JP3855307B2 - Transparent conductive film and method for producing the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a transparent conductive film and a method for producing the same, and more specifically, a transparent gas barrier thin film mainly composed of a metal oxide and a protection mainly composed of an organic crosslinked material on at least one surface of the transparent polymer film. The present invention relates to a transparent conductive film in which a film and a transparent conductive thin film are sequentially formed, and a method for producing the transparent conductive film.
[0002]
[Prior art]
  With the advancement of electronic device technology and the expansion of application fields, improvement in characteristics of transparent electrodes is required. The transparent electrode is generally formed on a glass substrate. For example, conductive glass in which a conductive metal thin film such as gold or silver is formed, ITO glass in which a thin film of a mixture of indium oxide and tin oxide (ITO) is known, and the like are known.
  However, transparent electrodes using glass substrates have drawbacks such as weakness to impact, heavyness, lack of flexibility, limitations in thinning, and difficulty in increasing the area. Thus, a transparent conductive film having a transparent polymer film as a substrate is also produced. Transparent polymer film has advantages such as impact resistance, high flexibility, low specific gravity, thinning, easy area enlargement, and high productivity by roll-to-roll method. A transparent conductive film having a substrate as a substrate is used for an antistatic film, a touch panel, a liquid crystal display element such as a calculator or a pager.
[0003]
  Furthermore, with the recent remarkable development of electronics technology, a higher performance transparent conductive film is required. In particular, liquid crystal display elements for personal digital assistants (PDAs), which are becoming increasingly popular in the multimedia era, are required to have a display using a reflective STN display method and a pen input function. Currently, a transparent substrate made of a glass substrate is used. Particularly in PDA applications, a liquid crystal display element using a polymer film as a substrate is suitable for the required characteristics. In the case of the STN display system, a substrate having a high surface flatness is required, and the current flatness of a transparent conductive film using a plastic film as a substrate does not satisfy the required characteristics. This seems to be because the surface flatness of the film used for the substrate was lowered as a result of the multi-layer coating. In a PDA equipped with a pen input device, a liquid crystal display element is disposed under a pen input panel made of a PET film or the like, so that the liquid crystal display element is particularly required to have impact resistance, and a liquid crystal display using a plastic film as a substrate. A device is preferred.
[0004]
  Currently, a transparent conductive film generally used for a liquid crystal display element is an organic gas barrier thin film mainly composed of a polymer having a low oxygen permeability or water vapor permeability such as polyvinyl alcohol or polyvinylidene chloride on a transparent polymer film. Further, a protective thin film mainly composed of a curable resin cured product is formed on the gas barrier thin film by a solution coating method, a laminating method, or the like, and a transparent conductive thin film is further formed thereon.
[0005]
  The reason why a protective thin film is required is that the gas barrier thin film used in the current film liquid crystal substrate is generally poor in durability against chemicals and solvents that are required in the liquid crystal panel manufacturing process, and the surface is in contact with the solvent. It is because it whitens or swells. Therefore, in order to protect the gas barrier thin film, it is necessary to further provide a protective thin film on the outside thereof.
[0006]
[Problems to be solved by the invention]
  Usually, these protective thin films are formed with a thickness of a few microns by a wet process such as solution coating, but there is a disadvantage that the surface flatness is reduced due to the mixing of repellency and dust, yield of products using transparent conductive film There is a problem in that it cannot be used for applications that require a reduction in surface roughness or a precise surface accuracy. Furthermore, in the production by the laminating process as described above, an anchor coat layer and a primer layer are further required for the purpose of improving the adhesion between the transparent polymer film and the gas barrier thin film, the gas barrier thin film and the protective thin film, and the layer configuration is complicated. In addition to this, an apparatus for removing the solvent and thermal energy used in the solvent removing apparatus are required, which causes an increase in manufacturing cost.
[0007]
  That is, the transparent conductive film laminated by the above-described method or the like has a low flatness because the coating layer formed by the wet process is stacked even if a base film having a flat surface is used. As a result, an increase in cost due to the multilayer coating is pointed out. It has also been pointed out that barrier performance is insufficient with only organic gas barrier thin films. The inventors of the present invention have reached the present invention as a result of intensive studies in order to solve such problems.
