JPH1016142A - Transparent gas barrier laminated film and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a laminated film, which is excellent in solvent resistance and gas barrier properties and has transparency, optical isotropy and planeness by a method wherein this laminated film is produced by forming a ceramic layer made of polysilazane and a specified hardened covering film on one side of a transparent polymer film. SOLUTION: This laminated film is produced by forming a ceramic layer made of polysilazane and a hardened covering layer containing vinyl alcohol crosslinked with the (partial) hydrolyzate, (partial) condensate or their mixture of the alkoxysilane represented by the formula contacting with each other on one side of a transparent polymer film. In the formula, R' is 1-4C alkylene group, R<2> and R<3> are 1-4C alkyl group, X is glycidoxy group or epoxycyclohexyl group and (n) is 1 or 0. In order to give the more favorable gas barrier properties, a transparent metal oxide layer may well be formed on at least one side of the transparent polymer film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent gas-barrier laminated film and a method for producing the same, and more particularly, to a film having excellent optical isotropy, flatness, solvent resistance, gas barrier properties, and flexibility. In addition, the present invention relates to a transparent gas barrier laminated film having good interlayer adhesion, and can be used as a transparent substrate for liquid crystal display devices, photoconductive photoconductors, surface light emitters, organic electroluminescence, and the like.

[0002]

2. Description of the Related Art In general, a glass substrate is used as a transparent substrate which has been applied to a liquid crystal display device or the like. However, in recent years, in addition to demands for weight reduction and enlargement of liquid crystal display elements, advanced requirements such as long-term reliability, freedom of shape, and curved surface display have been made. A film substrate made of transparent plastic or the like has been studied in place of a transparent glass substrate. In addition, the plastic substrate not only meets the above-mentioned requirements but also has a roll-to-roll system, so that it is advantageous in terms of productivity and cost reduction as compared with a glass substrate.

[0003] However, generally, a transparent plastic substrate has a drawback that gas barrier properties and solvent resistance are inferior to glass substrates. If the solvent resistance is poor, problems such as deformation and whitening of the substrate may occur at the time of cleaning the organic solvent in the liquid crystal cell forming step or forming the alignment film. On the other hand, if a substrate with poor gas barrier properties, i.e., oxygen barrier properties and water vapor barrier properties, is used, air and water vapor will permeate, bubbles will be generated inside the liquid crystal cell, and display will not be possible, deteriorating the display quality of the display. In particular, under severe conditions, such as for in-vehicle use, this defect easily occurs and becomes a serious problem.

[0004] Therefore, for the purpose of remedying the above-mentioned drawbacks, several proposals have been made in which an agent having solvent resistance and gas barrier properties is laminated on a transparent plastic substrate. For example, Japanese Patent Publication No. 5-52002 and Japanese Patent Publication No. 5-52003 disclose improving the adhesion between a polymer film and an oxygen gas barrier layer composed of a polyvinyl alcohol-based resin, and further improving the water vapor gas barrier property. Are described.

However, since polyvinyl alcohol is laminated on the outermost layer, these have insufficient solvent resistance and cause problems in the liquid crystal cell manufacturing process. In order to impart solvent resistance, it is necessary to further provide a layer having solvent resistance on the transparent substrate, which increases the cost.

Further, JP-A-2-137922 and JP-A-5-309794 disclose an anchor coat layer on a transparent polymer film, an ethylene-vinyl alcohol copolymer layer as a gas barrier layer, and a solvent resistant layer. A transparent substrate in which a curable resin layer is sequentially laminated on both sides as a layer is described. However, although these have satisfactory solvent resistance, they have a problem that the gas barrier properties are lowered at high humidity due to the characteristics of the gas barrier agent. In addition, as many as six coatings are costly.

[0007] Further, in the case of a transparent substrate such as a liquid crystal display device, in addition to the above-mentioned requirements for solvent resistance and gas barrier properties, there are also requirements for high transparency, optical isotropy, flatness and the like. This is because when the transparency of the substrate is low or when there is birefringence, problems such as coloring of display and reduction in contrast occur. When the flatness is low, the gap between the liquid crystal layers is not uniform, and the liquid crystal alignment also becomes uneven, and the substrate itself also becomes optically uneven, so that the display color becomes uneven.

Further, if the flatness, transparency, and gas barrier properties easily deteriorate due to mechanical and thermal influences, practicality utilizing characteristics of lightness, thinness, free shape, and curved surface display is required. This makes it difficult to adapt to applications where external influences such as pagers, mobile phones, electronic organizers, and pen input devices are greatly affected. In particular, in order to maintain such characteristics with respect to mechanical effects, good adhesion between the layers stacked for expressing the characteristics is also required.

[0009]

DISCLOSURE OF THE INVENTION The present invention is intended to solve such a problem and is excellent in solvent resistance and gas barrier properties, and has the above-mentioned transparency, optical isotropy, and flatness. An object of the present invention is to provide a transparent gas-barrier laminated film having excellent adhesiveness and good interlayer adhesion, further reducing the number of layers, and suppressing production cost.

[0010]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a ceramic layer (A layer) formed of polysilazane and (partial) hydrolysis of a specific alkoxysilane. A layer composed of a product, a (partial) condensate thereof, and a cured coating layer (B layer) containing a vinyl alcohol-based resin cross-linked with a mixture thereof, having a gas barrier property independent of humidity Furthermore, since both the layer A and the layer B were crosslinked and cured films, they were found to have very good solvent resistance. Further, it has been found that both the A layer and the B layer have good adhesion to the base material provided with the polymer film and the metal oxide layer, and the present invention has been completed.

