JPH1166969A - Transparent conductive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve interlayer adhesion of a plastic liquid crystal display panel base board using a metallic oxide as a gas barrier layer by laminating the gas barrier layer composed of the metallic oxide and a protective layer A in this order on one surface of a plastic film, and laminating a protective layer B and a transparent conductive layer in this order on the other surface of the plastic film. SOLUTION: Insulating oxide such as silicon, Al, Mg and Zn is cited as metallic oxide to be used. These are also known as a material excellent in gas barrier performance. Among these, metallic oxide mainly composed of a silicon oxide on which a rate of the oxygen atom number to the silicon atom number is 1.5 to 2.0, is desirably used from the viewpoint of gas barrier performance, transparency, surface flatness, bending performance, film stress and a cost. When this rate becomes smaller than 1.5, bending performance and transparency get worse. The thickness is desirably within a range of 5 nm to 200 nm, and when it becomes thinner than 5 nm, it is difficult to uniformly form a film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a transparent conductive film, and more particularly, to transparency, optical isotropy, smoothness, and the like.
In addition to the features of excellent properties such as solvent resistance, less curl of the laminated film, less gas barrier property, less change in gas barrier property due to the environment, especially when stress is applied to the transparent conductive film side on the transparent conductive layer side It relates to a transparent conductive film that has the characteristic of good adhesion, and has various properties as a base film for transparent electrode substrates for liquid crystal panels, transparent conductive substrates such as electroluminescent panels, electrochromic panels, and surface heating elements. It relates to an excellent transparent conductive film.

[0002]

2. Description of the Related Art In recent years, in addition to the demand for lighter and thinner liquid crystal display devices and the larger size of liquid crystal display devices, there have been demands for long-term reliability, flexibility in shape, and display of curved surfaces. In particular, as the use of portable devices such as pagers, mobile phones, electronic organizers, and pen input devices becomes more widespread, the use of plastic instead of the conventional thick, heavy, and fragile glass substrates A liquid crystal panel using a substrate as a substrate has been studied, and some of the panels have begun to be put to practical use. Such a plastic liquid crystal substrate meets the demand for lightness,
No. 6,13,0010, and the like.

[0003] Furthermore, plastic substrates having improved air-permeation resistance and water vapor-permeation resistance (hereinafter referred to as gas barrier properties) are also disclosed in JP-A-61-41122, JP-A-61-73924, and JP-A-6-73924. No. 9323, for example.

However, among these plastic substrates, those in which only a polyvinyl alcohol-based resin layer is laminated as a gas barrier layer for imparting gas barrier properties are not excellent in air permeability at a low humidity of 50% RH or less. However, there is a disadvantage that the gas barrier property at a higher humidity, for example, 90% RH is inferior. Further, when the polyvinyl alcohol-based resin layer is provided directly under the transparent conductive layer or as the outermost layer, there is a problem that the polyvinyl alcohol-based resin layer is easily affected by an aqueous solution. In addition, polyacrylonitrile, polyvinylidene chloride, and the like are used as organic gas barrier layer materials, but they are not preferred from the viewpoint of handleability and environmental problems.

On the other hand, a plastic substrate provided with a metal oxide as a gas barrier layer as described in JP-A-61-183810 and the like is described. In this case, gas barrier properties almost independent of humidity can be obtained,
When the layer is thickened, there are problems such as mechanical characteristics, that is, the gas barrier layer is broken by slight bending, and it has been difficult to provide good gas barrier properties while maintaining good mechanical characteristics. Also, such metal oxides, especially,
When silicon oxide, which has good productivity and is preferably used, is in the outermost layer, there is a disadvantage that it is easily eroded by an alkaline aqueous solution.

To solve such a problem, Japanese Patent Laid-Open Publication No.
No. 143 discloses that a curable resin is laminated above or below a metal oxide layer from the viewpoint of improving scratch resistance. However, high gas barrier properties, adhesiveness of each layer, and resistance to solvents including alkaline aqueous solutions have not been sufficiently studied.