  An object of the present invention is to solve the problems of the conventional transparent conductive film and to provide a transparent conductive film having good gas barrier properties, chemical resistance, surface flatness and productivity, and a method for producing the same. To do.
[0008]
[Means for Solving the Problems]
  As a result of intensive studies to achieve the above object, the present inventors have completed the present invention.
  In order to achieve the above object, the transparent conductive film of the present invention is formed on at least one side of a transparent polymer film.,Transparent gas barrier thin film mainly composed of metal oxide andProtective filmAre formed sequentially, and a transparent conductive thin film is formed on at least one side of the protective film.A protective film comprising a crosslinked organic material as a main component, wherein the protective film is formed using a vacuum vapor deposition method, a sputtering method, a vapor deposition polymerization method, an ion plating method, or a plasma CVD method. The center line average roughness (Ra) of the transparent conductive thin film surface is 10 nm or lessIt is characterized by being.
[0009]
  The transparent conductive film having the above structure has good gas barrier properties, solvent resistance, surface flatness, and productivity.
[0010]
  In this case, the protective film mainly composed of the crosslinked organic substance can be a film made of a cured resin mainly composed of epoxy resin, acrylate resin, silicone resin or imide resin. It can be a maleimide compound or a polyamideimide resin.
[0011]
  Moreover, as for the transparent conductive film, the protective film which has the organic substance crosslinked body which comprises it as a main component can contain 20 weight% or more of bismaleimide monomers.
[0012]
  The transparent conductive film having the above structure is particularly excellent in heat resistance and solvent resistance.
[0013]
  In the transparent conductive film, the transparent gas barrier thin film constituting the transparent conductive film may be composed of one or more metal oxides selected from silicon oxide, aluminum oxide, magnesium oxide, calcium oxide, zirconium oxide, or cerium oxide. it can.
[0014]
  The transparent conductive film having the above structure is particularly excellent in gas barrier properties and moisture permeability resistance.
[0015]
  The transparent conductive film may be a film made of one or more polymers selected from polyethylene terephthalate, syndiotactic polystyrene or alicyclic polyamideimide, as the transparent polymer film constituting the transparent conductive film. .
[0016]
  The transparent conductive film having the above structure is particularly excellent in optical characteristics and heat resistance.
[0017]
  The method for producing a transparent conductive film of the present invention is a roll-to-roll type vacuum film-forming apparatus, wherein a transparent gas barrier property comprising a metal oxide as a main component on at least one surface of a roll-shaped transparent polymer film. A protective film mainly composed of a thin film and a crosslinked organic substance is sequentially formed, and a transparent conductive thin film is continuously formed on at least one surface of the protective film.A method for producing a transparent conductive film, in which a protective film composed mainly of a crosslinked organic substance is formed using a vacuum deposition method, a sputtering method, a vapor deposition polymerization method, an ion plating method or a plasma CVD method.It is characterized by that.
[0018]
  The manufacturing method of the transparent conductive film which consists of the said structure has few faults, and can manufacture the transparent conductive film of this invention efficiently.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
  Hereinafter, embodiments of the transparent conductive film of the present invention and the production method thereof will be described.
[0020]
  The transparent polymer film used in the present invention is a cellulose resin represented by diacetyl cellulose and triacetyl cellulose, a polyolefin resin represented by polyethylene and polypropylene, an acrylic resin represented by polymethyl (meth) acrylate and polyethyl (meth) acrylate. , Thermoplastic resins such as polyethylene terephthalate, polyethylene isophthalate, polyester resin represented by polybutylene terephthalate, polyvinyl alcohol resin, polycarbonate resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyarylate resin, polyamideimide resin Polymer film, polymaleimide resin, polyimide resin, unsaturated polyester resin, epoxy resin, acrylate resin The film made of a thermosetting or photocurable polymers, such as commonly used.