That is, the present invention relates to a transparent polymer film or a transparent gas barrier laminated film having a metal oxide layer, on at least one side of which, a ceramic layer (A layer) formed of polysilazane, 1)

[0012]

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(Where R ¹ is an alkylene group having 1 to 4 carbon atoms, R ² and R ³ are alkyl groups having 1 to 4 carbon atoms, X is a glycidoxy group or an epoxycyclohexyl group, and n is 1 or 0) (Partial) hydrolyzate, (partial) condensate or a mixture thereof of an alkoxysilane having an epoxy group represented by the following general formula (2):

[0014]

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(Where R ⁴ is an alkylene group having 1 to ⁴ carbon atoms, R ⁵ and R ⁶ are alkyl groups having 1 to 4 carbon atoms, Y is a hydrogen atom or an aminoalkyl group, and m is 1 or 0) A) a cured resin layer (B layer) containing a vinyl alcohol-based resin cross-linked by a (partially) hydrolyzed product, a (partially) condensate or a mixture thereof of an alkoxysilane having an amino group and / or an imino group represented by And (b) have a layer formed in contact with each other.

The present invention also relates to a method for producing the above-mentioned laminated film having a transparent gas barrier property, wherein at least one side of a transparent polymer film or a transparent polymer film having a metal oxide layer (C layer) on at least one side. , Below (a)
To (d) (a) a vinyl alcohol resin, (b) a (partial) hydrolyzate of an alkoxysilane having an epoxy group represented by the above general formula (1), a partial condensate thereof, or a mixture thereof, (c) A (partial) hydrolyzate of an alkoxysilane having an amino group and / or an imino group represented by the general formula (2), a partial condensate thereof, or a mixture thereof, and (d) a vinyl alcohol resin soluble solvent in all solvents A solvent containing 50% by weight or more, (a) /
After applying the alkoxysilane coating composition in which [(b) + (c)] = 9/1 to 1/3 (weight ratio), at least a dry film is formed, and then polysilazane and polysilazane are formed on the dry film. After applying the polysilazane coating composition containing at least a soluble solvent,
The cured resin layer (B layer) in which the dried film is cured by inversion.
A ceramic layer (A layer) is formed thereon. A cured resin layer (B
On the layer), a polysilazane coating composition may be applied.

Further, the above-mentioned manufacturing method includes a method of forming the above-mentioned ceramic layer (layer A) and then forming the above-mentioned cured resin layer (layer B) in contact with the layer A.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
When the laminated film of the present invention is used for a transparent electrode or the like of a liquid crystal display device, it is preferable that the laminated film has a light transmittance at 550 nm of 80% or more and a retardation value of 30 nm or less. If the light transmittance at 550 nm is less than 80%, the image quality is not practically sufficient, and if the retardation value exceeds 30 nm, there are problems in coloring and viewing angle characteristics.

In the present invention, examples of the transparent polymer film include transparent plastic films such as polyester, polycarbonate, polyarylate, polysulfone, and polyethersulfone. Films of polycarbonate and polyarylate are more suitable from the viewpoint of the optical properties that the properties are low. The size of the transparent polymer film is usually 30 μm or more and 800 μm or less.

The transparent polymer film may be provided with a transparent metal oxide layer (C layer) on at least one surface thereof in order to give better gas barrier properties.

Examples of the metal oxide layer forming the C layer include transparent metal oxide layers of silicon, aluminum, magnesium, zinc and the like.
It is produced by a known sputtering method, vacuum deposition method, ion plating method, plasma CVD method, or the like. Above all,
As a metal oxide having a good gas barrier property, a silicon oxide is particularly preferable in terms of adhesiveness to a transparent polymer film, and further, transparency, flatness, flexibility, cost, and the like.

The composition of the silicon oxide is analyzed and determined by X-ray photoelectron spectroscopy, X-ray microspectroscopy, Auger electron spectroscopy, Rutherford backscattering, and the like. In view of the above, x is preferably in the range of 1.5 ≦ x ≦ 2 in the average composition represented by SiOx. If the x value is less than 1.5, the flexibility and transparency will be poor.

The thickness of the C layer is 5 nm to 200 nm.
Is preferable. If the thickness of the C layer is less than 5 nm, it is difficult to form a film uniformly, and a portion where the film is not formed occurs, and gas penetrates from this portion, resulting in poor gas barrier properties. On the other hand, when the thickness exceeds 200 nm, not only lacks transparency, but also has poor flexibility, cracks are generated, and gas barrier properties are impaired.

In the present invention, the ceramic layer (layer A) formed of polysilazane has a number average molecular weight of 100 to 50,000 having a main skeleton composed of repeating units represented by the following general formulas (3) and (4). It is obtained by applying a polysilazane coating composition containing a modified product thereof (hereinafter, simply referred to as polysilazane), forming a polysilazane film on a film, and then converting the film to ceramics.

[0025]

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The above polysilazane coating composition comprises:
It is obtained by dissolving polysilazane in a solvent.
Solvents for dissolving polysilazane include benzene, toluene, xylene, ethylbenzene, pentane, hexane, isohexane, methylpentane, heptane, isoheptane, octane, isooctane, cyclopentane, cyclohexane, ligroin, acetone, methyl isobutyl ketone, ethyl acetate, acetic acid Isobutyl, cyclohexyl acetate, ethyl ether, butyl ether, 1,4-dioxane, tetrahydrofuran, methylene chloride, ethylene chloride and the like. These solvents can be used alone or
More than one species can be used together.

The content of the polysilazane in the coating composition varies depending on the molecular weight of the polysilazane used, but is preferably in the range of 0.1% by weight to 50% by weight. In addition, various additives and fillers may be mixed in the coating composition as needed. The amount and type of these additives can be determined depending on the purpose of addition of the additives such as, for example, a ceramicization accelerator for polysilazane and the effects thereof.

In the present invention, a commonly used method such as dip coating, spray coating, flow coating, roll coating, bar coating, and spin coating is used as a coating method for forming the layer A. The thickness of the A layer is preferably in the range of 5 nm to 3,000 nm. If the thickness of the layer A 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 penetrates from this portion, and the gas barrier property deteriorates, which is not preferable. On the other hand, if the thickness exceeds 3,000 nm, cracks occur when the polysilazane is ceramicized, which is not preferable.