[0007]

The transparent conductive layer surface is subjected to various processes such as etching of the conductive layer, orientation treatment, and cell fabrication using a sealant. Among them, the stress due to the thermosetting of the partially patterned sealant is large,
Even if a layer shows sufficient adhesion in a normal cross-cut adhesion test, the metal oxide layer may be easily peeled off when the two substrates are separated after cell production. Such an example is often observed when a metal oxide layer is disposed as a gas barrier layer on the conductive layer side. This is because when a metal oxide layer is laminated by a vacuum process, thermal degradation of the underlying plastic film surface due to heat and stress concentration between layers due to the difference in the coefficient of thermal expansion between the metal oxide and the plastic film occur. Cause. An object of the present invention is to improve the adhesion between layers of a plastic liquid crystal display panel substrate using a metal oxide as a gas barrier layer, particularly when a stress is applied to the transparent conductive film surface on the transparent conductive layer side. And

[0008]

The transparent conductive film according to the present invention has a gas barrier layer composed of a metal oxide and a protective layer (A) laminated in this order on one surface of a plastic film, and the other side of the plastic film. The protective layer (B) and the transparent conductive layer are laminated on the surface in this order.

That is, by disposing the metal oxide layer, which is easily peeled off by the stress load in each step, on the surface opposite to the transparent conductive layer with respect to the plastic film surface, it is possible to prevent the metal oxide layer from being easily peeled off after cell production.

[0010] Here, when the adhesion after the cell fabrication was correlated with the T-type peel strength, the peel strength of each layer laminated on the transparent conductive layer side as viewed from the base plastic film was 200 g / cm or more. It was necessary to be.

Examples of the metal oxide that can be used here include insulating oxides such as silicon, aluminum, magnesium, and zinc, and are known as materials having excellent gas barrier properties. These oxide layers are formed by a vapor deposition method in which a material is deposited from a gas phase to form a film, such as a sputtering method, a vacuum deposition method, an ion plating method, and a plasma CVD method.

Among these, silicon oxide having a ratio of oxygen atoms to silicon atoms of 1.5 to 2.0 is mainly used in terms of gas barrier properties, transparency, surface flatness, flexibility, film stress, cost, and the like. The metal oxide as a component is good.

The ratio of the number of oxygen atoms to the number of silicon atoms in the silicon oxide is determined by X-ray photoelectron spectroscopy, X-ray microspectroscopy,
It is analyzed and determined by Auger electron spectroscopy, Rutherford backscattering method and the like. If this ratio is smaller than 1.5, the flexibility and the transparency deteriorate, so that 1.5 to 2.
0 is preferred.

The thickness is preferably in the range of 5 nm to 200 nm. If the thickness is less than 5 nm, it is difficult to form a uniform film, and a portion where the film is not formed occurs.
And gas permeates from this part, and gas barrier property deteriorates. On the other hand, when the thickness is more than 200 nm, not only lacks in transparency but also deteriorates flexibility, easily causes cracks, and impairs gas barrier properties and appearance.

For even higher transparency, the above-mentioned silicon oxide containing 5 to 20% by weight of magnesium fluoride with respect to the total weight is preferred. In this case, a film thickness of 50 nm or more can be preferably produced in order to dramatically improve transparency, and good gas barrier properties can be secured by the thickness effect. However, as the thickness increases, the amount of heat applied to a unit area of the plastic film increases in the vapor phase film deposition method, so that the thermal deterioration of the plastic film surface becomes more remarkable. In addition, the stress derived from the difference in the coefficient of thermal expansion becomes remarkable. Therefore, the formed metal oxide layer is more easily peeled. In such a case, the present invention is more effective.

As the plastic film, various resins such as polyester, polycarbonate, polyarylate, polysulfone and polyethersulfone can be used.
Among them, polycarbonate and polyarylate are more preferable for liquid crystal display applications where transparency and optical isotropy are particularly desired.

Here, transparency refers to wavelengths of 400 nm and 5 nm.
It means that the light transmittance at 50 nm is 80% or more and the haze value is 1% or less. Their light transmittance is 8
When it is lower than 0%, when a liquid crystal display element is formed using the same, the light use efficiency is reduced, and the display becomes darker.
The contrast is also reduced. The haze value is 1%
If it is higher than this, when a liquid crystal display element is constructed using this, transmitted light will be scattered and the degree of polarization of polarized light transmitted through the polarizing plate will be reduced. As a result, the contrast is reduced.