  A film made of polystyrene, polyethylene terephthalate, polycarbonate, polyarylate, polyethersulfone, or polyamideimide is preferable from the balance of optical properties such as transparency and birefringence, and heat resistance properties such as glass transition point and heat distortion temperature. Furthermore, 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.
[0021]
  The film made of syndiotactic polystyrene 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 longitudinal or lateral direction, and has an axis of anisotropy in refractive index. The retardation value of a film having a thickness of about 100 microns is several hundred to several thousand nm. Before and after.
  Films made of alicyclic polyamide-imide are composed of alicyclic diamine components such as isophorone diamine, cyclohexane diamine, and methylene dicyclohexane diamine, or alicyclic diisocyanate components such as isophorone diisocyanate, cyclohexane diisocyanate, and methylene dicyclohexane diisocyanate. It is a film made of a condensed polymer of acid anhydride, and is characterized by having both high light transmittance and high heat resistance. A solution cast method using an amide solvent or the like is often used as a film forming method for the alicyclic polyamideimide, but the alicyclic polyamideimide is also soluble in a relatively low boiling point solvent such as tetrahydroxyfuran or cyclohexanone. Therefore, the cast film can be dried at a low temperature for a short time. The greatest feature of the film formed by the casting method is that it is optically isotropic and has very little birefringence, but it uses a resin with a higher viscosity 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.
[0022]
  The thickness of the transparent polymer film used in the present invention is preferably 25 to 500 microns, more preferably 50 to 300 microns. The glass transition point (Tg) or heat distortion temperature of the transparent polymer film is preferably 60 ° C. or higher, more preferably 120 ° C. or higher, and still more preferably 150 ° C. or higher.
[0023]
  The total light transmittance of the transparent polymer film is preferably 60% or more, more preferably 85% or more. As for the surface roughness of the transparent polymer film, the center line average roughness (Ra) measured with a stylus roughness measuring instrument is preferably 100 nm or less, and more preferably 10 nm or less.
[0024]
  The birefringence of the transparent polymer film is preferably extremely small or extremely large. When the film is extremely small like a film formed by the solution casting method, the retardation value is preferably 30 nm or less, more preferably 10 nm or less. When it is extremely large like a uniaxially stretched film, the birefringence axes are aligned, and it is preferably 5000 nm or more, more preferably 8000 nm or more.
[0025]
  The transparent gas barrier thin film mainly composed of a metal oxide in the present invention is selected from aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, titanium oxide, indium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, and the like. It is preferable that the metal oxide is composed of one or more metal oxides, more preferably one or two selected from the group consisting of aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide, and cerium oxide. Consists of metal oxides of more than seeds.
[0026]
  The film thickness of the transparent gas barrier thin film is preferably 5 to 500 nm, more preferably 10 to 100 nm, from the viewpoint of imparting gas barrier properties to the film. The oxygen permeability is 5cc / m²・ Atm · day or less is preferable, more preferably 1 cc / m²・ Atm · day or less. Water vapor permeability is 10g / m²-Day or less is preferable, more preferably 2 g / m²-Day or less.
[0027]
  Formation of such a transparent gas barrier thin film containing a metal oxide as a main component includes 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). However, it is not limited to these.
[0028]
  For example, as a vapor deposition material used in the vacuum vapor deposition method, a metal such as silicon, aluminum, magnesium, calcium, zinc, tin, zirconium, titanium, indium, cerium, or an oxide or a mixture of these metals is used.
[0029]
  As a heating method at the time of vacuum deposition, resistance heating, high frequency induction heating, electron beam heating, laser heating, or the like can be used. In addition, reactive vapor deposition using oxygen, nitrogen, water vapor or the like as a reactive gas, ozone addition, ion assist, or the like may be used. Further, the preparation conditions may be changed as long as the object of the present invention is not impaired, such as applying a direct current, alternating current or high frequency bias to the transparent polymer film, raising the temperature of the transparent polymer film, or cooling the transparent polymer film .