In the present invention, the method for converting the polysilazane into a ceramic is not particularly limited. For example, when the transparent polymer film to be used is an amorphous polymer, the temperature does not exceed the glass transition point of the film. , Preferably 5
The heat treatment can be performed in the range of 0 to 300 ° C. In order to promote the conversion of polysilazane to ceramics, known conversion conditions such as exposure to a steam atmosphere and immersion in distilled water containing a catalyst, as reported in JP-A-7-223867, can also be used. It is.

In general, polysilazane is converted into ceramics such as silica by heat treatment in the air, which breaks Si—H and NH bonds and generates Si—O bonds.
The degree of this conversion can be evaluated semi-quantitatively by IR measurement according to the equation defined below.

[0031]

## EQU1 ## SiO / SiN ratio = SiO absorbance after conversion / SiN absorbance after conversion

Here, the SiO absorbance is about 1160 c
m ^-1 and SiN absorbance are calculated from characteristic absorption of about 840 cm ^-1 . The higher the SiO / SiN ratio, the more the conversion to ceramics with a silica composition closer to that.

In the present invention, the ratio of SiO / SiN, which is an index of the degree of conversion to ceramics, is preferably at least 0.3, more preferably at least 0.5. If it is less than 0.3, an expected gas barrier property may not be obtained, which is not preferable.

The cured resin layer containing a vinyl alcohol-based resin crosslinked with a (partial) hydrolyzate of a specific alkoxysilane, a (partial) condensate thereof or a mixture thereof, which is the layer B of the present invention, comprises (a) (B) a (partial) hydrolyzate of an alkoxysilane having an epoxy group, a (partial) condensate thereof or a mixture thereof, and (c) an alkoxysilane having an amino group and / or an imino group. An alkoxysilane coating composition comprising a (partial) hydrolyzate, a (partial) condensate thereof, or a mixture thereof, and a solvent containing (d) a vinyl alcohol-based resin-soluble solvent in an amount of 50% by weight or more based on the total solvent amount is applied. It is obtained by heating and curing, but in the case of the layer A, at least a dry film is formed, and then the layer A is formed. It can also be obtained by heating and curing.

Here, as the vinyl alcohol resin (a), a known commercially available resin can be used, and a polymer resin containing a vinyl alcohol component at 60 mol% or more is preferable. Specific examples include polyvinyl alcohol, vinyl alcohol-vinyl acetate copolymer, vinyl alcohol-vinyl butyral copolymer, ethylene-vinyl alcohol copolymer, and polyvinyl alcohol having a silyl group in the molecule. Above all, polyvinyl alcohol and polyvinyl alcohol having a silyl group in the molecule are preferably used from the viewpoint of gas barrier properties, solvent resistance and adhesion.

In the present invention, (b) an alkoxysilane which gives a (partial) hydrolyzate of an alkoxysilane having an epoxy group, a (partial) condensate thereof or a mixture thereof is represented by the following general formula (1)

[0037]

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An alkoxysilane having an epoxy group represented by the following formula:

In the above formula (1), R ¹ has 1 to ¹ carbon atoms.
4 is an alkylene group, R ² and R ³ are an alkyl group having 1 to 4 carbon atoms, X is a glycidoxy group or an epoxycyclohexyl group, and n is 1 or 0.

Examples of the alkoxysilane having an epoxy group include glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, glycidoxymethyltripropoxysilane, glycidoxymethyltributoxysilane, and 2-glycol Sidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 2-glycidoxyethyltripropoxysilane, 2-glycidoxyethyltributoxysilane, 1-
Glycidoxyethyltrimethoxysilane, 1-glycidoxyethyltriethoxysilane, 1-glycidoxyethyltripropoxysilane, 1-glycidoxyethyltributoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Glycidoxypropyltriethoxysilane, 3-glycidoxypropyltripropoxysilane,
3-glycidoxypropyltributoxysilane, 2-glycidoxypropyltrimethoxysilane, 2-glycidoxypropyltriethoxysilane, 2-glycidoxypropyltripropoxysilane, 2-glycidoxypropyltributoxysilane, 1-glycidoxypropyltrimethoxysilane, 1-glycidoxypropyltriethoxysilane, 1-glycidoxypropyltripropoxysilane, 1-glycidoxypropyltributoxysilane,
(3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, (3,4-epoxycyclohexyl) methyltripropoxysilane, (3,4-epoxycyclohexyl) methyltributoxy Silane, 2-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltripropoxysilane, 2- (3
4-epoxycyclohexyl) ethyltributoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, 3- (3,4-
Epoxy (cyclohexyl) propyltripropoxysilane, 3- (3,4-epoxycyclohexyl) propyltributoxysilane, 4- (3,4-epoxycyclohexyl) butyltrimethoxysilane, 4- (3,4-epoxycyclohexyl) butyltrisilane Ethoxysilane, 4
-(3,4-epoxycyclohexyl) butyltripropoxysilane, 4- (3,4-epoxycyclohexyl) butyltributoxysilane, diethoxy-3-glycidoxypropylmethylsilane and the like.

Among them, particularly preferred alkoxysilanes having an epoxy group are 3-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. These compounds can be used alone or in combination of two or more.

In the present invention, (c) an alkoxysilane having a (partial) hydrolyzate, (partial) condensate or a mixture thereof of an alkoxysilane having an amino group and / or an imino group is represented by the following general formula (2) )

[0043]

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An alkoxysilane having an amino group and / or an imino group represented by

In the above formula (2), R ⁴ has 1 to 1 carbon atoms.
4, an alkylene group, R ⁵ and R ⁶ are an alkyl group having 1 to 4 carbon atoms, Y is a hydrogen atom or an aminoalkyl group, and m is 1 or 0.

