JP2004330673A - High barrier laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas barrier film as a transparent high barrier laminate with advantages such as improved oxygen and water vapor barrier properties over a conventional barrier film, less dependence upon humidity while maintaining transparency and less properties deterioration even under high humidity. <P>SOLUTION: The high barrier laminate is constituted of at least an inorganic oxide thin film layer composed of an inorganic oxide and a modified polyvinyl alcohol resin layer composed of a modified polyvinyl alcohol resin, laminated on at least one side of a transparent plastic film. The inorganic oxide thin film layer is transparent and the modified polyvinyl alcohol resin layer is 0.1 to 1.0 μm thick. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００５３】
【発明の効果】
以上のように、本願発明にかかるハイバリア性積層体によれば、透明プラスチックフィルムの少なくとも片面に、少なくとも、無機酸化物による無機酸化物薄膜層と、変性ポリビニルアルコール樹脂による変性ポリビニルアルコール樹脂層と、を積層してなり、無機酸化物薄膜層が透明であって、変性ポリビニルアルコール樹脂層の厚みが０．１μｍ〜１．０μｍである構成とすることにより、その目的は、従来の物よりも酸素バリア性及び水蒸気バリア性を向上させたものであって、かつ透明性を確保しつつ、湿度依存性が少なく、高湿度下において性質劣化の少ない透明ハイバリア積層体であるガスバリアフィルムを得られる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a high-barrier laminate excellent in gas barrier properties, specifically, a high-barrier laminate suitable for packaging materials for articles requiring air permeability and moisture resistance, such as foods and pharmaceuticals. About the body.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, a so-called gas barrier film that does not allow external oxygen or moisture to enter therein has been used as a packaging material in order to store a substance such as a food or a pharmaceutical which is desired to prevent deterioration of its contents. Conventionally, a large amount of a gas barrier film obtained by depositing an aluminum foil on a plastic film has been used for reasons of cost, ease of manufacture, etc. However, there is a problem that the visibility cannot be secured.
[0003]
Therefore, as an alternative to the gas barrier film in which aluminum foil is deposited on this plastic film, a transparent gas barrier film in which a metal oxide such as silicon oxide or aluminum oxide is deposited on a transparent plastic film has been developed and used. It is becoming. In addition, a transparent plastic film coated with a polymer having excellent oxygen barrier properties and water vapor barrier properties has been proposed and developed (for example, see Patent Document 1).
[0004]
[Patent Document 1] Japanese Patent Application Laid-Open No. 2002-166489
However, as described in the prior art of Patent Document 1, a transparent gas barrier composed of a metal oxide such as silicon oxide or aluminum oxide deposited on a transparent plastic film. Since the film is inferior in gas barrier properties as compared with the conventional gas barrier film on which aluminum foil is vapor-deposited, the thickness of the metal oxide film is increased as a countermeasure, but as a result, light absorption of the vapor-deposited film occurs. A problem is that the film becomes brownish or grayish as a whole, that is, the transparency of the film is reduced.
[0006]
Further, in the gas barrier film as described in the claims of Patent Document 1, the barrier properties are inevitably equal to the conventional metal oxide vapor-deposited films in oxygen barrier properties and water vapor barrier properties, Furthermore, the gas barrier film described in Patent Document 2 is sensitive to a change in humidity, and therefore has a problem that the gas barrier property is significantly reduced in a high humidity environment.
[0007]
The present invention has been made in view of such problems, the purpose of which is to improve the oxygen barrier properties and water vapor barrier properties than conventional products, and while ensuring transparency, An object of the present invention is to provide a gas barrier film which is a transparent high barrier laminate having little humidity dependency and little property deterioration under high humidity.
[0008]
[Means for Solving the Problems]
In order to solve the above-mentioned problem, the invention according to claim 1 of the present invention is directed to a transparent plastic film, in which at least one surface includes at least an inorganic oxide thin film layer made of an inorganic oxide and a modified polyvinyl alcohol resin layer made of a modified polyvinyl alcohol resin Wherein the inorganic oxide thin film layer is transparent, and the modified polyvinyl alcohol resin layer has a thickness of 0.1 μm to 1.0 μm.
[0009]
According to a second aspect of the present invention, in the high barrier laminate according to the first aspect, the modified polyvinyl alcohol resin layer contains a metal compound catalyst.