Next, a protective layer (A) on the metal oxide layer and a protective layer (B) between the plastic film and the transparent conductive layer.
As for (2), a substance which adheres to the metal oxide layer and the plastic film and has chemical resistance and flexibility is preferable.
At this time, the same protective layer (A) on the metal oxide layer and the same protective layer (B) between the plastic film and the transparent conductive layer are preferred from the viewpoints of the process and the economy, but they are derived from asymmetry. Different materials will not work without problems, such as strong curl deformation. When forming a liquid crystal display element, an alignment film is formed on a film surface having a conductive layer. A polyimide resin is generally used for the alignment film, but a strong polar solvent such as N-methylpyrrolidone is used for such a resin or a precursor thereof. Therefore, a high solvent resistance is required particularly on the film surface of the protective layer (B) between the plastic film and the transparent conductive layer. For such a reason, the protective layer (A) on the metal oxide layer is required. In some cases, it is preferable to use a different material for the protective layer (B) between the plastic film and the transparent conductive layer.

Such a protective layer (A) and a protective layer (B)
As a specific example, a cured resin obtained by mixing an epoxy silicon compound and an amino silicon compound with a thermosetting epoxy resin, a radiation-curable resin, or a polyvinyl alcohol-based polymer on a plastic film and performing a thermal crosslinking reaction. Polymers and the like.

The epoxy resin is preferably a novolak type epoxy resin from the viewpoint of solvent resistance. As the curing agent for curing the epoxy resin, a known material can be used. For example, amines, polyaminoamides, acids and acid anhydrides,
A curing agent such as imidazole, mercaptan, and phenol resin is used.

Among these, acid anhydrides and polymers containing an acid anhydride structure or aliphatic amines are preferably used in view of solvent resistance, optical characteristics, heat characteristics and the like, and more preferably acid anhydrides and acid anhydride structures are used. Containing polymer.

Further, it is preferable to add an appropriate amount of a known curing catalyst such as a tertiary amine or imidazole in order to increase the reaction rate.

The radiation-curable resin refers to a resin that cures when irradiated with radiation such as ultraviolet rays or electron beams. Specifically, a molecule or a unit structure contains an acryloyl group, a methacryloyl group, a vinyl group, or the like. A resin containing a saturated double bond. Among these, a resin containing an acryloyl group is particularly preferable from the viewpoint of reactivity. The composition may be a single composition or a mixed composition of several kinds, but from the viewpoint of solvent resistance, a polyfunctional acrylate component having two or more acryloyl groups in a molecule or a unit structure is contained in the resin composition. Is preferred. Examples of such polyfunctional acrylate components include various acrylate monomers such as dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and trimethylolpropane triacrylate, and polyester-modified or urethane-modified polyacrylates. Functional acrylate oligomers and the like,
It is not limited to these.

Further, a hydrolyzate of an alkoxysilane represented by the following general formula (1) or (2) is added to such a radiation-curable resin composition for the purpose of imparting further adhesion and solvent resistance. It may be mixed so that the weight ratio is within 75% by weight or less.

[0025]

Embedded image R ¹ —Si (OR ² ) ₃ ... (1) Si (OR ² ) ₄ ... (2) (In the above formula, R ¹ is an organic group containing a methyl group, an ethyl group or a vinyl group, an acryloyl group, a methacryloyl group, an amino group, and an epoxy group. , R ² represents a methyl group or an ethyl group.) When the mixing ratio exceeds 75% by weight, on the contrary, solvent resistance,
The tendency of the curability to decrease is observed, which is not preferable.

When the ultraviolet curing method is used, an appropriate amount of a known photoreaction initiator is added to the above-mentioned resin composition. For example, diethoxyacetophenone, 2-methyl-1- {4
Acetophenone-based compounds such as-(methylthio) phenyl} -2-morpholinopropane, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1-hydroxycyclohexylphenyl ketone; benzoin such as benzoin and benzyldimethylketal Benzophenone compounds such as benzophenone and benzoylbenzoic acid; and thioxanthone compounds such as thioxanthone and 2,4-dichlorothioxanthone. Further, in order to further improve curability, triethanolamine,
It is also effective to add an appropriate amount of a known reaction initiation aid such as methyldiethanolamine and ethyl 4-dimethylaminobenzoate.