Examples of the alkoxysilane having an amino group and / or an imino group include, for example, aminomethyltriethoxysilane, 2-aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane, 2-aminoethyltripropoxysilane, -Aminoethyltributoxysilane, 1-aminoethyltrimethoxysilane,
1-aminoethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltripropoxysilane, 3-aminopropyltributoxysilane, 2-aminopropyltrimethoxysilane, 2- Aminopropyltriethoxysilane, 2-aminopropyltripropoxysilane, 2-aminopropyltributoxysilane, 1-
Aminopropyltrimethoxysilane, 1-aminopropyltriethoxysilane, 1-aminopropyltripropoxysilane, 1-aminopropyltributoxysilane,
N-aminomethylaminomethyltrimethoxysilane, N
-Aminomethylaminomethyltripropoxysilane, N
-Aminomethyl-2-aminoethyltrimethoxysilane, N-aminomethyl-2-aminoethyltriethoxysilane, N-aminomethyl-2-aminoethyltripropoxysilane, N-aminomethyl-3-aminopropyltrimethoxysilane , N-aminomethyl-3-aminopropyltriethoxysilane, N-aminomethyl-3-aminopropyltripropoxysilane, N-aminomethyl-2-aminopropyltrimethoxysilane, N-aminomethyl-2-aminopropyltriethoxysilane Ethoxysilane, N-
Aminomethyl-2-aminopropyltripropoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -2-aminoethyltrimethoxysilane, N- (2
-Aminoethyl) -2-aminoethyltriethoxysilane, N- (2-aminoethyl) -2-aminoethyltripropoxysilane, N- (2-aminoethyl) -1-aminoethyltrimethoxysilane, N- ( 2-aminoethyl) -1-aminoethyltriethoxysilane, N- (2
-Aminoethyl) -1-aminoethyltripropoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-
Aminopropyltripropoxysilane, N- (3-aminopropyl) -2-aminoethyltrimethoxysilane,
N- (3-aminopropyl) -2-aminoethyltriethoxysilane, N- (3-aminopropyl) -2-aminoethyltripropoxysilane, N-methyl-3-aminopropyltrimethoxysilane, 3-aminopropyl Methyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-diethylenetriaminepropyltriethoxysilane, 3- [2- (2-
Aminoethylaminoethylamino) propyl] trimethoxysilane, trimethoxysilylpropyldiethylenetriamine and the like.

Among them, particularly preferred alkoxysilanes having an amino group and / or imino group are 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-
Aminopropylmethyldimethoxysilane. These compounds can be used alone or in combination of two or more.

The (partial) hydrolyzate of alkoxysilane and its (partial) condensate include those obtained by partially or wholly hydrolyzing the alkoxysilane and those obtained by subjecting part or all of the hydrolyzate to a condensation reaction. And the (partial) hydrolyzate condensed with the unhydrolyzed raw material alkoxysilane, which is obtained by a so-called sol-gel reaction.

When the alkoxysilane is used, it can be added as a component as it is, or after hydrolysis in advance, a (partial) hydrolyzate of the alkoxysilane and a partial condensate thereof are used. It is also possible.

For hydrolysis, a usual method, for example, a method of hydrolysis with an inorganic acid such as hydrochloric acid, an organic acid such as acetic acid or an alkali such as caustic soda, or using only water can be used. It is also possible to carry out the hydrolysis after mixing the alkoxysilane and the solvent for the purpose of performing the hydrolysis uniformly. Depending on the purpose, cooling or heating can be performed during the hydrolysis. Further, the alcohol or the like after hydrolysis is heated and / or
Alternatively, it is also possible to remove an appropriate amount under reduced pressure before use, or to add an appropriate solvent thereafter.

The solvent of the component (d) is a solvent containing a vinyl alcohol resin soluble solvent in an amount of 50% by weight or more based on the total amount of the solvent. The vinyl alcohol-based resin soluble solvent may be appropriately selected according to the resin used,
For example, water and dimethylimidazoline are used for polyvinyl alcohol (having a saponification degree of 99% or more), and a mixed solvent of water and propanol is used for an ethylene-vinyl alcohol copolymer.

The solvent that can be used in combination may be any solvent that can be uniformly mixed with the vinyl alcohol-based resin-soluble solvent, and is appropriately selected to adjust the evaporation rate, leveling property, and the like of the coat film.

Each of the components (a) to (d) has the following ratio. That is, component (a), component (b), and component (c)
Weight ratio (a) / [(b) + (c)] is 9/1 to 1/3
Use within the range. Here, the component (b) is represented by the following formula (5)

[0054]

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The component (c) based on the weight of the compound represented by the following formula is represented by the following formula (6).

[0056]

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Based on the weight of the compound represented by
When (a) / [(b) + (c)] is more than 9/1, the solvent resistance tends to be inferior, and when it is less than 1/3, the gas barrier property tends to decrease.

The mixing ratio of the component (b) and the component (c) affects the performance of the cured resin film to be obtained, and (epoxy group) / (sum of amino group and imino group) is calculated in terms of molar equivalent. When 2/1 to 1/4, adhesion, heat resistance, chemical resistance,
A cured resin film having excellent water resistance and durability can be obtained. Either the component (b) or the component (c) becomes excessive relative to the other, and the performance of the cured resin film deteriorates as it deviates from the above range.

Component (c) is a condensation catalyst for the hydrolyzate of component (b), and at the same time acts as a polymerization catalyst for epoxy groups. Therefore, when component (c) is added to the hydrolyzate of component (b), The reaction occurs rapidly and the coating solution gels. Therefore, it is preferable to adjust the pot life by adding a carboxylic acid to the component (c) and using it as a weakly acidic organic acid salt in the preparation.

The carboxylic acid includes, for example, formic acid, acetic acid, propionic acid, butyric acid and the like, and acetic acid is most preferable in view of its acidity and volatility. The amount of the carboxylic acid to be added is in the range of 0.1 to 10 mol, preferably 0.5 to 5.0 mol, per 1 mol of the total of the amino groups and imino groups of the component (c). Is 0.
If the amount is less than 1 mol, the pot life of the coating solution prepared from this becomes short, and the coating solution tends to gel. On the other hand 10
If the molar amount is exceeded, the curing of the coating liquid becomes insufficient, and the performance of the obtained cured resin film is reduced.