[0010]
In the invention according to claim 3 of the present invention, in the high-barrier laminate according to claim 1 or 2, the inorganic oxide is one or both of a silicon oxide and an aluminum oxide. There is a feature.
[0011]
According to a fourth aspect of the present invention, in the high barrier laminate according to the second or third aspect, the catalyst of the metal compound is a metal complex.
[0012]
According to a fifth aspect of the present invention, there is provided the high-barrier laminate according to any one of the first to fourth aspects, wherein oxygen permeation in an environment at a temperature of 22 ° C. and a relative humidity of 65% is provided. The difference between the rate and the oxygen permeability in an environment where the temperature is 22 ° C. and the relative humidity is 90% is within 3.0 ml / (m ² · d · MPa).
[0013]
According to a sixth aspect of the present invention, there is provided the high-barrier laminate according to any one of the first to fifth aspects, wherein water vapor permeation in an environment where the temperature is 40 ° C. and the relative humidity is 90%. The rate is 0.7 g / (m ² · d) or less.
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described. The embodiment described below is merely an example, and is not necessarily limited to this embodiment.
[0015]
(Embodiment 1)
The high barrier laminate according to the present invention will be described as a first embodiment.
The high-barrier laminate according to the present invention is formed by laminating at least one surface of a transparent plastic film, at least an inorganic oxide thin film layer of an inorganic oxide, and a modified polyvinyl alcohol resin layer of a modified polyvinyl alcohol resin. The inorganic oxide thin film layer is transparent, and the modified polyvinyl alcohol resin layer has a thickness of 0.1 μm to 1.0 μm. The order of lamination of the inorganic oxide thin film layer and the modified polyvinyl alcohol resin layer may be arbitrary, but in the following description, it is assumed that the layers are laminated in the order described.
[0016]
The description will be made in the following order.
The transparent plastic film used for the high-barrier laminate according to the present embodiment is not particularly limited, but may be any material having excellent heat resistance, machining suitability, and chemical stability. Any of those used can be used. For example, polyethylene terephthalate, polyarylate, polyethylene naphthalate, polycarbonate, (meth) acrylonitrile film, polyether sulfone film, polyphenylene sulfide film, polyimide, polystyrene, polyethylene, polyvinyl chloride, acrylic resin, polynorbornene resin Films such as a film made of a single polymer such as, a synthetic resin film such as a film made of these copolymers, and an artificial resin film such as cellulose are conceivable. Further, two or more of these films may be a composite film that is a multilayer film in which two or more types are laminated, or a film made from a blend of two or more types of the above various polymers. For example, a film obtained by blending polyethylene terephthalate with isophthalate as a raw material and improving its strength may be used.
[0017]
Although not specifically described in detail, a physical treatment such as a plasma treatment or a silane coupling agent is previously performed on the surface of the transparent plastic film in order to facilitate lamination of an inorganic oxide thin film or the like as described later. A pretreatment such as a chemical treatment may be performed, or an undercoat layer may be formed. Further, various known primers may be applied, or a primer layer, a protective layer, a coloring layer, a printing layer, a seal layer, and the like may be provided as long as the effects of the present invention described below are not impaired. Further, when forming a transparent plastic film, a modifier such as an ultraviolet absorber or a static induction-induced antistatic agent may be contained in the film by a known method.
[0018]
Although the thickness of the transparent plastic film described above is not particularly limited here, it is preferably within a range of 4 μm to 20 μm. By setting the content in this range, the sheet processing can be easily performed, and the barrier performance can be prevented from lowering due to cracks or the like during handling.
[0019]
Next, the inorganic oxide forming the inorganic oxide thin film layer will be described. The inorganic oxide imparts a high oxygen barrier property and a high water vapor barrier property, and preferably has excellent transparency. It is more preferable that the viewpoints of economy, environmental preservation, safety and the like be added. More specifically, if the inorganic oxide is any one or both of silicon oxide and aluminum oxide, that is, a mixture of one or both of silicon oxide and aluminum oxide, An inorganic oxide that forms the oxide thin film layer is more preferable.
