JP2001287319A - Gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film having a layer containing polyvinyl alcohol, which keeps high barrier properties even under a high humidity condition, as a component. SOLUTION: The gas barrier film is constituted by providing a composite film layer, which is formed from a mixture containing polyvinyl alcohol with a 1,2-glycol bond content of 0.01-1.9% and an inorganic laminar compound as main components, on the single surface of a base material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas barrier film, and
The present invention relates to a gas barrier film suitable as a packaging film that suppresses deterioration and deterioration of electronic members, electronic devices, and the like due to oxygen, water vapor, and the like.

[0002]

2. Description of the Related Art Packaging materials are required to have various functions. Among them, the protection of contents is the most important function. Deterioration or deterioration of the contents is promoted mainly by the influence of oxygen, moisture, light, heat and the like, and the influence of oxygen and moisture is particularly large. When considering the protection of the contents, it is important to block them, and there is a demand for a gas barrier film having excellent gas barrier properties.

[0003] Further, under the circumstances where tastes are diversified and additives are regulated as in today, not only are there no barriers from the outside, but also inert gas-filled packaging and internal measures such as prevention of deterioration of flavor and aroma. It is necessary to block transmission from However, plastic films generally have poor gas barrier properties, and when used alone, there is no material that satisfies the requirements except for some uses. Therefore, a method of forming a gas barrier film by laminating another layer having excellent gas barrier properties is often adopted.

It is known that a film having a layer containing polyvinyl alcohol as a component has a high crystallinity and excellent oxygen barrier properties in a dry state, but has a low crystallinity under high humidity conditions. The problem is that oxygen barrier properties are significantly reduced. Various methods have been devised to solve this problem.

For example, a gas barrier film provided with a polyvinylidene chloride layer as a non-hydroxyl group has been put to practical use, but has a drawback of generating harmful dioxins during disposal. In addition, in order to improve the water resistance of polyvinyl alcohol, the results of an ethylene-vinyl alcohol copolymer in which an ethylene unit is introduced into polyvinyl alcohol are also known. In recent years, a method of producing a composite coating layer of polyvinyl alcohol and an inorganic layered compound has been considered (for example, Japanese Patent Application Laid-Open Nos. 7-41685, 7-33909, and 7-251475). Although their effects are known, their resistance to humidity is not yet sufficient.

[0006]

As described above, the conventional gas barrier film having a layer containing polyvinyl alcohol as a component has a problem that the barrier properties are remarkably reduced under high humidity conditions. An object of the present invention is to provide a gas barrier film which is a gas barrier film having a layer containing polyvinyl alcohol as a component, but maintains a higher barrier property than conventional gas barrier films even under high humidity conditions, and has excellent barrier properties. It is assumed that.

[0007]

According to the present invention, there is provided an inorganic layered compound comprising polyvinyl alcohol having a 1,2-glycol bond content of at least 0.01% and at most 1.9% on at least one surface of a substrate. And a composite coating layer formed from a mixture mainly comprising:

[0008] The present invention also relates to a method for producing a poly (vinyl alcohol) having a 1,4-glycol bond content of 0.01% or more and 2.0% or less on at least one surface of a substrate. A gas barrier film provided with a composite coating layer formed from a mixture of:

The present invention also provides the gas barrier film according to the present invention, wherein the weight ratio of the polyvinyl alcohol (A) to the inorganic layered compound (B) in the composite coating layer is A.
/ B = 10/90 to 99/1.

[0010] The present invention is also the gas barrier film according to the above invention, wherein the substrate is a plastic film or a ceramic vapor-deposited film provided with a ceramic vapor-deposited layer.

Further, the present invention is the gas barrier film according to the above invention, wherein the ceramic of the ceramic deposited layer is a silicon oxide-based, aluminum oxide-based, or titanium oxide-based ceramic.

Further, the present invention is the gas barrier film according to the above invention, wherein the composite coating layer further contains a hydrolyzate of a metal alkoxide as a component.

[0013] Further, the present invention is the gas barrier film according to the above invention, wherein the metal forming the metal alkoxide is silicon, aluminum or titanium.