Further, the component (d) is composed of the components (a) and (b)
And 100 parts by weight of the total solid content of (c), 20
A range of 0 to 99900 parts by weight is preferably used. When the amount is less than 200 parts by weight, the storage stability of the composition is deteriorated. On the other hand, when the amount is more than 99900 parts by weight, the storage stability of the composition itself is improved, but the solid content in the composition is reduced and the composition is obtained by coating. The thickness of the cured resin film to be obtained is limited.

Further, a curing catalyst can be added to the alkoxysilane coating composition, if necessary. As the curing catalyst, for example, aluminum acetylacetonate, aluminum ethyl acetoacetate bisacetylacetonate, aluminum bisacetoacetate acetylacetonate, aluminum di-n-
Aluminum chelate compounds such as butoxide monoethyl acetoacetate and aluminum di-i-propoxide monomethyl acetoacetate; alkali metal salts of carboxylic acids such as sodium acetate, potassium acetate and potassium formate; dimethylamine acetate, ethanol acetoate, dimethylaniline phosphate Amine carboxylates such as mate; quaternary ammonium salts such as benzyltrimethylammonium hydroxide, tetramethylammonium acetate and benzyltrimethylammonium acetate; metal carboxylate salts such as tin octoate; triethylamine, triethanolamine and pyridine Such amines; and 1,8-diazabicyclo [5,4,0] -7-undecene are used. These compounds can be used alone or in combination of two or more.

Various surfactants can be added to the coating composition for the purpose of improving the surface smoothness. For example, silicone compounds, fluorine surfactants, organic surfactants and the like can be used. it can. Further, as a modifier, various epoxy resins, melamine resins, amide resins, colloidal silica, etc., which are compatible with the coating composition may be added. Such components (a) to (d)
The additional components other than the above have various practical properties depending on the application to which the present invention is applied, such as heat resistance, weather resistance, water resistance, durability, adhesion, or solvent resistance to the cured resin film of the present invention. Can be improved.

In preparing the alkoxysilane coating composition used in the present invention, for example, components (a) to
(D) may be mixed at once. At that time, the compounds represented by the general formula (1) and the compounds of the general formula (2) can be used even if the components (b) and (c) have been subjected to a treatment such as hydrolysis in advance. . Both are useful methods for preparing the alkoxysilane coating composition used in the present invention. Preferably, a carboxylic acid is added to a solution composed of (a) and (d), and then represented by the general formula (2). It is preferable to add the compound and the compound represented by the general formula (1). Moreover, you may heat at each adjustment stage of this coating composition as needed. Furthermore, you may ripen as needed.

In the manufacturing method of the present invention, the coating method for forming the layer B is the same as that for the layer A, such as dip coating, spray coating, flow coating, roll coating, bar coating,
A commonly used coating method such as spin coating is used. The thickness of the layer B is preferably in the range of 0.01 to 100 μm, and more preferably 0.1 to 100 μm. If the thickness of the cured resin layer is less than 0.01 μm, the gas barrier properties are insufficient, and if it exceeds 100 μm, it takes a long time to cure the coat film, which is economically undesirable.

The polymer film coated with the alkoxysilane coating composition is usually subjected to evaporation of the solvent at a temperature from room temperature to a temperature not higher than the glass transition point of the film, and then to a temperature of 50 ° C. or higher, preferably 80 ° C. or higher. And heat cure.

In this process, the reaction such as the crosslinking of the component (a) vinyl alcohol resin in the alkoxysilane coating composition by the (partial) hydrolyzate of the alkoxysilane of the components (b) and (c) is performed. Then, a layer B composed of a transparent cured resin film is formed.

In the transparent gas barrier laminate film of the present invention, the layer A and the layer B only need to be in contact with each other. Therefore, the production method includes a metal oxide layer (C layer).
Alternatively, the layer in contact with the transparent polymer film includes a production method in which any layer is formed.

That is, both the A layer and the B layer of the laminated film of the present invention are crosslinked and cured coatings, have extremely good adhesion to a polymer film, especially a polycarbonate film, and have an alkali resistance and an N resistance. -It is extremely excellent in solvent resistance such as methylpyrrolidone (NMP) property. This means that the degree of freedom of the laminated structure is high, that is, the laminated film only needs to have the layer A and the layer B in contact with and laminated on at least one side of the transparent polymer film. Either a method of laminating the layer A and then the layer B on the molecular film, or a method of laminating the layer B and laminating the layer A may be used.

Since the A layer and the B layer have good adhesion to the metal oxide layer (C layer) described above, the laminating method is not limited even in a transparent laminated film having the C layer. In the case of the transparent laminated film having only the C layer, the method of laminating the A layer on the C layer and then laminating the B layer, or the method of laminating the B layer on the C layer and then laminating the A layer Good.

At this time, the preferred mode of the above-mentioned method for forming the ceramics of the A layer and curing the B layer differs depending on whether the A layer or the B layer is formed on the C layer. That is, when the layer B is laminated on the layer A, the conversion to ceramics is performed on the layer A with the SiO / SiN ratio of 0.3 or more.
Preferably, the layers are laminated and cured by heating. The heat treatment time at this time depends on the treatment temperature, and cannot be said unconditionally. For example, when the heat treatment is performed at a temperature of 130 ° C., the heat treatment time is 3 minutes or more, preferably 5 minutes or more, more preferably 10 minutes or more. Is performed. If it is less than 3 minutes, gas barrier properties may not be obtained, which is not preferable.

On the other hand, when the layer A is laminated on the layer B,
The layer A may be laminated before the layer B is heat-cured, or the layer A may be laminated after the layer B is cured. The heat treatment time of the layer B depends on the processing temperature. For example, when the temperature is 130 ° C., the time can be reduced to less than 3 minutes to about 1 minute.

Therefore, if the order of laminating the A layer and the B layer is changed, a suitable heat treatment time is different, and from the viewpoint of productivity,
It is preferable to stack the layer B, which can shorten the heat treatment time, and then stack the layer A.