[0020]
Specifically, when a mixture of silicon oxide and aluminum oxide is used, the weight ratio is preferably 9/1 to 5/5. In the case of silicon oxide shown in the _Si x _{O y,} those relative to X = 1 is Y = 1.1 to 1.9, Y preferably for X = 1 = 1.2 to 1.8 It is very suitable to choose
[0021]
The method of laminating the inorganic oxide thin film layer on the transparent plastic film may be a known method, and specifically, a conventionally known physical method such as a vacuum deposition method, a sputtering method, an ion plating method, and a plasma deposition method. A vapor deposition method (PVD method), or a mixture of one or both of silicon and aluminum in a metal state, in an oxygen gas atmosphere, or a mixture of oxygen gas and an inert gas such as argon gas or nitrogen gas In a gas atmosphere, one side of a transparent plastic film is formed by a conventionally known chemical vapor deposition method (CVD method) such as a reactive vacuum deposition method, a reactive sputtering method, a reactive ion plating method, and a reactive plasma deposition method. It is formed directly on both surfaces, or formed via an undercoat layer or the like.
[0022]
The thickness of the inorganic oxide thin film layer thus formed is preferably from 10 nm to 300 nm, and if it is from 15 nm to 100 nm, a more favorable barrier property can be obtained. When the thickness is 10 nm or less, the barrier performance obtained by the inorganic oxide thin film layer is insufficient, and when the thickness is 300 nm or more, cracks are easily generated in the inorganic oxide thin film layer. The barrier properties are deteriorated, none of them are preferable, and further, they are not preferable from the viewpoint of economy.
[0023]
Next, the modified polyvinyl alcohol resin layer will be described. As a modified polyvinyl alcohol resin forming this layer, a modified polyvinyl alcohol resin obtained by subjecting a known polyvinyl alcohol to acetalization, formalization, butyralization, or the like is used. Can be used. The modified polyvinyl alcohol resin layer using such a modified polyvinyl alcohol resin further contains the modified polyvinyl alcohol resin on the surface of the inorganic oxide thin film layer on the transparent plastic film formed as described above. The liquid is applied by a known ordinary coating method such as a roll coating method, a gravure coating method, a reverse coating method, and the like, and dried to form a liquid. In some cases, it may be possible to further perform a heat treatment.
[0024]
The thickness of the modified polyvinyl alcohol resin layer thus obtained may be freely determined, but in the present embodiment, the thickness is preferably from 0.1 μm to 1.0 μm, and preferably from 0.3 μm to 0 μm. 0.7 μm is more preferable. With this thickness, the adhesion between the inorganic oxide thin film layer and the modified polyvinyl alcohol resin layer becomes suitable, and the oxygen permeability and the moisture permeability easily become excellent without depending on the humidity. This is because it greatly contributes to the formation of a high barrier laminate having excellent printability and flexibility.
[0025]
When the thickness is less than 0.1 μm, the effect of using the modified polyvinyl alcohol resin and the inorganic oxide in combination cannot be obtained, and when the thickness exceeds 1.0 μm, not only is it not economically favorable, but also the inorganic oxide Since the adhesion to the thin film layer is reduced, and as a result, delamination occurs when used as a packaging material, the thickness is preferably within the above range.
[0026]
Further, by adding a metal compound catalyst to the modified polyvinyl alcohol resin layer, more preferable properties can be obtained. Furthermore, if the catalyst of the metal compound is a metal complex, more preferable properties can be obtained. Specifically, any metal complex such as aluminum acetylacetonate or zinc acetylacetonate may be used, and by containing these, the oxygen barrier property and the water vapor barrier property are further improved, and the interlayer adhesion is further increased. . The content of the metal compound in the modified polyvinyl alcohol resin is preferably 1% by weight to 10% by weight based on the main agent.
[0027]