In the cured polymer obtained by mixing an epoxy silicon compound and an amino silicon compound with a polyvinyl alcohol-based polymer and subjecting it to a cross-linking reaction, a known commercially available polyvinyl alcohol-based polymer can be used. A polymer resin containing 50 mol% or more of at least one selected from the group consisting of vinyl alcohol copolymer components is applied. The vinyl alcohol copolymer may be a vinyl alcohol-vinyl acetate copolymer, a vinyl alcohol-vinyl butyral copolymer, an ethylene-vinyl alcohol copolymer, or a polyvinyl alcohol polymer having a silyl group in the molecule. And the like. Of these, a saponification degree of 80% is preferred.
The above polyvinyl alcohols, ethylene-vinyl alcohol copolymers, and polyvinyl alcohol-based polymers having a silyl group in the molecule are preferred, and ethylene-vinyl alcohol copolymers are more preferred.

The epoxy silicon compound is selected from the group consisting of a silicon compound having an epoxy group and an alkoxysilyl group, a (partly) hydrolyzate thereof, a (partly) condensate thereof, and a mixture thereof. ).

[0029]

X—R ³ —Si (R ⁴ ) _n (OR ⁵ ) _3-n (3) (where R ³ is an alkylene group having 1 to 4 carbon atoms, and R ⁴ and R ⁵ are An alkyl group having 1 to 4 carbon atoms, X is a glycidoxy group or an epoxycyclohexyl group, and n is 0 or 1.)

Among these, particularly preferred epoxy silicon compounds are 3-glycidoxypropyltrimethoxysilane,
(3,4-epoxycyclohexyl) ethyltrimethoxysilane. These compounds can be used alone or in combination of two or more.

The aminosilicon compound is selected from the group consisting of a silicon compound having an amino group and an alkoxysilyl group, a (partial) hydrolyzate thereof, a (partial) condensate thereof, and a mixture thereof. ).

[0032]

Embedded image Y—HN—R ⁶ —Si (R ⁷ ) _m (OR ⁸ ) _3-m (4) (where R ⁶ is an alkylene group having 1 to 4 carbon atoms, R ⁷ and R ⁸ is an alkyl group having 1 to 4 carbon atoms, Y is a hydrogen atom or an aminoalkyl group, and m is 0 or 1.)

Among these, particularly preferred aminosilicon compounds are 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane. These compounds can be used alone or in combination of two or more.

The mixing ratio of the epoxy silicon compound and the amino silicon compound is 1/6 <A / B <6 for the mixture of the epoxy group molar equivalent A and the amino group molar equivalent B, respectively. / 1 is more preferable, and 1/4 <A / B <4/1 is more preferable. When the mixing ratio is out of this range, adhesion, heat resistance, solvent resistance, water resistance, and durability are reduced. When such a mixture of the epoxy silicon compound and the amino silicon compound is mixed with the polyvinyl alcohol-based polymer, they are mixed so that the solid content after curing becomes 20 to 90% by weight. 20
If the amount is less than 10% by weight, water resistance and chemical resistance are poor, and adhesion to the transparent conductive layer laminated thereon is lacking. If it is more than 90% by weight, it becomes brittle and may break when bent.

Such a polyvinyl alcohol-based polymer and a silicon compound can be made into a solution by dissolving in a solvent in which the polyvinyl alcohol-based polymer is soluble. For example, polyvinyl alcohol includes water, dimethylimidazoline and the like. When an ethylene-vinyl alcohol copolymer is used, a mixed solvent of water / propanol may be used. The mixing ratio of propanol to water is preferably 30 to 70% by weight by weight.

The protective layer (A) and the protective layer (B)
When laminating the layers, the surface of the plastic film may be activated or the base layer may be laminated in order to further improve the adhesion to the plastic film. Examples of the surface activation treatment include a corona discharge treatment and a plasma discharge treatment.
Examples of the underlayer include a polyester resin having a hydrophilic group, an acrylic resin, a cured polyurethane resin, a cured phenoxy resin, and an ionic polymer complex.

On the metal oxide layer, the above-mentioned radiation-curable resin is coated with a hydrolyzate of alkoxysilane in an amount of 5 to 7 μm.
A radiation-cured film of a resin composition in which 5% by weight is mixed, or a cured polymer obtained by mixing an epoxy silicon compound and an amino silicon compound with a polyvinyl alcohol-based polymer and subjecting them to a thermal crosslinking reaction are preferable.

In the mixture of the radiation-curable resin and the hydrolyzate of the alkoxysilane, the adhesion of the hydrolyzate of the alkoxysilane to the metal oxide layer needs to be 5% by weight or more. Become.