[0030]
  In the sputtering method, metals such as silicon, aluminum, magnesium, calcium, zinc, tin, zirconium, titanium, indium, and cerium, and simple or mixed oxides of these metals are used as targets. Sputtering methods include ion beam sputtering, DC / AC / RF bipolar sputtering, hot cathode plasma sputtering, microwave sputtering, DC / RF magnetron sputtering, DC / RF counter cathode sputtering, and magnetic pressure bonding. A mold sputtering method or the like is used, but is not limited to these.
[0031]
  In addition, as the atmosphere for performing the sputtering method, reactive sputtering using oxygen, nitrogen, water vapor, or the like, ozone addition, ion assist, or the like may be used. In addition, the preparation conditions may be changed as long as the object of the present invention is not impaired, such as applying a direct current, an alternating current or a high frequency bias to the substrate, raising the substrate temperature, or cooling the substrate. The same applies to other production methods such as the CVD method.
[0032]
  The protective film mainly composed of a crosslinked organic substance in the present invention is preferably a film made of a cured resin mainly composed of an epoxy resin, an acrylate resin, a silicone resin, an imide resin or the like, and more preferably a bismaleimide compound or a polyamide. It is a cured crosslinked film of an imide resin. Particularly preferred is a film whose main component is a crosslinked product of a monomer comprising 20% by weight or more of a bismaleimide compound. To these monomer components, a crosslinkable reactive group may be added to promote crosslinking, an acrylate crosslinking agent or an epoxy crosslinking agent may be mixed, and a reaction initiator or the like may be blended. . 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, the film thickness is difficult to increase. However, some of them, such as alicyclic polyamideimide resins, have very little coloration and are suitable for this application.
[0033]
  The protective film mainly composed of the organic crosslinked product isSuch as vapor depositionAlthough formed by a dry process, it is preferable to form a film under a reduced pressure of 10 Torr or less, preferably 5 Torr or less. In general, when a film is formed by a dry process, the film quality tends to be uniform and a dense structure is obtained, so that a performance can be obtained with a thinner film. In addition, in the micron order coating by the wet process, the flatness is worse than that of the base, but in the submicron order or less by the dry process, it is possible to form the film while maintaining the flatness of the base. The thickness of the protective film is preferably 1 micron or less, more preferably 0.2 microns or less. As a method for forming a film under reduced pressure, a vacuum deposition method or a sputtering method is used.,Examples include, but are not limited to, vapor deposition polymerization, ion plating, and plasma CVD.
[0034]
  As a heating method used in the vacuum evaporation method, resistance heating, high frequency induction heating, electron beam heating, laser heating, or the like can be used. Alternatively, oxygen, nitrogen, water vapor, or the like may be introduced as a reactive gas, reactive vapor deposition using means such as ozone addition, or vapor deposition 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. Moreover, as ion species, it is preferable to use ions generated from an active gas such as hydrogen, oxygen, or methane, or an inert gas such as argon or helium, but not limited thereto. Further, the production conditions may be changed as long as the object of the present invention is not impaired, such as applying a direct current, an alternating current or a high frequency bias to the base material, increasing the base material temperature, or cooling the base material. The same applies to the sputtering method.
[0035]
  Plasma CVD methodIn the case of forming a film, the methods for generating plasma include high frequency discharge, microwave discharge, electron cyclotron resonance discharge, and the like. These discharges may be steady or pulsed. Moreover, you may irradiate an ion beam to the base-material surface at the time of film forming. The energy of the ion beam at this time is preferably in the range of 0.03 to 100 KV. In addition, as ion 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 it is not particularly limited thereto. In addition, the preparation conditions may be changed as long as the object of the present invention is not impaired, such as applying direct current, alternating current or high frequency bias to the base material, raising the base material temperature, or cooling the base material.
