JP3027315B2 - Laminated film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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]

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, as the gas barrier layer, SiO ₂ or Al ₂ O ₃ or the like is vapor-deposited on at least one surface of the polymer film, or a gas barrier layer such as a vinylidene chloride polymer or a vinyl alcohol polymer is formed on the polymer film. It is known to provide a coating layer of a polymer having a property. 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]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to provide a transparent and conductive laminated film having excellent transparency, gas barrier properties and durability.

[0004]

The above-mentioned object is achieved by the present invention described below. That is, according to the present invention, a barrier layer composed of SiOx (1.5 <x ≦ 2.0) or Al ₂ O _3, a coating layer of an epoxy acrylate ultraviolet curable resin containing a silane coupling agent, and a transparent layer are formed on one surface of a polymer film. It is a laminated film characterized by sequentially laminating conductive layers, and SiOx (1.
5 <x ≦ 2.0) or a barrier film composed of Al ₂ O _3, a coating layer of an epoxy acrylate ultraviolet curable resin containing a silane coupling agent, and a transparent conductive layer, which are sequentially laminated. And a barrier layer made of SiOx (1.5 <x ≦ 2.0) or Al ₂ O ₃ and a coating layer of an epoxy acrylate ultraviolet curable resin containing a silane coupling agent are sequentially laminated on both surfaces of the polymer film. And a laminated film comprising a transparent conductive layer laminated on only one side.

[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.

In the present invention, the gas barrier layer is made of SiOx
(1.5 <x ≦ 2.0) or Al ₂ O ₃ . The gas barrier layer can be formed by known EB evaporation. The thickness of the barrier layer is 100 to 100.
0 ° is desirable. Preferably, 200-600 ° is desirable. When the angle is 100 ° or less, the unevenness of the SiOx layer
Since it is difficult to suppress the temperature to 0 ° or less, a continuous structure cannot be maintained, and good gas barrier properties cannot be obtained. 1
If it is more than 000 °, the transparency due to coloring and the gas barrier property due to the generation of cracks due to the internal stress of the gas barrier layer are undesirably reduced. Furthermore, in order to enhance the gas barrier property, the thickness of the gas barrier layer must be set so that cracks due to internal stress do not occur.
About 0 ° is preferable.

[0007] The coating layer covering the gas barrier layer used in the present invention must 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] 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]

【Example】

Example 1 A polyethersulfone film having a thickness of 100 μm was used as a polymer film, and an SiO _1.9 layer was formed on both sides of the film by EB evaporation to a thickness of 400 °, and a coating layer having a molecular weight of about 104 was formed so as to cover the gas barrier layer.
0, 100 parts by weight of an epoxy acrylate prepolymer having a melting point of 55 ° C. (VR-90 manufactured by Showa Polymer Co., Ltd.), 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 (Shin-Etsu Chemical Co., Ltd.) 1 part by weight of KMB-503 manufactured by Co., Ltd. was stirred and dissolved at 50 ° C., and a uniform solution was applied to both surfaces 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. Before the ITO was formed on the transparent conductive film thus prepared, the oxygen barrier property was measured before and after immersion in HCl at a concentration of 1N and a liquid temperature of 30 ° C. for 5 minutes. m ² · day. <Comparative Example 1> A transparent conductive film was prepared in the same manner as in Example except that the coating layer was omitted.
^2.5 cc / m ² · d of oxygen barrier property before forming
Although it was ay, 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 1N and a liquid temperature of 30 ° C.

<Example 2> A polymer film having a thickness of 10
Using a 0 μm polyethersulfone film, an Al ₂ O ₃ layer was formed on both sides by EB vapor deposition at 400 °, and an epoxy acrylate prepolymer having a molecular weight of about 1040 and a melting point of 55 ° C. was formed as the coating layer so as to cover the gas barrier layer. (Showa Polymer Co., Ltd. VR-90) 100 parts by weight, diethylene glycol 200 parts by weight, ethyl acetate 1
00 parts by weight, benzene ethyl ether 2 parts by weight, silane coupling agent (KMB-503 manufactured by Shin-Etsu Chemical Co., Ltd.)
One part by weight is stirred and dissolved at 50 ° C., and a uniform solution is applied on both sides by a dipping method, heated at 80 ° C. for 10 minutes, irradiated with ultraviolet rays to form the coating, and then roll-to-roll method An ITO film having a thickness of 300 ° was formed by the reactive magnetron sputtering apparatus of the above. Before the ITO was formed on the transparent conductive film thus prepared, the oxygen barrier property was measured before and after immersion in HCl at a concentration of 1N and a liquid temperature of 30 ° C. for 5 minutes. m ² · day. <Comparative Example 2> A transparent conductive film was prepared in the same manner as in Example except that the coating layer was omitted.
^2.5 cc / m ² · d of oxygen barrier property before forming
Although it was ay, it was confirmed that the sample had been degraded to 3 cc / m ² · day when immersed in HCl for 5 minutes in HCl having a concentration of 1N and a liquid temperature of 30 ° C.

[0011]

According to the present invention, it has become possible to provide a transparent conductive film having excellent transparency, gas barrier properties and durability.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI B32B 27/16 B32B 27/16 27/18 27/18 D 27/30 27/30 A C08J 7/04 C08J 7/04 D G02F 1/1343 G02F 1/1343

Claims (3)

(57) [Claims] 1. A method according to claim 1, wherein one side of the polymer film is made of SiOx.
(1.5 <x ≦ 2.0) or a barrier layer made of Al ₂ O _3, a coating layer of an epoxy acrylate ultraviolet curable resin containing a silane coupling agent, and a transparent conductive layer are sequentially laminated. Laminated film. 2. A polymer film having SiOx on both sides.
(1.5 <x ≦ 2.0) or a barrier layer made of Al ₂ O _3, a coating layer of an epoxy acrylate ultraviolet curable resin containing a silane coupling agent, and a transparent conductive layer are sequentially laminated. Laminated film. 3. A polymer film having SiOx on both sides.
(1.5 <x ≦ 2.0) or a barrier layer composed of Al ₂ O ₃ and a coating layer of an epoxy acrylate ultraviolet curable resin containing a silane coupling agent are sequentially laminated, and a transparent conductive layer is laminated only on one side. A laminated film comprising: