JPH09314729A - Transparent conductive film and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain good gas barrier, chemical resistance, surface smoothness, and productivity by a method in which a transparent gas barrier thin film containing metal oxide as a main component and a protective film mainly containing an organic crosslinked substance are formed in sequence on one side of a transparent polymer film, and a transparent conductive thin film is formed on one side the protective film. SOLUTION: A transparent gas barrier thin film 2 containing metal oxide as a main component and a protective film 3 containing a crosslinked organic substance as a main component are formed at least on one side of a transparent polymer film 1, a transparent conductive thin film 4 is formed at least on one side of the protective film 3. The central line average roughness on the surface of the thin film 4 is made not exceeding 10nm, and as regards the protective film 3, the variation in the total light transmittance of the protective film 3 after being contacted with one or more kinds of liquids selected from among γ-butyrolactone dimethyl acetammde, acetone, ethyl alcohol, 5% hydrochloric acid aqueous solution and 5% sodium hydroxide and a haze value is made within 3%. The protective film 3 is made to be a crosslinked substance of a monomer in which at least 20wt.% is made from a bismaleimide type compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a transparent conductive film and a method for producing the same, more specifically, a transparent gas barrier thin film containing a metal oxide as a main component and an organic substance crosslinked on at least one surface of a transparent polymer film. The present invention relates to a transparent conductive film in which a protective film containing a body as a main component and a transparent conductive thin film are sequentially formed, and a method for producing the same.

[0002]

2. Description of the Related Art With the progress of electronic device technology and the expansion of application fields, it is required to improve the characteristics of transparent electrodes.
The transparent electrode is generally formed on a glass substrate. For example,
Conductive glass on which a conductive metal thin film such as gold or silver is formed,
Known is ITO glass or the like formed with a thin film of a mixture of indium oxide and tin oxide (ITO). However, a transparent electrode using a glass substrate has drawbacks such as weakness to impact, heavy, lack of flexibility, limitation in thinning, and difficulty in increasing the area, and so on. Thus, a transparent conductive film having a transparent polymer film as a substrate is also manufactured. The transparent polymer film has advantages such as impact resistance, high flexibility, low specific gravity, thinness, large area, and high productivity by roll-to-roll method. The transparent conductive film using as a substrate is used in antistatic films, touch panels, liquid crystal display devices such as calculators and pagers.

Further, with the recent remarkable development of electronics technology, higher performance transparent conductive film is required. Particularly in the multimedia age, liquid crystal display devices for personal digital assistants (PDAs), which have been remarkably popularized, are required to have a display by a reflective STN display system and a pen input function. At present, a transparent substrate made of a glass substrate is used, but especially for PDA applications, a liquid crystal display device using a polymer film as a substrate is suitable for its required characteristics. In the case of the STN display method, a substrate having a high surface flatness is required, and under the present circumstances, the required characteristics are not satisfied in the surface flatness of a transparent conductive film having a plastic film as a substrate. This is probably because the surface flatness of the film used for the substrate was lowered as a result of the multilayer coating by coating, rather than the problem of the surface flatness. PDA with pen input device
Since the liquid crystal display element is arranged under the pen input panel made of a PET film or the like, impact resistance of the liquid crystal display element is particularly required, and a liquid crystal display element using a plastic film as a substrate is suitable.

Currently, a transparent conductive film generally used in a liquid crystal display device is an organic compound containing a polymer such as polyvinyl alcohol and polyvinylidene chloride having a low oxygen permeability and a low water vapor permeability as a main component on a transparent polymer film. A gas barrier thin film, a protective thin film mainly composed of a curable resin cured product formed on the gas barrier thin film by a solution coating method or a laminating method, and a transparent conductive thin film formed thereon. Is.

The reason why the protective thin film is required is that the gas barrier thin film used in the current film liquid crystal substrate is poor in durability against chemicals and solvents generally required in the liquid crystal panel manufacturing process and comes into contact with the solvent. This is because the surface is whitened and swells. Therefore, in order to protect the gas barrier thin film, it is necessary to further provide a protective thin film on the outer side thereof.