By forming a high-barrier laminate composed of such layers and films, a laminate having a large interlayer adhesion, and excellent oxygen barrier properties and water vapor barrier properties, suitable for packaging materials such as foods and pharmaceuticals can be obtained. You get it. At the same time as the above configuration, the difference between the oxygen permeability in an environment with a temperature of 22 ° C. and a relative humidity of 65% and the oxygen permeability in an environment with a temperature of 22 ° C. and a relative humidity of 90% is 3.0 ml. / (M ² · d · MPa), the water vapor transmission rate is 0.7 g / (m ² · d) or less in an environment where the temperature is 40 ° C. and the relative humidity is 90%. By doing so, it is possible to obtain a high-barrier laminate having properties not obtained conventionally.
[0028]
【Example】
Hereinafter, the present invention and examples according to the above-described embodiments will be described more specifically. However, it is to be noted that the present invention is not limited to only the following examples.
[0029]
(Example 1)
_Si x _O y (x = 1.0 polyethylene terephthalate film having a thickness of 12μm as a transparent plastic film (manufactured by Teijin NS Ltd.) as an inorganic oxide to form an inorganic oxide thin layer, y = 1.5 ) To prepare a modified polyvinyl alcohol resin (manufactured by Nippon Synthetic Chemical Industry Co., Ltd .; trade name “Gosefimer Z-100”) for forming a modified polyvinyl alcohol resin layer.
[0030]
On one side of the transparent plastic film are formed such that the inorganic oxide thin layer with a thickness of 20nm to Si _x O _y by evaporation. Next, the modified polyvinyl alcohol resin was diluted with pure water to a solid content ratio of 10%, and aluminum acetylacetonate (manufactured by Nacalai Tesque, Inc.) as a metal complex was added thereto at 2% based on the solid content. The surface of the inorganic oxide thin film layer is further applied by gravure coating so as to have a dry film thickness of 0.5 g / m ² to form a modified polyvinyl alcohol resin layer. Thus, the high barrier laminate according to the present invention is obtained.
[0031]
The oxygen permeability of the obtained high barrier laminate was 7.0 ml / (m ² · d · MPa) in an environment with a temperature of 22 ° C. and a relative humidity of 65%, and a temperature of 22 ° C. and a relative humidity of 90%. ^{8.9ml / (m 2 · d ·} MPa) in an environment, the difference was ^{3.0ml / (m 2 · d ·} MPa) within, i.e. ^{1.9ml / (m 2 · d ·} MPa) . The water vapor transmission rate in an environment where the temperature was 40 ° C. and the relative humidity was 90% was 0.6 g / (m ² · d).
[0032]
As described above, in Example 1, a high-barrier laminate having little humidity dependence of oxygen gas barrier properties and having excellent water vapor barrier properties even in a high-humidity environment was obtained.
[0033]
(Example 2)
Using a polyurethane-based adhesive (manufactured by Toyo Morton Co., Ltd .; trade name “TM-215”), a low-profile layer having a thickness of 50 μm was further applied to the surface of the modified polyvinyl alcohol resin layer of the high barrier laminate obtained in Example 1. A heat-sealing layer was provided by bonding a high-density polyethylene film (manufactured by Tocelo Co., Ltd .; trade name “FCS”), and oxygen gas barrier properties and water vapor barrier properties were evaluated.
[0034]
As a result, the oxygen permeability of the high-barrier laminate obtained in this example was 4.8 ml / (m ² · d · MPa) under an environment of a temperature of 22 ° C. and a relative humidity of 65%, and the temperature was 22 ° C. In an environment with a relative humidity of 90%, the difference was 5.9 ml / (m ² · d · MPa), and the difference was 1.1 ml / (m ² · d · MPa). The water vapor transmission rate in an environment where the temperature was 40 ° C. and the relative humidity was 90% was 0.5 g / (m ² · d).
[0035]
Therefore, similarly to Example 1, in this example, a high-barrier laminate having little humidity dependence of oxygen gas barrier properties and excellent water vapor barrier properties even in a high humidity environment was obtained.
[0036]
(Example 3)
In the same manner as in Example 1, except that the metal complex used was zinc acetylacetonate (manufactured by Nacalai Tesque, Inc.), a high barrier laminate was obtained, and the oxygen gas barrier property and the water vapor barrier property were evaluated.
[0037]
As a result, the oxygen permeability of the high-barrier laminate obtained in the present example was 7.7 ml / (m ² · d · MPa) in an environment where the temperature was 22 ° C. and the relative humidity was 65%, and the temperature was 22 ° C. In an environment with a relative humidity of 90%, the difference was 8.9 ml / (m ² · d · MPa), and the difference was 1.2 ml / (m ² · d · MPa). The water vapor transmission rate in an environment where the temperature was 40 ° C. and the relative humidity was 90% was 0.6 g / (m ² · d).