[0036]
  Vapor deposition polymerizationIn the case of a plasma CVD method or the like, a monomer having a desired polymer unit skeleton may be used. As these monomers, one-component polymers such as (meth) acrylate polymers represented by polymethyl methacrylate, ethylene polymers represented by polytetrafluoroethylene, vinyl polymers represented by polystyrene, The raw material monomer may be used, and in a condensation polymer such as polyester, polyamideimide, polyimide, polyarylate, and polycarbonate, for example, in the case of polyester, a plurality of raw materials such as an acid component and an alcohol component are used. Monomers can be used. Further, a plurality of components may be used as a copolymer system. As a raw material of the protective film of the present invention,Vapor deposition polymerizationIt is preferable to have two or more reactive functional groups that are less damaged by process thermal energy such as plasma CVD, and specifically, a vinyl monomer typified by divinylbenzene, bisphenol A Epoxy monomers typified by epoxy, (meth) acrylate monomers typified by ethylene glycol di (meth) acrylate, bismaleimide monomers typified by phenylene bismaleimide, and the like are more preferable. Is a bismaleimide monomer and is preferably contained in an amount of 20% by weight or more in view of the balance of properties such as heat resistance and chemical resistance.
[0037]
  The protective film mainly composed of an organic crosslinked product obtained by the above-described method has excellent solvent resistance, and γ-butyrolactone, dimethylacetamide, acetone, ethyl alcohol, a 5% hydrochloric acid aqueous solution, 5% on the surface thereof. % Aqueous solution of sodium hydroxide, in other words, the transparent polymer film does not whiten or swell after contact with the alignment film solvent, the transparent conductive film etchant, or the resist stripper liquid. The gas barrier thin film does not dissolve or peel off. From this, it can be seen that a cross-linked structure excellent in solvent resistance is taken. The protective film constituting the present invention is suitable for protecting a gas barrier thin film containing a metal oxide as a main component from scratches caused by sliding accompanied by scratching from the outside.
[0038]
  In the present invention, the surface flatness of the protective film mainly composed of the above-mentioned organic crosslinked material formed on the laminate of the transparent polymer film and the gas barrier thin film mainly composed of the metal oxide is the transparent polymer. There is no substantial difference from the surface flatness of the film itself, and it clearly shows the superiority in surface flatness over the case where a film having the same film thickness is formed by a wet process such as a coating method. As for the surface roughness of the protective film, the center line average roughness (Ra) is preferably 20 nm or less, more preferably 10 nm or less.
[0039]
  In the present invention, when a protective film mainly composed of a crosslinked organic material 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 of the present invention is usually composed mainly of indium oxide, but preferably contains 20% or less of tin oxide and cadmium oxide, more preferably 5 to 10%.
  As a method for forming the transparent conductive thin film, means 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.
[0040]
  The thickness of the transparent conductive thin film is preferably 10 to 500 nm, more preferably 50 to 200 nm. The sheet resistance of the transparent conductive thin film is preferably 100 ohm / square or less, more preferably 50 ohm / square or less.
[0041]
  In the present invention, the gas barrier thin film mainly composed of a metal oxide is formed on one or both surfaces of a transparent polymer film, and a protective film mainly composed of an organic crosslinked material is formed on the surface of the gas barrier thin film. Yes. Moreover, a transparent conductive thin film is formed in the single side | surface or both surfaces of the said protective film according to the use of a 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.
[0042]
  As a method for producing a transparent conductive film of the present invention, a transparent gas barrier thin film, a protective film, and a transparent conductive thin film are continuously formed on a roll-shaped transparent polymer film in a roll-to-roll vacuum film forming apparatus. Can be formed. The advantage of this manufacturing method is that the film is continuously formed in a vacuum chamber with a very clean degree without being exposed to the outside air, so that a product with very few defects can be obtained. The film can be supplied in a long roll, and there are few manufacturing processes due to the integrated production by the all dry process, and the manufacturing cost is reduced.
[0043]
  As described above, the transparent conductive film of the present invention has excellent gas barrier properties and solvent resistance without reducing the surface flatness of the transparent polymer film. Moreover, the transparent conductive film manufacturing method of the present invention is a manufacturing method with a low manufacturing cost because of a high yield and a high manufacturing speed.
[0044]
  In addition, the meaning of the characteristic value in this specification and its measuring method are as follows.
(1) Oxygen permeability: according to JIS K-7126, using an oxygen permeability measuring device (OX-TRAN100 type) manufactured by Modern Controls, in an atmosphere with a measurement temperature of 25 ° C. and a relative humidity of 0% RH. .