[0006]

Usually, these protective thin films are formed in a thickness of several microns by a wet process such as a solution coating method, but they have the disadvantage of lowering the surface flatness due to cissing and mixing of dusts. There are problems that the yield of the product using the conductive film is reduced and the product cannot be used for applications requiring precise surface accuracy. Furthermore, in the production by the above-described lamination process, an anchor coat layer or a primer layer is further required for the purpose of improving the adhesion between the transparent polymer film and the gas barrier thin film, and the gas barrier thin film and the protective thin film, which complicates the layer structure. In addition to doing so, equipment for removing the solvent, heat energy used in the solvent removal equipment, etc. are required,
This is a cause of rising manufacturing costs.

In other words, the transparent conductive film laminated by the above-mentioned method has low flatness because it has many coating layers formed by the wet process even if a base film having a flat surface is used. Furthermore, as a result, it has been pointed out that the cost increase due to the multilayer coating. It has also been pointed out that the barrier performance is insufficient only with the organic gas barrier thin film. The inventors of the present invention have reached the present invention as a result of earnest studies to solve such problems. The present invention aims to solve the problems with the above-mentioned conventional transparent conductive film, and to provide a gas barrier property, chemical resistance, surface flatness, a transparent conductive film having good productivity and a method for producing the same. To do.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have completed the present invention. In order to achieve the above object, the transparent conductive film of the present invention, a transparent gas barrier thin film mainly composed of a metal oxide and a protective film mainly composed of a crosslinked organic material are sequentially formed on at least one surface of a transparent polymer film. Is
Furthermore, a transparent conductive thin film is formed on at least one surface of the protective film.

The transparent conductive film having the above structure is
Good gas barrier properties, solvent resistance, surface flatness, and productivity.

In this case, the center line average roughness (Ra) of the surface of the transparent conductive thin film forming the transparent conductive film can be 10 nm or less.

The transparent conductive film having the above structure is
The surface flatness is particularly excellent.

Further, in the transparent conductive film, the protective film containing a cross-linked organic substance as a main component is composed of γ-butyrolactone, dimethylacetamide, acetone, ethyl alcohol, 5% hydrochloric acid aqueous solution or 5% sodium hydroxide aqueous solution. The change in total light transmittance and haze value after contact with one or more liquids selected from the above for 5 minutes can be within 3%, respectively.

The transparent conductive film having the above structure is
It has particularly excellent solvent resistance.

Further, in the transparent conductive film, the protective film containing a crosslinked organic substance as a main component, which constitutes the transparent conductive film, may contain 20% by weight or more of the bismaleimide-based monomer.

The transparent conductive film having the above structure is
It has particularly excellent heat resistance and solvent resistance.

Further, in the transparent conductive film, the protective film mainly composed of the crosslinked organic material constitutes 10 Tor.
The film can be formed in a vacuum of r or less.

The transparent conductive film having the above structure is
The surface flatness is particularly excellent.

In the transparent conductive film, the transparent gas barrier thin film constituting the transparent conductive film is made of one or more metal oxides selected from silicon oxide, aluminum oxide, magnesium oxide, calcium oxide, zirconium oxide or cerium oxide. Can be

The transparent conductive film having the above structure is
It is particularly excellent in gas barrier properties and moisture permeation resistance.

The transparent conductive film is a film in which the transparent polymer film constituting the transparent conductive film is made of one or more polymers selected from polyethylene terephthalate, syndiotactic polystyrene or alicyclic polyamideimide. be able to.

The transparent conductive film having the above structure is
It has particularly excellent optical characteristics and heat resistance.

The method for producing the transparent conductive film of the present invention is carried out in a roll-to-roll type vacuum film forming apparatus,
It is characterized in that a transparent gas barrier thin film containing a metal oxide as a main component, a protective film containing an organic crosslinked product as a main component, and a transparent conductive thin film are continuously formed on a roll-shaped transparent polymer film. .