[0038]
Therefore, similarly to Example 1, in this example, a high-barrier laminate having little humidity dependence of oxygen gas barrier properties and excellent water vapor barrier properties even in a high humidity environment was obtained.
[0039]
(Example 4)
A high-barrier laminate having a heat-sealing layer provided on the surface of the modified polyvinyl alcohol resin layer of the high-barrier laminate obtained in Example 3 in the same manner as in Example 2 was obtained. The barrier properties were evaluated.
[0040]
As a result, the oxygen permeability of the high-barrier laminate obtained in the present example was 4.9 ml / (m ² · d · MPa) in an environment with a temperature of 22 ° C. and a relative humidity of 65%, and a temperature of 22 ° C. In an environment with a relative humidity of 90%, the difference was 5.9 ml / (m ² · d · MPa), and the difference was 1.0 ml / (m ² · d · MPa). The water vapor transmission rate in an environment where the temperature was 40 ° C. and the relative humidity was 90% was 0.5 g / (m ² · d).
[0041]
Therefore, similarly to Example 2, in this example, a high-barrier laminate having little humidity dependence of oxygen gas barrier properties and excellent water vapor barrier properties even in a high humidity environment was obtained.
[0042]
(Comparative Example 1)
Example 1 was the same except that the modified polyvinyl alcohol resin layer was not provided. The obtained laminate was evaluated for oxygen gas barrier properties and water vapor barrier properties.
[0043]
As a result, the oxygen permeability was 17.7 ml / (m ² · d · MPa) in an environment of a temperature of 22 ° C. and a relative humidity of 65%, and was 24 in an environment of a temperature of 22 ° C. and a relative humidity of 90%. ^{.6ml / (m 2 · d ·} MPa), the difference was ^{6.9ml / (m 2 · d ·} MPa). The water vapor transmission rate in an environment where the temperature was 40 ° C. and the relative humidity was 90% was 2.0 g / (m ² · d).
[0044]
(Comparative Example 2)
A heat-sealing layer was provided on the laminate obtained in Comparative Example 1 in the same manner as in Example 2 to obtain a new laminate. The obtained laminate was evaluated for oxygen gas barrier properties and water vapor barrier properties.
[0045]
As a result, the oxygen permeability was 11.8 ml / (m ² · d · MPa) in an environment with a temperature of 22 ° C. and a relative humidity of 65%, and was 15 in an environment with a temperature of 22 ° C. and a relative humidity of 90%. ^{.8ml / (m 2 · d ·} MPa), the difference was ^{4.0ml / (m 2 · d ·} MPa). The water vapor transmission rate in an environment where the temperature was 40 ° C. and the relative humidity was 90% was 1.5 g / (m ² · d).
[0046]
(Comparative Example 3)
Instead of the modified polyvinyl alcohol resin used in Example 1, an unmodified polyvinyl alcohol resin (manufactured by Kuraray Co., Ltd.) was used to provide a resin layer instead of the modified polyvinyl alcohol resin layer. This was the same as in Example 1). Note that no metal compound was added to the resin layer. The obtained laminate was evaluated for oxygen gas barrier properties and water vapor barrier properties.
[0047]
As a result, the oxygen permeability was 6.9 ml / (m ² · d · MPa) in an environment with a temperature of 22 ° C. and a relative humidity of 65%, and was 13 in an environment with a temperature of 22 ° C. and a relative humidity of 90%. 0.8 ml / (m ² · d · MPa), and the difference was 6.9 ml / (m ² · d · MPa). The water vapor transmission rate in an environment where the temperature was 40 ° C. and the relative humidity was 90% was 1.5 g / (m ² · d).
[0048]
(Comparative Example 4)
A laminate in which a heat seal layer was provided on the laminate obtained in Comparative Example 3 in the same manner as in Example 2 was obtained. The obtained laminate was evaluated for oxygen gas barrier properties and water vapor barrier properties.
[0049]
As a result, the oxygen transmission rate was 5.2 ml / (m ² · d · MPa) in an environment with a temperature of 22 ° C. and a relative humidity of 65%, and 9 in an environment with a temperature of 22 ° C. and a relative humidity of 90%. ^{.8ml / (m 2 · d ·} MPa), the difference was ^{4.6ml / (m 2 · d ·} MPa). The water vapor transmission rate in an environment where the temperature was 40 ° C. and the relative humidity was 90% was 1.2 g / (m ² · d).
[0050]
The oxygen permeability was measured according to JIS K-7126, and the water vapor permeability was measured according to JIS K-7129.
[0051]
The results of Examples 1 to 4 and Comparative Examples 1 to 4 are summarized as follows.
[0052]
[Table 1]