(2) Water vapor permeability: Measured at a measurement temperature of 40 ° C. using a water vapor permeability measuring device (L80-4000 type) manufactured by Rissy in accordance with JIS K-7129.
(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 a 3 cm square was held on a hot plate at 85 ° C. for 5 minutes with the measurement surface side up, and then the test chemical collected in a pipette was placed on the sample and the diameter of the droplet. Was dropped to 5 mm or more and 15 mm or less, left for 5 minutes, washed with pure water, then dried in an atmosphere at 80 ° C., and the sample before processing was compared visually. Dissolution, whitening, swelling, etc. were determined.
(5) Surface flatness: Centerline average roughness (Ra) was measured using a surface roughness measuring device (Surfcom 721B) manufactured by Tokyo Seimitsu Co., Ltd. according to JIS B-0601 and JIS B-0651.
(6) Glass transition point (Tg): TMA tensile load method. 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 representing the degree of birefringence is a value obtained by multiplying a biaxial refractive index difference Δn forming a right angle on the film plane by the film thickness d (nm), and R (nm). = Δn × d.
[0045]
【Example】
  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples. Moreover, the comparative example was described with the Example.
[0046]
    (Example 1)
  As the transparent polymer film, an alicyclic polyamideimide film having a thickness of 100 microns formed by a casting method was used. This film had a total light transmittance of 90%, a retardation value of 10 nm or less, a glass transition point (Tg) of 260 ° C., and a surface roughness (Ra) of 5 nm.
[0047]
  In the first chamber in the vacuum chamber, on one side of this film, an AI chip (purity 99.99%) was used on a Si target (purity 99.99%), and a thickness of 30 nm was formed by DC discharge reactive sputtering. An aluminum oxide-silicon oxide thin film was formed. Argon and oxygen gas are supplied, and the pressure during oxygen atmosphere sputtering is 1.0 × 10^-3Fixed 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. A vapor-deposited film of an imide-based crosslinked organic substance having a thickness of 0.2 microns was formed on an aluminum oxide-silicon oxide thin film 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 also formed on the back surface by the same method.
[0048]
  The performance of the film laminate produced as described above was evaluated. As a result, the oxygen permeability is 0.2 cc / m.²・ Atm ・ day, water vapor permeability 0.4g / m²-It showed an extremely excellent gas barrier property and moisture resistance of day. The total light transmittance was 89%, the centerline average roughness (Ra) was 5 nm, which was a value comparable to that of an alicyclic polyamideimide film, which is a transparent polymer film of a substrate. Chemical resistance did not change with respect to γ-butyrolactone, dimethylacetamide, acetone, ethyl alcohol, 5% aqueous hydrochloric acid, and 5% aqueous sodium hydroxide. Even after this chemical resistance test, oxygen permeability, water vapor permeability, total light transmittance, and surface flatness did not change. From the above, it was found that the laminate is extremely excellent in optical properties, gas barrier properties, moisture permeability resistance, surface flatness, and solvent resistance.
[0049]
  An ITO transparent conductive thin film having a thickness of 100 nm was formed on one surface of the film laminate by a sputtering method. The performance of the transparent conductive film thus obtained was evaluated. As a result, oxygen permeability is 0.1 cc / m²・ Atm ・ day, water vapor permeability 0.2g / m²-Day, the total light transmittance was 88%, the centerline average roughness (Ra) was 5 nm, and it was a value comparable to the film laminate of the substrate. Moreover, the peel strength of the adhesion between the protective film of the imide-based crosslinked organic material and the ITO film was 100 g / cm or more.