The method for producing the transparent conductive film having the above-mentioned constitution has few defects, and the transparent conductive film of the present invention can be efficiently produced.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the transparent conductive film and the method for producing the same according to the present invention will be described below.

The transparent polymer film used in the present invention is represented by a cellulose resin represented by diacetyl cellulose or triacetyl cellulose, a polyolefin resin represented by polyethylene or polypropylene, a polymethyl (meth) acrylate or a polyethyl (meth) acrylate. Acrylic resin, polyethylene terephthalate, polyethylene isophthalate, polyester resin typified by polybutylene terephthalate, polyvinyl alcohol resin, polycarbonate resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyarylate resin, polyamideimide resin, etc. A film made of a thermoplastic polymer, or polymaleimide resin, polyimide resin, unsaturated polyester resin,
A film made of a thermosetting or photocurable polymer such as an epoxy resin or an acrylate resin is usually used. And, from the balance of optical characteristics such as transparency and birefringence, and heat resistance characteristics such as glass transition point and heat distortion temperature, a film made of polystyrene, polyethylene terephthalate, polycarbonate, polyarylate, polyether sulfone, or polyamideimide is preferable. Further, a film made of syndiotactic polystyrene, uniaxially stretched polyethylene terephthalate, and alicyclic polyamideimide is more preferable. The transparent polymer film used in the present invention may be a single layer or a laminate of two or more layers.

The syndiotactic polystyrene film has higher transparency and heat resistance than a general polystyrene film due to its three-dimensional structure. A uniaxially stretched polyethylene terephthalate film is a film stretched only in one direction in the longitudinal direction or the transverse direction, and the axes of anisotropy of the refractive index are aligned, and the retardation value of a film having a thickness of about 100 microns is several hundreds to several thousands nm. Before and after. A film made of an alicyclic polyamideimide is an alicyclic diamine component such as isophorone diamine, cyclohexane diamine, or methylene dicyclohexane diamine, or an alicyclic diisocyanate component such as isophorone diisocyanate, cyclohexane diisocyanate, or methylene dicyclohexane diisocyanate, and trimellitate. It is a film made of a condensation polymer of an acid anhydride, and is characterized in that it has both high light transmittance and high heat resistance. As a means for forming an alicyclic polyamideimide into a film, a solution casting method using an amide solvent or the like is often used, but the alicyclic polyamideimide is also dissolved in a solvent having a relatively low boiling point such as tetrahydroxyfuran or cyclohexanone. It has the characteristic that the cast film can be dried at a low temperature and in a short time because it can be made to work. The most distinctive feature of the film formed by the casting method is that it is optically isotropic and has extremely low birefringence.However, a resin with higher viscosity is used than the film formed by the melt extrusion method. It has the advantages of being able to form a high molecular weight, high strength film with little deterioration due to heat.

The thickness of the transparent polymer film used in the present invention is preferably 25 to 500 μm, more preferably 50 to 300 μm. The glass transition point (Tg) or heat deformation temperature of the transparent polymer film is 60
C. or higher is preferable, 120.degree. C. or higher is more preferable, and 150.degree. C. or higher is still more preferable.

The total light transmittance of the transparent polymer film is preferably 60% or more, more preferably 85% or more. Regarding the surface roughness of the transparent polymer film, the center line average roughness (Ra) measured by a stylus roughness measuring device is 100 nm.
The following is preferable, and 10 nm is more preferable.
It is the following.

The birefringence of the transparent polymer film is preferably extremely small or extremely large. When the film is extremely small, such as a film formed by a solution casting method, the retardation value is preferably 30 nm or less,
More preferably, it is 10 nm or less. In the case of an extremely large size such as a uniaxially stretched film, the axes of birefringence are aligned, and preferably at least 5,000 nm,
More preferably, it is 8000 nm or more.

The transparent gas barrier thin film containing a metal oxide as a main component according to the present invention includes aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, titanium oxide,
It is preferably composed of one or more kinds of metal oxides selected from indium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, and more preferably aluminum oxide, silicon oxide, magnesium oxide, and oxide. It is composed of one or more metal oxides selected from the group consisting of calcium, zirconium oxide and cerium oxide.