These resin compositions are wet-coated on a plastic film and on a metal oxide layer laminated on the plastic film. As a coating method, for example, a known method such as a reverse roll coating method, a microgravure coating method, a direct gravure coating method, a kiss coating method, and a die coating method is used. Further, by diluting the resin composition with an appropriate organic solvent, it is possible to adjust the viscosity of the coating solution and the thickness of the layer.

Further, regarding the coating on the metal oxide layer, the surface treatment of the metal oxide layer is suitably performed for the purpose of enhancing the wettability of the coating liquid. As such a surface treatment, a known technique such as a corona discharge treatment, a plasma discharge treatment, or an alkali treatment can be used.

The transparent conductive layer is mainly composed of amorphous indium oxide, which is widely used for a transparent conductive film, contains 5 to 15% by weight of tin as a component thereof, and is used for the transparent conductive layer. Suitably, the film thickness is in the range from 20 to 200 nm.

An indium oxide film having high crystallinity has higher transparency and conductivity than an amorphous material, and is preferable as a transparent electrode material. However, a crystalline film is formed on a film having high flexibility. However, when the film is bent, it is easily broken and the handling property is deteriorated. In addition, the temperature at which thermocompression bonding can be performed is significantly reduced.

Here, the crystallinity and non-crystallinity of the formed indium oxide are defined as follows. When indium oxide is formed into a film by any method and its surface is observed with a transmission electron microscope, if there is a crystal, it is clearly observed as an aggregate of grains, that is, a polycrystal. With such an observation method, the case where the crystal grain area ratio per unit area is 20% or less is regarded as non-crystalline.

Indium oxide is a transparent electrical insulator by nature, but becomes a semiconductor when it contains a small amount of impurities or when oxygen is slightly insufficient. Preferred semiconductor metal oxides include, as impurities, indium oxide containing tin or fluorine. Particularly preferred is indium oxide containing 5 to 15% by weight of tin.
Shows good conductivity while maintaining high transparency.

The thickness is 20 to 200
The range of nm is appropriate. If the thickness is less than 20 nm, the sheet resistance becomes electrically high, and it is difficult to utilize the sheet as a good transparent conductive film. On the other hand, if the thickness is more than 200 nm, it is difficult to obtain a value of 80% or more as the light transmittance of the transparent conductive film at 550 nm, and it is easily broken when bent, which makes handling difficult. Such a transparent conductive layer can be provided by a known method such as an evaporation method and a sputtering method.

As described above, the present invention improves the adhesion between layers of a plastic liquid crystal display panel substrate using a metal oxide as a gas barrier layer, particularly when a stress is applied to the transparent conductive film surface on the transparent conductive layer side. With respect to the transparent conductive film having such a feature, for example, a base film such as a transparent electrode substrate of a liquid crystal panel, a transparent conductive substrate such as an electroluminescence panel, an electrochromic panel, and a surface heating element can be easily provided.

[0047]

EXAMPLES Various evaluations described in the following examples and comparative examples were performed in the following manner. Regarding the evaluation of adhesion, after the transparent conductive layer of the produced transparent conductive film was removed by etching treatment, a cross-cut adhesion test and a T-peel test were performed on the surface from which the transparent conductive layer was removed.

In the etching treatment, a 3% by weight aqueous hydrochloric acid solution containing 3% by weight of ferric chloride is used as an etching solution.
This was carried out by immersing the transparent conductive film at 30 ° C. for 10 minutes, thoroughly washing with water, removing the etching solution sufficiently, and completely wiping off the moisture.

The cross-cut adhesion test is JIS K54.
According to No. 00, a cross-cut test (cross-cut tape method) was performed. Then, the remaining rate of the cells was displayed in%.

The T-type peel test conformed to JIS standard K7113. The test piece was prepared by bonding two transparent conductive layer-removed films with their transparent conductive layer sides facing each other.
At this time, Bond Quick 30 manufactured by Konishi Co., Ltd. was used as the adhesive, and the bonding was performed so that the thickness of the bonding layer was 30 μm. The peel strength was measured at a peel speed of 200 mm / min using an Instron Model 4302, which is a known tensile tester.

[Example 1] A polycarbonate resin having an average molecular weight of 37000 comprising bisphenol A as a bisphenol component alone was dissolved in methylene chloride at 20% by weight. Then, this solution was cast on a polyester film having a thickness of 175 μm by a die coating method. Next, the residual solvent concentration was adjusted to 13% by weight in a drying oven, and the film was peeled off from the polyester film. Then, this polycarbonate film was dried in a drying furnace at a temperature of 120 ° C. while balancing the tension in the vertical and horizontal directions until the residual solvent concentration became 0.08% by weight.