Also, a laminated film in which the layer A and the layer B are laminated on the surface of the transparent polymer film on which the layer C is not provided is a preferred example of the present invention.
In particular, in the case where 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 aqueous alkali solution. In this case, it is preferable to provide a solvent-resistant layer. As a solvent-resistant layer, it shows solvent resistance,
What has good adhesion with the metal oxide to be used may be appropriately selected. For example, when silicon oxide is used as the metal oxide layer, the crosslinked vinyl alcohol-based resin as the B layer of the present invention, A radiation-curable resin mixed with a hydrolyzate of an alkoxysilane as described in JP-A-7-336664 is exemplified.

[0075]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. Various measurements in the examples were performed as described below.

Appearance of laminated film: Coloring and the presence of uneven coating were examined by visual observation.

Transparency: Spectrophotometer (U-Made by Hitachi, Ltd.)
3500), the light transmittance of a parallel light beam having a wavelength of 550 nm was measured. The haze value (ΔH%) was measured using COH-300A manufactured by Nippon Denshoku.

Optical Isotropy: The retardation value for light having a wavelength of 590 nm was measured using a multi-wavelength birefringence measuring apparatus M-150 manufactured by JASCO Corporation.

Flatness: Surface roughness Ra was measured using TOPO-3D manufactured by WYCO. Here, Ra is the center line average roughness obtained when measuring a rectangular surface having a side length of 256 μm on the film surface at an interval of 1 μm at a magnification of 400 times using a phase shift interferometer as a measurement principle. That is.

Solvent resistance: immersed in a 3.5% NaOH aqueous solution at 25 ° C. for 10 minutes, washed sufficiently with running water,
After drying, the appearance was visually observed.

Solvent resistance: The film was immersed in a 5.0% HCl aqueous solution at 25 ° C. for 10 minutes, washed sufficiently with running water, dried, and visually observed.

Solvent resistance: A few drops of N-methylpyrrolidone at 80 ° C. were dropped on the laminated film, left for 5 minutes, sufficiently washed with running water, and the appearance was visually observed.

Gas barrier property: Oxygen permeability was measured at 30 ° C. and 50% RH using OX-TRAN 2/20 manufactured by Modern Control (MOCON). Gas barrier property: OX-TRAN manufactured by MOCON
Oxygen permeability was measured using a 2/20 type at 30 ° C. and 90% RH atmosphere.

Adhesion: 1 m vertically and horizontally on the surface of the test piece with a knife
Cuts are made at m intervals to form 100 grids.
After a cellophane tape (Cellotape, trade name, manufactured by Nichiban Co., Ltd.) was stuck thereon, the film was peeled off at once from the surface in a direction of 90 degrees, and the adhesiveness was evaluated by the number of eyes remaining on the surface. Therefore, 100/100 is perfect adhesion, 0/10
0 means complete peeling (based on JIS K5400).

Flexibility: The laminated film was wound around a lot of 10 mmφ, and the presence or absence of appearance change such as crack generation was observed.

Durability: 60 ° C., 90% RH in a constant temperature and humidity oven
For 100 hours, and the presence or absence of an appearance change of the cured film after natural cooling was observed.

The production of a polymer film common to Examples 1 to 6 and Comparative Examples 1 to 4 is as follows.

(1) Production of Polymer Film A polycarbonate resin having an average molecular weight of 37,000, consisting of bisphenol A alone, was dissolved in methylene chloride to a concentration of 20% by weight. This solution is applied to a thickness of 1 by die coating method.
It was cast on a 75 μm polyester film. Next, it was dried in a drying oven until the residual solvent concentration became 13% by weight, and was peeled off from the polyester film. Then, the obtained polycarbonate film was dried in a drying furnace at a temperature of 120 ° C. while balancing the longitudinal and horizontal tensions until the residual solvent concentration became 0.08% by weight.

The transparent film thus obtained has a thickness of 103 μm and a light transmittance at a wavelength of 550 nm of 91 μm.
%Met.

Further, an average molecular weight of 2
A polyethersulfone film was obtained using 2,000 polyethersulfone resins. This film has a thickness of 95 μm and a light transmittance of 8 at a wavelength of 550 nm.
9%.

(2) Preparation of Polysilazane Coating Composition Perhydropolysilazane (low-temperature firing type) manufactured by Tonen Co., Ltd. was used as polysilazane, and a mixed solvent of m-xylene and n-hexane was used as polysilazane-soluble solvent. The polysilazane content was adjusted to 1% by weight (composition) or 5% by weight (composition), and the mixture ratio of m-xylene and n-hexane was adjusted to 50:50 (weight ratio).

(3) Preparation of Alkoxysilane Coating Composition Next, with the charged compositions shown in Tables 2 and 3, the alkoxysilane coating compositions a to g of the transparent gas barrier laminate film of the present invention, which provide layer B, were prepared. Types were prepared. A specific preparation method will be described later. In the following examples,
As for the components (b) and (c), each coating composition was prepared using a compound before hydrolysis (alkoxysilane represented by the general formula (1) or (2)). Also in Tables 2 and 3, the charged composition describes the compound as components (b) and (c).

(4) Formation of Metal Oxide Layer (C Layer) A metal oxide layer (C layer) was formed on one surface of the polyethersulfone film. As a metal oxide, a small piece of SiO was heated and evaporated in a vacuum of 5 × 10 ⁻⁵ torr to a thickness of 20 μm.
nm of a silicon oxide film was formed. In this silicon oxide, x was about 1.7 in the average composition of SiOx.

(5) Operation of Examples and Comparative Examples The polycarbonate films (200 × 3
00 mm), or 20 nm thick as a metal oxide thin film
A polysilazane coating composition on a polyethersulfone film (200 × 300 mm) provided with SiO _1.7 and alkoxysilane coating compositions a to g after aging at room temperature for 24 hours after preparation
Were respectively coated using a Meyer bar in the order shown in Table 2 or 3, and heat-treated under the conditions shown in Tables 2 and 3 to obtain laminated films having the respective film thicknesses shown in Tables 2 and 3. Various tests were performed using the test pieces thus obtained. The results are shown in Tables 2 and 3.