The thickness of the transparent gas barrier thin film is from 5 to 500 nm from the viewpoint of imparting gas barrier property to the film.
Is preferable, and more preferably 10 to 100 nm. The oxygen permeability is 5 cc / m ² · atm · da.
y or less is preferable, and more preferably 1 cc / m ² ·
It is below atm · day. Water vapor transmission rate is 10g / m
^It is preferably ² · day or less, more preferably 2 g / m ²
・ Day or less.

To form such a transparent gas barrier thin film containing a metal oxide as a main component, a PVD method (physical vapor deposition method) such as a vacuum vapor deposition method, a sputtering method, an ion plating method, or a CVD method (chemical vapor deposition method). Etc., but
It is not limited to these.

For example, as the vapor deposition material used in the vacuum vapor deposition method, metals such as silicon, aluminum, magnesium, calcium, zinc, tin, zirconium, titanium, indium and cerium, and simple substances or mixtures of oxides of these metals are used. To be

As a heating method during vacuum deposition, resistance heating, high frequency induction heating, electron beam heating, laser heating or the like can be used. Further, as the reactive gas, oxygen, nitrogen, water vapor or the like may be introduced, or reactive vapor deposition using means such as ozone addition or ion assist may be used. Further, the production conditions may be changed as long as the object of the present invention is not impaired by applying a direct current, an alternating current or a high frequency bias to the transparent polymer film, raising the temperature of the transparent polymer film or cooling it. .

In the sputtering method, a metal such as silicon, aluminum, magnesium, calcium, zinc, tin, zirconium, titanium, indium or cerium, or a simple substance or a mixture of oxides of these metals is used as a target. As the sputtering method, an ion beam sputtering method, a DC / AC / high frequency bipolar sputtering method, a hot cathode plasma sputtering method, a microwave sputtering method, a DC / high frequency magnetron sputtering method,
A direct current / high frequency opposed cathode sputtering method, a magnetic field pressure bonding type sputtering method and the like are used, but the present invention is not limited to these.

As the atmosphere for the sputtering method, oxygen, nitrogen, water vapor or the like may be introduced, or reactive sputtering using means such as ozone addition or ion assist may be used. Further, the preparation conditions may be changed as long as the object of the present invention is not impaired by applying a direct current, an alternating current or a high frequency bias to the base material, raising the base material temperature or cooling the base material. The same applies to other fabrication methods such as the CVD method.

The protective film containing a crosslinked organic material as a main component in the present invention is preferably a film made of a cured resin containing an epoxy resin, an acrylate resin, a silicone resin, an imide resin or the like as a main component, and more preferably bismaleimide. It is a cured cross-linked film of a compound or a polyamide-imide resin. Particularly preferred is a film containing 20% by weight or more as a main component of a cross-linked body of a monomer composed of a bismaleimide compound. A crosslinkable reactive group may be added to these monomer components to promote crosslinking, an acrylate crosslinking agent or an epoxy crosslinking agent may be mixed, and a reaction initiator or the like may be added. .
A cured crosslinked film of a bismaleimide compound or a polyamideimide resin is particularly excellent in heat resistance and mechanical properties. However, since the resin itself is often yellowish, it is difficult to make the film too thick. However, some of them, such as alicyclic polyamideimide resin, have very little coloring, and are suitable for this application.

The protective film containing the crosslinked organic material as a main component is formed by a wet process such as a solution coating method or a dry process such as a vapor deposition method.
Preferably, the pressure is reduced to 10 Torr or less, preferably 5
It is preferable to form the film under a reduced pressure of Torr or less. Generally, when a film is formed by a dry process, the film quality tends to be uniform and a dense structure is likely to occur, so that a thinner film can provide performance. Further, in the micron-order coating by the wet process, the flatness is worse than that of the base, but in the film formation of the submicron order or less by the dry process, the film can be formed while maintaining the flatness of the base. The thickness of the protective film is preferably 1 micron or less, more preferably 0.2 micron or less. Examples of the method for forming a film under reduced pressure include, but are not limited to, vacuum vapor deposition method, sputtering method, plasma polymerization method, vapor deposition polymerization method, ion plating method, and plasma CVD method.

