理により、欠陥が生じ
ガスバリヤ−性が劣化するため実用不可能であったが、
ガスバリヤー層、透明導電層の双方に密着力優れ、か
つ、ガスバリヤー層に必要な耐久性が付与可能な該コー
ティングを施すことにより克服することができた。尚、
上述の透明導電層の形成法としては、従来から公知の真
空蒸着法、イオンプレーティング法、スパッタ法等の物
理的堆積法が適用できる。[0008] That is, the gas barrier layer is made of NaOH necessary for producing an LCD using the transparent conductive film.
The solution immersion treatment and the HCl immersion treatment caused defects and deteriorated gas barrier properties, so that it was not practical.
The problem could be overcome by applying the coating which has excellent adhesion to both the gas barrier layer and the transparent conductive layer and can impart the necessary durability to the gas barrier layer. still,
As a method for forming the above-described transparent conductive layer, a conventionally known physical vapor deposition method such as a vacuum deposition method, an ion plating method, and a sputtering method can be applied.
【０００９】[0009]
＜実施例＞高分子フィルムにに厚さ１００μｍのポリエ
ーテルスルフォンフィルムを用い、その両側にＥＢ蒸着
で順次Ａｌ2Ｏ3を１００Å、ＳｉＯ1.9 を３００Å形成
し、該ガスバリヤー層を覆うように該コーティング層と
して分子量約１０４０、融点５５℃のエポキシアクリレ
ートプレポリマー（昭和高分子株式会社製ＶＲ−９０）
１００重量部、ジエチレングリコール２００重量部、酢
酸エチル１００重量部、ベンゼンエチルエーテル２重量
部、シランカップリング剤（信越化学株式会社製ＫＭＢ
−５０３）１重量部を５０℃にて撹はん溶解して均一な
溶液をディップ法により両面に塗布し８０℃１０分加熱
した後紫外線を照射して該コーティングを形成した後、
ロール・ツ・ロール方式のリアクティブマグネトロンス
パッタ装置により厚さ３００ÅのＩＴＯ膜を形成した。
このようにしてつっくた透明導電性フィルムにおいてＩ
ＴＯを形成する前の状態で濃度１規定、液温３０℃のＨ
Ｃｌに５分間浸せきする前後で酸素バリヤー性を測定し
たところ処理前後ともに１.４ｃｃ／ｍ2・ｄａｙであっ
た。 ＜比較例＞コーティング層を省略した以外は実施例と同
様にしてつっくた透明導電性フィルムにおいてＩＴＯ形
成前の状態での酸素バリヤー性が１.４ｃｃ／ｍ2・ｄａ
ｙであったが濃度１規定、液温３０℃のＨＣｌに５分間
浸せきごに測定したところ５ｃｃ／ｍ2・ｄａｙと劣化し
ていることが確認された。<Example> A 100 μm-thick polyether sulfone film was used as a polymer film, and Al 2 O 3 was sequentially formed on both sides of the film by EB vapor deposition at 100 ° and SiO 1.9 at 300 °, and the film was formed so as to cover the gas barrier layer. Epoxy acrylate prepolymer having a molecular weight of about 1040 and a melting point of 55 ° C. as a coating layer (VR-90 manufactured by Showa Polymer Co., Ltd.)
100 parts by weight, 200 parts by weight of diethylene glycol, 100 parts by weight of ethyl acetate, 2 parts by weight of benzene ethyl ether, a silane coupling agent (KMB manufactured by Shin-Etsu Chemical Co., Ltd.)
-503) 1 part by weight is stirred and dissolved at 50 ° C., a uniform solution is applied on both sides by a dipping method, heated at 80 ° C. for 10 minutes, and then irradiated with ultraviolet rays to form the coating.
An ITO film having a thickness of 300 mm was formed by a roll-to-roll type reactive magnetron sputtering apparatus.
In the transparent conductive film thus prepared, I
Before forming TO, the concentration of H is 1N and the liquid temperature is 30 ° C.
Oxygen barrier properties before and after immersion in Cl for 5 minutes were 1.4 cc / m 2 · day both before and after the treatment. <Comparative Example> A transparent conductive film prepared in the same manner as in the Example except that the coating layer was omitted had an oxygen barrier property before the formation of ITO of 1.4 cc / m 2 · da.
Although it was y, it was confirmed that the sample had been degraded to 5 cc / m 2 · day when immersed in HCl for 5 minutes in HCl at a concentration of 1 N and a liquid temperature of 30 ° C.
【００１０】[0010]
【発明の効果】本発明により、透明性、ガスバリヤー
性、耐久性の優れた透明導電性フィルムを提供すること
が可能となった。According to the present invention, it has become possible to provide a transparent conductive film having excellent transparency, gas barrier properties and durability.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０８Ｊ 7/04 Ｃ０８Ｊ 7/04 Ｄ Ｇ０２Ｆ 1/1343 Ｇ０２Ｆ 1/1343 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI C08J 7/04 C08J 7/04 D G02F 1/1343 G02F 1/1343
Claims (3)
ＳｉＯｘ（１．５＜ｘ≦２．０）を順次積層したガスバ
リヤー層、シランカップリング剤を含むエポキシアクリ
レート紫外線硬化樹脂のコーティング層並びに透明導電
層を順次積層してなることを特徴とする積層フィルム。1. A gas barrier layer in which Al 2 O 3 and SiOx (1.5 <x ≦ 2.0) are sequentially laminated on one surface of a polymer film, and a coating of an epoxy acrylate ultraviolet curable resin containing a silane coupling agent. A laminated film comprising a layer and a transparent conductive layer sequentially laminated.
ＳｉＯｘ（１．５＜ｘ≦２．０）を順次積層したガスバ
リヤー層、シランカップリング剤を含むエポキシアクリ
レート紫外線硬化樹脂のコーティング層並びに透明導電
層を順次積層してなることを特徴とする積層フィルム。2. A gas barrier layer in which Al 2 O 3 and SiOx (1.5 <x ≦ 2.0) are sequentially laminated on both surfaces of a polymer film, and a coating of an epoxy acrylate ultraviolet curable resin containing a silane coupling agent. A laminated film comprising a layer and a transparent conductive layer sequentially laminated.
ＳｉＯｘ（１．５＜ｘ≦２．０）を順次積層したガスバ
リヤー層並びにシランカップリング剤を含むエポキシア
クリレート紫外線硬化樹脂のコーティング層を順次積層
し、更に片面のみに透明導電層を積層してなることを特
徴とする積層フィルム。 3. A coating of a gas barrier layer in which Al 2 O 3 and SiOx (1.5 <x ≦ 2.0) are sequentially laminated on both surfaces of a polymer film and an epoxy acrylate ultraviolet curable resin containing a silane coupling agent. A laminated film, comprising: laminating layers sequentially, and further laminating a transparent conductive layer on only one side.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7102850A JP3027316B2 (en) | 1995-04-27 | 1995-04-27 | Laminated film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7102850A JP3027316B2 (en) | 1995-04-27 | 1995-04-27 | Laminated film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08294990A JPH08294990A (en) | 1996-11-12 |
| JP3027316B2 true JP3027316B2 (en) | 2000-04-04 |
Family
ID=14338417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7102850A Expired - Fee Related JP3027316B2 (en) | 1995-04-27 | 1995-04-27 | Laminated film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3027316B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3403882B2 (en) * | 1995-12-25 | 2003-05-06 | 帝人株式会社 | Transparent conductive film |
-
1995
- 1995-04-27 JP JP7102850A patent/JP3027316B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08294990A (en) | 1996-11-12 |
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