The film thus obtained has a thickness of 10
It was 2 μm. Then, on one surface of the polycarbonate film, a 100-nm-thick magnesium-fluoride-containing oxide was deposited by vacuum deposition at a degree of vacuum of 67 mPa using a silicon oxide to which 10% by weight of magnesium fluoride was added as a deposition source. A silicon layer was laminated. This silicon oxide had an average composition of SiO _X and x was about 1.7.

Subsequently, after a corona discharge treatment was performed on the surface of the magnesium fluoride-containing silicon oxide layer at an integrated energy of 100 W · min / m 2, the following protective layer was laminated.

Vinyl trimethoxysilane (trade name: KBM100 manufactured by Shin-Etsu Chemical Co., Ltd.) is placed in a stirring vessel whose outside is cooled with water.
3) Add 148 parts by weight, and add 0.1 g with vigorous stirring.
54 parts of 01N hydrochloric acid was gradually added, and the mixture was slowly stirred for 3 hours to obtain a hydrolyzed liquid of vinyltrimethoxysilane.

Next, 50 parts by weight of an acrylic resin represented by the following chemical formula (5):

[0056]

Embedded image

50 parts by weight of the above-mentioned hydrolyzate of vinyltrimethoxysilane, 10 parts by weight of unhydrolyzed vinyltrimethoxysilane, and a photoinitiator 2-hydroxy-2-methyl-1-phenylpropan-1-one ( A coating liquid was prepared by mixing 5 parts by weight of Darocure 1173 (trade name, manufactured by Merck) and 0.02 parts by weight of silicone oil (SH28PA, manufactured by Dow Corning Toray Silicone Co., Ltd.) as a leveling agent.

This coating solution was coated on a magnesium fluoride-containing silicon oxide subjected to a corona discharge treatment by a microgravure roll coating method, and heated at 60 ° C. for 1 minute to volatilize and remove the residual solvent in the coating film. , 120W
/ Cm high pressure mercury lamp, 800mJ / m
The coating film is cured by irradiating it with ultraviolet light under the conditions of 2.
A μm solvent-resistant layer was formed.

Next, 50 W · mi is applied to the opposite film surface.
After performing a corona discharge treatment at an integrated energy of n / m2, the same protective layer as the protective layer laminated on the magnesium fluoride-containing silicon oxide layer was provided.

Next, an indium-tin oxide layer was formed as a transparent conductive layer on the protective layer side of the laminated film opposite to the magnesium fluoride-containing silicon oxide layer by a sputtering method to form a transparent conductive film. did. An indium-tin oxide target having a composition of indium and tin in a weight ratio of 9: 1 and a packing density of 90% was used as a sputtering target. After the laminated film was set in the continuous sputtering apparatus, the gas was evacuated to a pressure of 1.3 mPa, a mixed gas of Ar and O2 in a volume ratio of 98.5: 1.5 was introduced, and the atmospheric pressure was set to 0.27 Pa. I made it. DC sputtering was performed at a film temperature of 50 ° C. and an input power density of 1 W / cm 2. The transparent conductive layer obtained as a result had a crystal grain existence ratio of 0% in area ratio and was non-crystalline. Further, the film thickness was 130 nm, and the surface resistance value was 40Ω / □.

Table 1 shows the results of the cross-cut adhesion test and the T-peel test performed on the transparent conductive film.
From this, it was found that the adhesiveness was good and the mechanical properties after cell production were good.

Example 2 A polycarbonate film having a magnesium fluoride-containing silicon oxide layer laminated under the same manufacturing conditions as in Example 1 was used. 100 W · min / m on the surface of the magnesium fluoride-containing silicon oxide layer.
After performing the corona discharge treatment with the integrated energy of 2, the following protective layers were laminated.

Mixing of 100 parts by weight of EVAL-F (ethylene copolymerization ratio 32 mol%) manufactured by Kuraray Co., Ltd. as an ethylene vinyl alcohol copolymer, 720 parts by weight of water, 1080 parts by weight of n-propanol, and 100 parts by weight of n-butanol It was dissolved by heating in a solvent to obtain a homogeneous solution. SH30PA manufactured by Toray Dow Corning Co., Ltd. was added to this solution as a leveling agent.
0.1 part by weight and 62.4 parts by weight of acetic acid.
85.8 parts by weight of (3,4-epoxycyclohexyl) ethyltrimethoxysilane was added and stirred for 10 minutes. Further, 3-aminopropyltrimethoxysilane was added to the solution.
4 parts by weight were added and stirred for 3 hours to obtain a coating liquid.