Further, the present invention provides the gas barrier film according to the above invention, wherein the inorganic layered compound is montmorillonite.

[0015]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. The 1,2-glycol bond and 1,4-glycol bond of the polyvinyl alcohol in the present invention refer to a bond of a repeating unit in a polymer chain in which two hydroxyl groups are bonded to adjacent carbon atoms. In addition,
The quantification of the 1,2-glycol bond content and the 1,4-glycol bond content can be quantified by a known method such as X-ray diffraction, infrared absorption spectroscopy, and high-resolution nuclear magnetic resonance.

The 1,2-glycol bond content is desirably 0.1% or more and 1.8% or less, but is not limited thereto. Here, when the 1,2-glycol bond content is higher than 1.8%, the crystallinity under high humidity conditions is not much different from that of the conventional polyvinyl alcohol, and when the content is lower than 0.1%, there is no inconvenience, but synthesis is performed. Above impractical. Further, the 1,4-glycol bond content is desirably 0.1
% Or more and 1.5% or less is preferable, but not limited to this. Here, the 1,4-glycol bond content is 1.
If it is higher than 5%, the crystallinity under high humidity conditions is not much different from that of the conventional polyvinyl alcohol, and if it is lower than 0.1%, it is not inconvenient, but is not practical in synthesis.

The inorganic layer compound in the present invention includes:
Chalcogenite, pnicticite, transition metal oxides, halides, and other inorganic layered compounds are not particularly limited as long as they have high chemical activity such as swelling and complex formation, and include smectite, hectorite, Clay minerals such as saponite, mica, and montmorillonite, and metal salts such as zinc phosphate, cobalt phosphate, vanadium oxide salt, aluminum phosphate, vanadium phosphate, oxovanadium phosphate, and zinc bisphosphonate are preferred.

In the present invention, the weight ratio of the polyvinyl alcohol (A) to the inorganic layered compound (B) is A / B = 1.
0/90 to 99/1. Weight ratio of 10/90
If it is lower, the stability of the formed film is reduced, and 99
When it is higher than / 1, the effect of the inorganic layered compound on the polyvinyl alcohol is not sufficient, and the barrier property is not excellent under high humidity conditions. In the present invention, an undercoat layer may be provided in order to improve the adhesion between the substrate and the composite coating layer. It is desirable that the components of the undercoat layer include imine, urethane and the like, but the invention is not limited thereto.

The substrate on which the mixture containing polyvinyl alcohol and an inorganic layered compound as main components is applied is not particularly limited, and a known plastic film such as polyolefin, nylon or polyester may be appropriately used according to the intended use. Further, in order to further enhance the barrier property, a ceramic vapor-deposited film having a ceramic vapor-deposited layer provided on a plastic film may be appropriately used depending on the application.

When a ceramic deposited film is used as the substrate, the type of ceramic is not particularly limited, but silicon oxide, aluminum oxide, titanium oxide, etc. are preferred in consideration of ease of handling and economy. . Examples of the vapor deposition method include, but are not limited to, a vacuum vapor deposition method, a sputtering method, and a plasma chemical vapor deposition method (plasma CVD method). As a method of applying the mixture, a known application method such as a dipping method, a roll coating method, a screen printing method, and a spray method can be used. The mixture applied on the substrate is dried to form a composite coating layer on the substrate.

In the case where the composite coating layer is formed on one side of the substrate, the thickness of the composite coating layer after drying is about 0.0
It is preferable to apply so as to be 1 to 100 μm
More preferably, the thickness is 0.01 to 50 μm. If the thickness is smaller than this, it is difficult to form a composite coating layer, and if formed, it is unstable. If it is too thick, it is uneconomical. Further, a solvent such as alcohol, a metal alkoxide hydrolyzate, or the like may be added depending on the use. When a metal alkoxide hydrolyzate or the like is added, moisture resistance is improved as compared with polyvinyl alcohol alone.