[0053]
【The invention's effect】
As described above, according to the high barrier laminate of the present invention, at least one surface of the transparent plastic film, at least an inorganic oxide thin film layer of an inorganic oxide, a modified polyvinyl alcohol resin layer of a modified polyvinyl alcohol resin, Are laminated, the inorganic oxide thin film layer is transparent, and the modified polyvinyl alcohol resin layer has a thickness of 0.1 μm to 1.0 μm. It is possible to obtain a gas barrier film which is a transparent high barrier laminate having improved barrier properties and water vapor barrier properties, having low humidity dependency and little property deterioration under high humidity while ensuring transparency.

[0006]
Further, in the gas barrier film as described in the claims of Patent Document 1, the barrier properties are inevitably equal to the conventional metal oxide vapor-deposited films in oxygen barrier properties and water vapor barrier properties, Furthermore, the gas barrier film disclosed in Patent Document 1 is sensitive to a change in humidity, which causes a problem that the gas barrier property is significantly reduced in a high humidity environment.

[0008]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the invention according to claim 1 of the present invention provides at least one surface of a transparent plastic film, at least an inorganic oxide thin film layer made of an inorganic oxide, and acetalization, formalization of polyvinyl alcohol, or A modified polyvinyl alcohol resin layer obtained by performing any of the following processes: butyralization, and a modified polyvinyl alcohol resin layer obtained by performing any of the following treatments: the inorganic oxide thin film layer is transparent, and the thickness of the modified polyvinyl alcohol resin layer is Is 0.1 μm to 1.0 μm , and the modified polyvinyl alcohol resin layer contains a metal compound catalyst .

[0010]
The invention according to claim 2 of the present invention relates to the high barrier laminate according to claim 1 , wherein the inorganic oxide is one or both of a silicon oxide and an aluminum oxide. Features.

[0011]
According to a third aspect of the present invention, in the high barrier laminate according to the first or second aspect , the catalyst of the metal compound is a metal complex.

[0012]
According to a fourth aspect of the present invention, there is provided the high barrier laminate according to any one of the first to third aspects, wherein oxygen permeation in an environment at a temperature of 22 ° C. and a relative humidity of 65% is provided. The difference between the rate and the oxygen permeability in an environment where the temperature is 22 ° C. and the relative humidity is 90% is within 3 ml / (m ² · d · MPa).

[0013]
According to a fifth aspect of the present invention, there is provided the high barrier laminate according to any one of the first to fourth aspects, wherein water vapor permeation in an environment where the temperature is 40 ° C. and the relative humidity is 90%. The rate is 0.7 g / (m ² · d) or less.

[0008]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the invention according to claim 1 of the present invention provides at least one surface of a transparent plastic film, at least an inorganic oxide thin film layer made of an inorganic oxide, and acetalization, formalization of polyvinyl alcohol, or Lamination with a modified polyvinyl alcohol resin layer formed of a modified polyvinyl alcohol resin obtained by subjecting to any one of butyralization and a metal complex containing 1% by weight to 10% by weight with respect to the main component. The inorganic oxide thin film layer is transparent and has a thickness of 10 nm to 300 nm, and the inorganic oxide thin film layer is composed of silicon oxide and aluminum oxide in a weight ratio of 9/1 to 5%. / 5 ones were mixed in a range of, or _Si x _O y silicon oxide alone represented by (x = 1 with respect to y = 1.1 to 1.9), Or the aluminum complex alone, and the metal complex is one or both of aluminum acetylacetonate and zinc acetylacetonate, and the modified polyvinyl alcohol resin layer has a thickness of 0.1 μm. １．０1.0 μm, and the modified polyvinyl alcohol resin layer contains a metal compound catalyst.

[0012]
The invention according to claim 2 of the present invention is the high barrier laminate according to claim 1 , wherein the oxygen permeability under an environment of a temperature of 22 ° C and a relative humidity of 65%, and a temperature of 22 ° C and a relative humidity Is within 3 ml / (m ² · d · MPa) with the oxygen permeability in an environment of 90%.

[0013]
The invention according to claim 3 of the present invention is the high-barrier laminate according to claim 1 or 2 , wherein the water vapor transmission rate in an environment at a temperature of 40 ° C and a relative humidity of 90% is 0.7 g. / (M ² · d) or less.

[0008]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the invention according to claim 1 of the present invention provides at least one surface of a transparent plastic film, at least an inorganic oxide thin film layer made of an inorganic oxide, and acetalization, formalization of polyvinyl alcohol, or A modified polyvinyl alcohol resin layer formed by adding 1% by weight to 10% by weight of a metal complex to a modified polyvinyl alcohol resin obtained by subjecting to any one of butyralization. The inorganic oxide thin film layer is transparent, has a thickness of 10 nm to 300 nm, and has a weight ratio of silicon oxide to aluminum oxide of 9/1 to 5/5. those mixed in the range of, or _Si x _O y silicon oxide alone represented by (x = 1 with respect to y = 1.1 to 1.9), Moshiku Is formed of any of aluminum oxide alone, and the metal complex is one or both of aluminum acetylacetonate and zinc acetylacetonate, and the modified polyvinyl alcohol resin layer has a thickness of 0.1 μm. １．０1.0 μm.

Claims (6)

On at least one side of the transparent plastic film,
At least, an inorganic oxide thin film layer of an inorganic oxide,
By laminating a modified polyvinyl alcohol resin layer with a modified polyvinyl alcohol resin,
The inorganic oxide thin film layer is transparent,
A high barrier laminate, wherein the thickness of the modified polyvinyl alcohol resin layer is 0.1 μm to 1.0 μm. The high-barrier laminate according to claim 1,
A high via laminate, wherein the modified polyvinyl alcohol resin layer contains a metal compound catalyst. The high barrier laminate according to claim 1, wherein the inorganic oxide is one or both of a silicon oxide and an aluminum oxide. 4. . The high-barrier laminate according to claim 2 or 3,
The high-barrier laminate, wherein the catalyst of the metal compound is a metal complex. The high-barrier laminate according to any one of claims 1 to 4, wherein
Oxygen permeability in an environment with a temperature of 22 ° C. and a relative humidity of 65%,
Oxygen permeability in an environment with a temperature of 22 ° C. and a relative humidity of 90%,
The high barrier laminate has a difference of 3 ml / (m ² · d · MPa) or less. The high-barrier laminate according to any one of claims 1 to 5, wherein
A high barrier laminate having a water vapor transmission rate of 0.7 g / (m ² · d) or less in an environment where the temperature is 40 ° C. and the relative humidity is 90%.