As the heating method used in the vacuum deposition method, resistance heating, high frequency induction heating, electron beam heating, laser heating or the like can be used. Further, as the reactive gas, oxygen, nitrogen, water vapor, or the like may be introduced, reactive vapor deposition using means such as ozone addition may be used, or vapor deposition may be performed while irradiating the surface of the substrate with an ion beam. The energy of the ion beam at this time is preferably in the range of 0.05 to 50 KV. Further, as the ionic species, it is preferable to use ions generated from an active gas such as hydrogen, oxygen and methane, or an inert gas such as argon and helium, but not limited thereto. In addition, applying DC, AC or high frequency bias to the base material,
The production conditions may be changed as long as the object of the present invention is not impaired, such as the temperature of the base material being raised or the temperature being cooled. The same applies to the sputtering method.

When the film is formed by the plasma polymerization method or the plasma CVD method, there are high frequency discharge, microwave discharge, electron cyclotron resonance discharge, etc. as a method for generating plasma. Further, these discharges may be steady or pulsed. Also, the surface of the base material may be irradiated with an ion beam during film formation. The energy of the ion beam at this time is preferably in the range of 0.03 to 100 KV. Further, as the ionic species, it is preferable to use ions generated from an active gas such as hydrogen, oxygen and methane, or an inert gas such as argon and helium, but not limited thereto. In addition, direct current on the base material,
The preparation conditions may be changed as long as the object of the present invention is not impaired, for example, by applying an alternating current or high frequency bias, raising the substrate temperature, or cooling.

Plasma polymerization method, vapor deposition polymerization method, plasma C
In the case of the VD method or the like, a monomer having a desired polymer unit skeleton may be used. These monomers include (meth) acrylate-based polymers typified by polymethylmethacrylate, ethylene-based polymers typified by polytetrafluoroethylene, and one-component polymers such as vinyl-based polymers typified by polystyrene.
The raw material monomer may be used, polyester,
In a condensation polymer such as polyamideimide, polyimide, polyarylate, or polycarbonate, for example, in the case of polyester, a plurality of raw material monomers can be used, such as two components of an acid component and an alcohol component. Furthermore, a plurality of each component may be used as a copolymer system. As a raw material of the protective film of the present invention, it is preferable that there is little damage due to process thermal energy such as plasma polymerization method, vapor deposition polymerization method and plasma CVD method, and that it has two or more reactive functional groups. Specifically, vinyl monomers represented by divinylbenzene, epoxy monomers represented by bisphenol A epoxy, (meth) acrylate monomers represented by ethylene glycol di (meth) acrylate, and phenylene bis. Bismaleimide-based monomers typified by maleimide are preferable,
More preferably, it is a bismaleimide-based monomer, and is preferably contained in an amount of 20% by weight or more in terms of the balance of properties such as heat resistance and chemical resistance.

The protective film containing a cross-linked organic material as a main component obtained by the above-mentioned method has excellent solvent resistance, and γ-butyrolactone, dimethylacetamide, acetone, ethyl alcohol, 5% hydrochloric acid is formed on the surface of the protective film. Aqueous solution, 5
% Aqueous sodium hydroxide solution, in other words, the alignment film solvent, the etching solution for the transparent conductive film, the transparent polymer film does not whiten or swell even after contact with the liquid of the resist stripping solution, The gas barrier thin film does not dissolve or peel off. From this, it can be seen that it has a crosslinked structure with excellent solvent resistance. In addition, the protective film constituting the present invention is suitable for protecting the gas barrier thin film containing a metal oxide as a main component from scratches caused by sliding accompanied by scratches from the outside.