In Tables 2 and 3, the heat treatment conditions for the B layer indicate the heat treatment conditions for the B layer only when the coating of the alkoxysilane coating composition was performed before that of the polysilazane coating composition.

Reference Examples 1 to 6 (Evaluation of Ceramic Conversion of Polysilazane) The degree of conversion to ceramics was determined by IR measurement according to the following equation.

[0097]

## EQU2 ## SiO / SiN ratio = SiO absorbance after conversion / SiN absorbance after conversion

The SiO absorbance is about 1160 cm ^-1 , SiN
Absorbance was calculated from characteristic absorption at about 840 cm ^-1 . Si
The higher the O / SiN ratio, the more conversion to ceramics having a silica composition is progressing.

More specifically, the polysilazane coating composition prepared in the examples (in the table, the coating composition)
On a silicon wafer (15 × 25 × 0.5 mm)
Is coated using a spin coater and has a thickness of 50n.
A polysilazane coating having a thickness of 150 nm was obtained. This coating film was treated under the conditions shown in Table 1, and the SiO / SiN ratio was determined from the IR spectrum of the treated coating film. Reference Example 4
Indicates processing conditions of 130 ° C. × 15 minutes after 150 ° C. × 30 minutes. Table 1 shows the results.

[0100]

[Table 1]

Next, examples and comparative examples will be described. [Example 1] In this example, a transparent polymer film is made of polycarbonate, layer A is laminated thereon, heat-treated, and layer B is laminated.

As the vinyl alcohol resin (a) of the alkoxysilane coating composition, polyvinyl alcohol (Gohsenol NM- manufactured by Nippon Synthetic Chemical Co., Ltd.)
11Q (a degree of saponification of 99% or more)), using 3-glycidoxypropyltrimethoxysilane as an alkoxysilane having an epoxy group, and aminopropyltrimethoxysilane as an alkoxysilane having an amino group,
(A) / [(b) + (c)] = 2/1 (weight ratio), (epoxy group) / (sum of amino group + imino group) = 1/1
(Molar ratio). In preparing the coating composition, acetic acid is mixed with a solution composed of polyvinyl alcohol and distilled water (d), and after the solution is homogenized, aminopropyltrimethoxysilane is added dropwise to carry out a hydrolysis reaction, and the reaction is carried out for 30 minutes. After continuing stirring as it is, 3-glycidoxypropyltrimethoxysilane was added.

The degree of conversion of the layer A to ceramics was 1.1 in terms of the SiO / SiN ratio obtained in Reference Example 3. As shown in Table 2, the obtained test pieces had good evaluation results.

Example 2 In this example, a transparent polymer film is made of polycarbonate, a layer B is laminated thereon, a heat treatment is performed for 2 minutes, and a layer A is laminated.

The alkoxysilane coating composition comprises:
About the kind of each component and the preparation method, it carried out similarly to Example 1. The degree of conversion of the A layer to ceramics was 0.7 in terms of the SiO / SiN ratio obtained in Reference Example 1. All evaluation results were good.

Example 3 In this example, a transparent polymer film is made of polycarbonate, a layer B is laminated thereon, heat-treated for 2 minutes, and then a layer A is laminated.

Silanol group-containing polyvinyl alcohol (R1130) manufactured by Kuraray Co., Ltd. was added to (a) vinyl alcohol resin of the alkoxysilane coating composition.
2- (3,4) is added to the alkoxysilane having an epoxy group.
(A) / [(b) + (c)] using (epoxycyclohexyl) ethyltrimethoxysilane and N- (2-aminoethyl) -3-amino-propyltrimethoxysilane as an alkoxysilane having an amino group. = 3/1 (weight ratio), (epoxy group) / (sum of amino group + imino group)
= 3/4 (molar ratio), the charge composition was adjusted,
The preparation method was the same as in Example 1.

The degree of conversion of the layer A into ceramics was 0.7 in terms of the SiO / SiN ratio obtained in Reference Example 1. As shown in Table 2, all the evaluation results were good.

[Example 4] A transparent polymer film is a polyethersulfone film having a silicon oxide film (C layer) formed thereon, in which a B layer is laminated on a C layer and then an A layer is laminated. .

The alkoxysilane coating composition comprises:
About the kind and preparation method of each component, (a) / [(b) +
(C)] = 2/1 (weight ratio), (epoxy group) / (sum of amino group + imino group) = 1/2 (molar ratio), except that it was the same as in Example 1. The degree of conversion of the layer A into ceramics was 1.0 in terms of the SiO / SiN ratio obtained in Reference Example 2. All evaluation results were good.

Example 5 A transparent polymer film is a polyethersulfone film having a silicon oxide film (C layer) formed thereon, wherein an A layer is laminated on a C layer, and then a B layer is laminated. .

The (a) vinyl alcohol resin of the alkoxysilane coating composition for providing the layer B is the same as that in Example 1 except that the alkoxysilane having an epoxy group is
(3,4-epoxycyclohexyl) ethyltrimethoxysilane was used, and aminopropyltrimethoxysilane was used as alkoxysilane having an amino group. (A) /
[(B) + (c)] = 2/1 (weight ratio), (epoxy group) / (sum of amino group + imino group) = 1/1 (molar ratio). Preparation of the coating composition was performed in the same manner as in Example 1. The degree of conversion of the layer A to ceramics was 1.3 in terms of the SiO / SiN ratio determined in Reference Example 4. All evaluation results were good.

Example 6 A transparent polymer film is a polyethersulfone film on which a silicon oxide film (C layer) is formed. A layer B is laminated on the layer C, and a layer B is formed on the opposite surface. This is an example in which layer A is laminated after lamination.

An ethylene-vinyl alcohol copolymer (EV manufactured by Kuraray Co., Ltd.) may be used as the vinyl alcohol resin (a) of the alkoxysilane coating composition for providing the layer B.
OH-F (ethylene copolymerization ratio 32 mol%))
The alkoxysilane having an epoxy group and the alkoxysilane having an amino group are the same as those in Example 5, (a)
/ [(B) + (c)] = 2/1 (weight ratio), (epoxy group) / (sum of amino group + imino group) = 1/1 (molar ratio) Prepared similarly. The degree of conversion of the layer A into ceramics was determined by the SiO 2 obtained in Reference Example 5.
/ SiN ratio was 1.5. As shown in Table 3, all the evaluation results were good.