This coating solution was coated on a magnesium fluoride-containing silicon oxide that had been subjected to corona discharge treatment by a microgravure roll coating method, and heat-treated at 130 ° C. for 3 minutes to form a solvent-resistant layer having a thickness of 2 μm.

Next, 50 W · mi is applied to the opposite film surface.
After performing a corona discharge treatment with an integrated energy of n / m 2, the following underlayer and protective layer were sequentially provided. The underlayer was a phenoxy-based cured resin layer. Specifically, as a phenoxy resin, phenototo YP manufactured by Toto Kasei Co., Ltd.
A solution obtained by mixing 20 parts by weight of -50, 50 parts by weight of methyl ethyl ketone and 30 parts by weight of 2-ethoxyethyl acetate as a solvent, and then mixing 10 parts by weight of A3 manufactured by Takeda Pharmaceutical Co., Ltd. as a curing agent isocyanate. Was coated using a Meyer bar and then at 130 ° C. for 2 hours.
A layer having a thickness of 1.5 μm was formed by performing a partial heat treatment and used as an underlayer. As the protective layer, the same protective layer as in Example 1 was laminated.

Next, the same transparent conductive layer as in Example 1 was laminated on the protective layer side provided on the surface of the laminated film opposite to the magnesium fluoride-containing silicon oxide layer.

Table 1 shows the results of the cross-cut adhesion test and the T-peel test for this transparent conductive film.
From this, it was found that the adhesiveness was good and the mechanical properties after cell production were good.

Example 3 A polycarbonate film having a magnesium fluoride-containing silicon oxide layer laminated under the same manufacturing conditions as in Example 1 was used. 100 W · min / m on the surface of the magnesium fluoride-containing silicon oxide layer.
After performing the corona discharge treatment with the integrated energy of 2, the same protective layer as the protective layer laminated on the magnesium fluoride-containing silicon oxide layer used in Example 2 was laminated. Next, the same protective layer was laminated on the opposite film surface. Next, the same transparent conductive layer as in Example 1 was laminated on the protective layer side provided on the surface of the laminated film opposite to the magnesium fluoride-containing silicon oxide layer. Table 1 shows the results of the cross-cut adhesion test and the T-peel test performed on this transparent conductive film.
Shown in From this, it was found that the adhesiveness was good and the mechanical properties after cell production were good.

Comparative Example 1 In the laminated structure of Example 3, the same transparent conductive layer as that of Example 1 was laminated on the protective layer side provided on the surface of the magnesium fluoride-containing silicon oxide layer.
The other conditions were the same as in Example 3. Table 1 shows the results of the cross-cut adhesion test and the T-peel test performed on the transparent conductive film. The peel interface at this time was polycarbonate / metal oxide. From this, it can be judged that even a material which can be determined to have adhesion in the cross-cut adhesion test has insufficient adhesion in the T-type peel test, and in fact, it is a material lacking in mechanical properties after cell production. Was.

[0070]

The present invention is intended to improve the adhesion between layers of a plastic liquid crystal display panel substrate using a metal oxide as a gas barrier layer, especially when a stress is applied to the transparent conductive film surface on the transparent conductive layer side. Regarding the transparent conductive film having features, for example, it is necessary to provide a transparent conductive film excellent in various properties as a base film of a transparent electrode substrate of a liquid crystal panel, a transparent conductive substrate of an electroluminescence panel, an electrochromic panel, a surface heating element, and the like. it can.

[0071]

[Table 1]

Claims (2)

[Claims] A gas barrier layer made of a metal oxide and a protective layer (A) are laminated in this order on one surface of a plastic film, and a protective layer (B) and a transparent conductive layer are formed on the other surface of the plastic film. Are laminated in this order. 2. A gas barrier layer made of a metal oxide having a thickness of 5 to 200 nm and containing silicon oxide having a ratio of the number of oxygen atoms to the number of silicon atoms of 1.5 to 2.0 as a main component. The transparent conductive film according to claim 1, wherein