In the present invention, the surface flatness of the protective film containing a crosslinked organic material as a main component formed on a laminate of a transparent polymer film and a gas barrier thin film containing a metal oxide as a main component is Substantially the same as the surface flatness of the transparent polymer film itself, in the case of forming a film having an equivalent film thickness by a wet process such as a coating method,
It shows a clear advantage in surface flatness. Regarding the surface roughness of the protective film, the center line average roughness (Ra) is preferably 20 nm or less, and more preferably 10 nm or less.

In the present invention, when a protective film containing a cross-linked organic material as a main component is present on both surfaces of the laminate, a transparent conductive thin film is formed on at least one surface thereof. The transparent conductive thin film as a constituent component of the present invention is usually composed mainly of indium oxide, but preferably contains tin oxide and cadmium oxide in an amount of 20% or less, more preferably 5 to 10%. As a method for forming the transparent conductive thin film, a method such as a vacuum deposition method, an ion plating method, a sputtering method such as a direct current method or a magnetron method can be used.

The thickness of the transparent conductive thin film is 10 to 500.
nm is preferable, and more preferably 50 to 200 nm.
It is. The sheet resistance of the transparent conductive thin film is 100 ohm /
□ or less is preferable, and more preferably 50 ohm / □ or less.

In the present invention, the gas barrier thin film containing a metal oxide as a main component is formed on one side or both sides of the transparent polymer film, and a protective film containing an organic crosslinked product as a main component is formed on the surface of the gas barrier thin film. Is forming. The transparent conductive thin film is formed on one side or both sides of the protective film depending on the use of the transparent conductive film. 1 and 2 show a typical structure of the transparent conductive film of the present invention. In the figure, 1 is a transparent polymer film, 2 is a transparent gas barrier thin film, 3 is a protective film, and 4 is a transparent conductive thin film.

As a method for producing the transparent conductive film of the present invention, in a roll-to-roll type vacuum film forming apparatus,
A transparent gas barrier thin film, a protective film, and a transparent conductive thin film can be continuously formed on a roll-shaped transparent polymer film. The advantage of this manufacturing method is that the film is continuously formed in a vacuum chamber with an extremely high degree of cleanliness without being exposed to the outside air, so that a product with very few defects can be obtained. The film can be supplied by a long roll, and the manufacturing process is small due to the integrated production by the all dry process, and the manufacturing cost can be reduced.

As described above, the transparent conductive film of the present invention has excellent gas barrier properties and solvent resistance without deteriorating the surface flatness of the transparent polymer film. Also,
The transparent conductive film production method of the present invention is a production method with low production cost because of high yield and high production rate.

The meaning of the characteristic values in this specification and the method of measuring them are as follows. (1) Oxygen permeability: According to JIS K-7126, Modern Controls Inc. oxygen permeability measuring device (OX-TR
AN100 model), measurement temperature 25 ℃, relative humidity 0
It was performed under an atmosphere of% RH. (2) Water vapor permeability: According to JIS K-7129, a water vapor permeability measuring device (L80-4000 manufactured by Lissie Co., Ltd.)
Type) was used and the measurement temperature was 40 ° C. (3) Total light transmittance: Measured using a turbidimeter (NDH-1001DP type) manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K-7125. (4) Solvent resistance: A sample cut into 3 cm squares was held on a hot plate at 85 ° C for 5 minutes with the measurement surface side facing up, and then the test chemical sampled with a pipette was placed on the sample and the diameter of the droplets. Is 5 mm or more and 15 mm or less, left for 5 minutes, washed with pure water, then dried in an atmosphere of 80 ° C. and visually compared with a sample before treatment, The dissolution, whitening and swelling were evaluated. (5) Surface flatness: JIS B-0601 and JIS
According to B-0651, using a surface roughness measuring device (surfcom 721B) manufactured by Tokyo Seimitsu Co., Ltd., the center line average roughness (R
a) was measured. (6) Glass transition point (Tg): TMA tensile load method. The measurement was performed under the conditions of a weight of 1 g, a sample size of 5 × 20 mm, and a heating rate of 10 ° C./min. (7) Birefringence: The retardation value R indicating the degree of birefringence is the difference in refractive index Δ between two axes that form a right angle on the plane of the film.
n is a value obtained by multiplying the film thickness d (nm) by R (n
m) = Δn × d.