[Comparative Example 1] In an alkoxysilane coating composition providing a layer B, (a) / [(b) +
(C)]> 9/1 (weight ratio), which is inferior in alkali resistance, acid resistance (solvent resistance), NMP resistance, adhesion and durability.

[Comparative Example 2] In the alkoxysilane coating composition, (a) / [(b) + (c)] <1 /
3 (weight ratio), which is inferior in gas barrier properties at 30 ° C. and 90% RH.

Comparative Example 3 This is an example in which the layer A and the layer B are not laminated so as to be in contact with each other, and have poor gas barrier properties at 30 ° C. and 90% RH.

[Comparative Example 4] This is an example in which the conversion of the layer A to ceramics is low, and is inferior in gas barrier properties at 30 ° C and 90% RH.

[0119]

[Table 2]

[0120]

[Table 3]

[0121]

According to the present invention, the laminated film having a layer constituted by the layer A and the layer B in contact with each other is transparent, optically isotropic, flat, solvent-resistant, flexible, and has good adhesion between layers. This is a transparent gas-barrier laminated film that has excellent gas barrier properties independent of humidity in addition to its excellent characteristics.

Continued on the front page (72) Inventor Tatsuya Yuka 4-3-2 Asahigaoka, Hino-shi, Tokyo Teijin Co., Ltd. Tokyo Research Center

Claims (13)

[Claims] 1. A ceramic layer (A) formed of polysilazane on at least one surface of a transparent polymer film.
Layer) and the following general formula (1): (Where R ¹ is an alkylene group having 1 to 4 carbon atoms, R ² and R ³ are alkyl groups having 1 to 4 carbon atoms, X is a glycidoxy group or an epoxycyclohexyl group, and n is 1 or 0) A (partial) hydrolyzate, a (partial) condensate or a mixture thereof of an alkoxysilane having an epoxy group represented by the following general formula (2): (Where R ⁴ is an alkylene group having 1 to ⁴ carbon atoms, R ⁵ and R ⁶ are alkyl groups having 1 to 4 carbon atoms, Y is a hydrogen atom or an aminoalkyl group, and m is 1 or 0). A (partial) hydrolyzate of an alkoxysilane having an amino group and / or an imino group shown, a (partial) condensate thereof, or a cured resin layer (B layer) containing a vinyl alcohol-based resin cross-linked by a mixture thereof A transparent gas-barrier laminated film having layers that are in contact with each other. 2. The transparent gas-barrier laminated film according to claim 1, wherein the transparent polymer film has a metal oxide layer (C layer) on at least one surface thereof. 3. The transparent polymer film has a metal oxide layer (C layer) on at least one surface thereof, and a B layer is laminated on and in contact with the metal oxide layer (C layer). 2. The transparent gas barrier laminate film according to claim 1, wherein the layer A is further laminated in contact with the layer B. 4. A light transmittance at a wavelength of 550 nm of 8
The transparent gas barrier laminated film according to any one of claims 1 to 3, wherein the retardation value is 0 nm or more and the retardation value is 30 nm or less. 5. The following (a) to (d): (a) a vinyl alcohol-based resin on at least one surface of a transparent polymer film or a transparent polymer film having a metal oxide layer (C layer) on at least one surface. (B) a (partial) hydrolyzate of the alkoxysilane having an epoxy group according to claim 1, a partial condensate thereof or a mixture thereof, and (c) an alkoxy group having an amino group and / or an imino group according to claim 1. (A) / [(b) comprising a (partial) hydrolyzate of silane, a partial condensate thereof or a mixture thereof, and (d) a solvent containing at least 50% by weight of a vinyl alcohol resin soluble solvent in the total solvent. + (C)] = 9/1 to 1/3
(Weight ratio) after applying the alkoxysilane coating composition, at least as a dry film, and applying a polysilazane coating composition containing at least polysilazane and a polysilazane-soluble solvent on the dry film, followed by inversion. A method for producing a transparent gas barrier laminate film, comprising forming a ceramic layer (A layer) on a cured resin layer (B layer) in which the dried film has been cured. 6. The method for producing a transparent gas-barrier laminated film according to claim 5, wherein the dried film is a cured resin layer (layer B). 7. The polysilazane coating composition according to claim 5, which is applied on at least one surface of a transparent polymer film or a transparent polymer film having a metal oxide layer (C layer) on at least one surface, and then converted. To form a ceramic layer (A layer), and then, on the A layer,
A method for producing a transparent gas barrier laminate film, comprising applying the alkoxysilane coating composition according to claim 5, and then heating the alkoxysilane coating layer to form a cured resin layer (B layer). . 8. The method according to claim 5, wherein the alkoxysilane coating composition is applied on the metal oxide layer (C layer).
The method for producing a transparent gas barrier laminate film according to the above. 9. An alkoxysilane having an epoxy group is 3-glycidoxypropyltrimethoxysilane, and / or
The method for producing a transparent gas-barrier multilayer film according to any one of claims 5 to 8, wherein the method is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. 10. An alkoxysilane having an amino group and / or an imino group is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane,
At least one member selected from the group consisting of aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane The method for producing a transparent gas-barrier laminated film according to any one of claims 5 to 9, which is a compound. 11. The method according to claim 1, wherein the C layer has a thickness of 5 nm to 200 nm.
The method for producing a transparent gas barrier laminate film according to any one of claims 5 to 10, comprising a silicon oxide having an average composition represented by Ox (where 1.5 ≦ x ≦ 2). 12. The method for producing a transparent gas barrier laminated film according to claim 5, wherein the vinyl alcohol-based resin is polyvinyl alcohol. 13. A transparent polymer film comprising a polycarbonate resin or a polyarylate resin.
3. The method for producing a transparent gas-barrier laminated film according to any one of 2.