[0050]
    (Comparative Example 1)
  Aluminum oxide-silicon oxide thin films were formed on both sides of the same alicyclic polyamideimide film by the same method as in the examples. However, the imide organic film was not laminated. The performance of the film laminate produced as described above was evaluated. As a result, oxygen permeability 0.5cc / m²・ Atm ・ day, water vapor permeability 1.0g / m²-It was a day, and both gas barrier properties and moisture permeability resistance were sufficient. However, after this laminated film was removed by contact with γ-butyrolactone, dimethylacetamide, acetone, ethyl alcohol, 5% aqueous hydrochloric acid, 5% aqueous sodium hydroxide in an atmosphere of 85 ° C. or less for 5 minutes, respectively, Changes in the total light transmittance and haze value greatly deteriorated, making it unusable for optical applications. As mentioned above, it turned out that this laminated body has not enough solvent resistance.
[0051]
    (Comparative Example 2)
  Aluminum oxide-silicon oxide thin films were formed on both sides of the same alicyclic polyamideimide film by the same method as in the examples. However, the protective film was applied by a solution coating method so that a photocurable coating agent mainly composed of epoxy acrylate was 5 microns thick after drying and curing. The performance of the film laminate produced as described above was evaluated. As a result, oxygen permeability 0.5cc / m²・ Atm ・ day, water vapor permeability 1.0g / m²-It was a day, and both gas barrier properties and moisture permeability 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 in the same manner as in the example. The transparent conductive film can be used as a substrate for a TN display type liquid crystal panel due to its surface properties, but cannot be used as a substrate for an STN display type liquid crystal panel.
[0052]
【The invention's effect】
  Claims 1-3The transparent conductive film of the present invention described has excellent gas barrier properties, solvent resistance, surface flatness and productivity chemical resistance.
  The transparent conductive film of the present invention according to claim 4 has particularly excellent heat resistance and solvent resistance.
  Claim 5The transparent conductive film of the present invention described has excellent gas barrier properties and moisture permeability resistance.
  Claim 6The transparent conductive film of the present invention described has particularly excellent optical properties and heat resistance.
  Claim 7The method for producing the transparent conductive film of the present invention described has few defects and is efficient.
[Brief description of the 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 a 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 (7)

On at least one surface of the transparent polymer film, formed transparent gas barrier films and protective film composed mainly of metal oxide are sequentially further transparent conductive film at least a transparent conductive thin film on one surface is formed of the protective film The protective film is a protective film mainly composed of a crosslinked organic substance formed by using a vacuum vapor deposition method, a sputtering method, a vapor deposition polymerization method, an ion plating method or a plasma CVD method, and has a transparent conductive property. A transparent conductive film having a center line average roughness (Ra) of 10 nm or less on a thin film surface . 2. The transparent conductive film according to claim 1, wherein the protective film mainly composed of a crosslinked organic substance is a film made of a cured resin mainly composed of an epoxy resin, an acrylate resin, a silicone resin or an imide resin. The transparent conductive film according to claim 2, wherein the imide resin is a bismaleimide compound or a polyamide-imide resin.   4. The transparent conductive film according to claim 1, 2 or 3, wherein the protective film comprising a crosslinked organic substance as a main component is a crosslinked body of a monomer comprising 20% by weight or more of a bismaleimide compound. Transparent gas barrier thin film, silicon oxide, aluminum oxide, magnesium oxide, calcium oxide, claim 2, 3 or 4, characterized in that it consists of one or more metal oxide selected from zirconium oxide or cerium oxide The transparent conductive film as described. Transparent polymer film, polyethylene terephthalate, claim, characterized in that a film consisting of one or more polymers selected from syndiotactic polystyrene or alicyclic polyamide-imide, 2, 3, 4 or 5. The transparent conductive film according to 5. In a roll-to-roll vacuum film forming apparatus, a transparent gas barrier thin film mainly composed of a metal oxide and a protective film mainly composed of an organic crosslinked material are sequentially formed on at least one surface of a roll-shaped transparent polymer film. 7. The method for producing a transparent conductive film according to claim 1 , wherein the transparent conductive thin film is continuously formed on at least one surface of the protective film, wherein the organic conductive cross-linked product is formed. A method for producing a transparent conductive film, characterized in that a protective film mainly composed of is formed using a vacuum vapor deposition method, a sputtering method, a vapor deposition polymerization method, an ion plating method or a plasma CVD method.

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