[0050]

The present invention will be described in detail below based on examples, but the present invention is not limited to these examples. In addition, comparative examples are described together with the examples.

Example 1 As a transparent polymer film,
A 100-micron-thick alicyclic polyamideimide film formed by the casting method was used. The total light transmittance of this film is 90%, the retardation value is 10 nm or less, the glass transition point (Tg) is 260 ° C., and the surface roughness (R
a) was 5 nm.

In the first chamber of the vacuum chamber, on one side of this film, an AI chip (purity: 99.99%) on a Si target (purity: 99.99%) was used, and the thickness was measured by a direct current discharge reactive sputtering method. An aluminum oxide-silicon oxide thin film having a thickness of 30 nm was formed. Argon and oxygen gas are supplied, and the pressure during sputtering in an oxygen atmosphere is 1.0 × 10 ^-3.
It was fixed to Torr. The sputtering power was 2.5 kW. Subsequently, the alicyclic polyamideimide film / aluminum oxide-silicon oxide thin film laminate was continuously conveyed to the second chamber in the vacuum chamber without breaking the vacuum. On the aluminum oxide-silicon oxide thin film, a vapor deposition film of imide-based crosslinked organic material having a thickness of 0.2 micron was formed by reactive vapor deposition in an argon plasma atmosphere using m-phenylene bismaleimide powder as a vapor deposition material. An aluminum oxide-silicon oxide thin film / imide-based crosslinked organic film was formed on the back surface by the same method.

The performance of the film laminate produced as described above was evaluated. As a result, oxygen permeability is 0.2 cc
/ M ² · atm · day, water vapor permeability 0.4 g / m ² ·
It showed an extremely excellent gas barrier property of day and moisture permeation resistance. Total light transmittance is 89%, center line average roughness (Ra)
Was 5 nm, which was comparable to the alicyclic polyamideimide film which is the transparent polymer film of the base material. Chemical resistance is γ-butyrolactone, dimethylacetamide, acetone, ethyl alcohol, 5% hydrochloric acid aqueous solution, 5
There was no change relative to the% aqueous sodium hydroxide solution. Even after this chemical resistance test, there was no change in oxygen permeability, water vapor permeability, total light transmittance, and surface flatness. From the above, the laminate has optical properties, gas barrier properties, moisture permeability resistance,
It was found that the surface flatness and solvent resistance were extremely excellent.

An ITO transparent conductive thin film having a thickness of 100 nm was formed on one surface of this film laminate by a sputtering method. The performance of the transparent conductive film thus obtained was evaluated. As a result, the oxygen permeability was 0.1 cc / m ²
・ Atm ・ day, water vapor permeability 0.2g / m ²・ da
y, the total light transmittance was 88%, the center line average roughness (Ra) was 5 nm, which were comparable to the film laminate of the substrate. The adhesion between the protective film of the imide-based crosslinked organic material and the ITO film was such that the peel strength was 100 g / cm or more.

Comparative Example 1 An aluminum oxide-silicon oxide thin film was formed on both sides of the same alicyclic polyamideimide film by the same method as in the example. However, the imide-based organic film was not laminated. The performance of the film laminate manufactured as described above was evaluated. As a result, the oxygen permeability is 0.5 cc / m ² · atm · day,
The water vapor permeability was 1.0 g / m ² · day, and both the gas barrier property and the moisture permeation resistance were sufficient. However, after this laminated film was contacted with γ-butyrolactone, dimethylacetamide, acetone, ethyl alcohol, 5% aqueous hydrochloric acid solution, 5% aqueous sodium hydroxide solution for 5 minutes in an atmosphere of 85 ° C. or lower, and removed, The changes in total light transmittance and haze value were greatly deteriorated, and it became impossible to use for optical applications. From the above, it was found that this laminate had insufficient solvent resistance.

Comparative Example 2 An aluminum oxide-silicon oxide thin film was formed on both sides of the same alicyclic polyamideimide film by the same method as in the example. However, the protective film was applied by a solution coating method with a photocurable coating agent containing epoxy acrylate as a main component so as to have a thickness of 5 μm after being dried and cured. The performance of the film laminate manufactured as described above was evaluated. As a result, the oxygen permeability was 0.5 cc / m ² · atm · day and the water vapor permeability was 1.0 g / m ² · day, and both the gas barrier property and the moisture permeation resistance were sufficient. However, the center line average roughness (Ra) of this laminate was as low as 50 nm. A transparent conductive thin film was formed on this film laminate as in the example. This transparent conductive film has a T
It can be used for the substrate of N display type liquid crystal panel, but ST
It could not be used as a substrate of an N display type liquid crystal panel.

[0057]

The transparent conductive film of the present invention according to claim 1 has excellent gas barrier properties, solvent resistance, surface flatness,
Productivity Has chemical resistance. The transparent conductive film of the present invention according to claim 2 has particularly excellent surface flatness. The transparent conductive film of the present invention according to claim 3 has particularly excellent solvent resistance. The transparent conductive film of the present invention according to claim 4 has particularly excellent heat resistance and solvent resistance.
The transparent conductive film of the present invention according to claim 5 has particularly excellent surface flatness. The transparent conductive film of the present invention according to claim 6 has particularly excellent gas barrier properties and moisture permeation resistance. The transparent conductive film of the present invention according to claim 7 has particularly excellent optical characteristics and heat resistance. Claim 8
The described method for producing a transparent conductive film of the present invention has few defects and is efficient.

[Brief description of drawings]

FIG. 1 is a schematic view showing a layer structure of a transparent conductive film of the present invention.

FIG. 2 is a schematic view showing a layer structure of the transparent conductive film of the present invention.

[Explanation of symbols]

 1 Transparent Polymer Film 2 Transparent Gas Barrier Thin Film 3 Protective Film 4 Transparent Conductive Thin Film

Claims (8)

[Claims] 1. A transparent gas barrier thin film containing a metal oxide as a main component and a protective film containing an organic crosslinked product as a main component are sequentially formed on at least one surface of a transparent polymer film, and the transparent film is transparent on at least one surface. A transparent conductive film having a conductive thin film formed thereon. 2. The transparent conductive film according to claim 1, wherein the center line average roughness (Ra) of the surface of the transparent conductive thin film is 10 nm or less. 3. A protective film containing a crosslinked organic material as a main component,
Changes in total light transmittance and haze value after contact with one or more liquids selected from γ-butyrolactone, dimethylacetamide, acetone, ethyl alcohol, 5% hydrochloric acid aqueous solution or 5% sodium hydroxide aqueous solution are 3%, respectively.
It is below, The transparent conductive film of Claim 1 or 2 characterized by the above-mentioned. 4. A protective film containing a crosslinked organic material as a main component,
20% by weight or more is a cross-linked product of a monomer composed of a bismaleimide-based compound.
The transparent conductive film according to the above. 5. A protective film containing a crosslinked organic material as a main component,
The transparent conductive film according to claim 1, which is a film formed in a vacuum of 10 Torr or less. 6. The transparent gas barrier thin film is silicon oxide,
1 selected from aluminum oxide, magnesium oxide, calcium oxide, zirconium oxide or cerium oxide
Or it consists of a plurality of metal oxides, The transparent conductive film according to claim 1, 2, 3, 4, or 5. 7. The transparent polymer film is a film made of one or more polymers selected from polyethylene terephthalate, syndiotactic polystyrene and alicyclic polyamideimide.
The transparent conductive film according to 2, 3, 4, 5 or 6. 8. A roll-to-roll type vacuum film forming apparatus comprising a transparent gas barrier thin film containing a metal oxide as a main component and a crosslinked organic compound as a main component on at least one surface of a roll-shaped transparent polymer film. A method for producing a transparent conductive film, which comprises sequentially forming a protective film, and then continuously forming a transparent conductive thin film on at least one surface of the protective film.