[0022]

The present invention will be described below in detail with reference to examples. <Example 1> Polyvinyl alcohol (1,2-glycol bond content 1.3%, hereinafter referred to as PVA-α (A-α)) and montmorillonite (B) were prepared by mixing A-α / B = 40/60 (weight ratio). 2. Charge into the container in proportions, followed by a total solids content of 3.
Water was added to a concentration of 5%, and the mixture was stirred while heating to 100 ° C. or lower to prepare a mixture. As a substrate, a biaxially stretched polypropylene film having a thickness of 20 μm provided with a urethane-based undercoat layer is applied to the substrate using a gravure coater, and dried by passing through an oven at 100 ° C. A gas barrier film having a 0.3 μm composite coating layer formed with the obtained layer thickness was prepared.

<Example 2> Same as Example 1 except that PVA-α (A-α) and montmorillonite (B) were charged into a container at a ratio of A-α / B = 60/40 (weight ratio). To produce a gas barrier film.

Example 3 The same as Example 1 except that PVA-α (A-α) and montmorillonite (B) were charged into the container at a ratio of A-α / B = 80/20 (weight ratio). To produce a gas barrier film.

<Example 4> PVA-α (A-α), montmorillonite (B) and hydrolyzed tetraethoxysilane (C) were obtained by A-α / B / C = 30/30/40 (weight ratio).
, And then the total solid content is 3.5%
, And stirred while heating to 100 ° C. or lower to prepare a mixture. In the same manner as in Example 1, a 20 μm-thick biaxially stretched polypropylene film provided with a urethane-based undercoat layer as a substrate, the above mixture was applied on the substrate by a gravure coater, and the mixture was placed in an oven at 100 ° C. And dried to form a gas barrier film having a 0.3 µm composite coating layer with a dried layer thickness.

<Example 5> PVA-α (A-α), montmorillonite (B), and tetraethoxysilane hydrolyzate (C) were mixed with A-α / B / C = 23/23/54 (weight ratio).
A gas barrier film was prepared in the same manner as in Example 4 except that the gas barrier film was charged into the container at the ratio of

<Example 6> PVA-α (A-α), montmorillonite (B), and tetraethoxysilane hydrolyzate (C) were mixed with A-α / B / C = 20/20/60 (weight ratio).
A gas barrier film was prepared in the same manner as in Example 4 except that the gas barrier film was charged into the container at the ratio of

<Example 7> A polyethylene terephthalate film having a thickness of 12 µm was used as a base material, metal aluminum was used as a vapor deposition material, and an electron beam heating winding type vapor deposition apparatus was used to introduce oxygen onto the substrate while introducing oxygen. Aluminum was reactively vapor-deposited in an oxygen atmosphere to prepare an aluminum oxide-deposited film. A composite coating layer similar to that of Example 1 was formed on the obtained aluminum oxide vapor-deposited film, and a non-stretched polypropylene (thickness: 30 μm) was adhered thereon using a polyol isocyanate-based adhesive to form a gas barrier film. did.

<Example 8> A composite coating layer similar to that of Example 4 was formed on the aluminum oxide vapor-deposited film prepared in Example 7 and further stretched using a polyol isocyanate-based adhesive. Thickness 30μ
m) were bonded to form a gas barrier film.

Example 9 Polyvinyl alcohol (1,
4-glycol bond content 0.7%, hereinafter PVA-γ (A
-Γ)), montmorillonite (B) was converted to A-γ / B = 40.
/ 60 (weight ratio), water was added so that the total solid content became 3.5%, and the mixture was stirred while being heated to 100 ° C. or lower to prepare a mixture. As a substrate, a biaxially stretched polypropylene film having a thickness of 20 μm provided with a urethane-based undercoat layer is applied to the substrate using a gravure coater, and dried by passing through an oven at 100 ° C. A gas barrier film having a 0.3 μm composite coating layer formed with the obtained layer thickness was prepared.

Example 10 The same as Example 9 except that PVA-γ (A-γ) and montmorillonite (B) were charged into the container at a ratio of A-γ / B = 60/40 (weight ratio). To produce a gas barrier film.

<Example 11> Same as Example 9 except that PVA-γ (A-γ) and montmorillonite (B) were charged into a container at a ratio of A-γ / B = 80/20 (weight ratio). To produce a gas barrier film.

Example 12 PVA-γ (A-γ), montmorillonite (B), and tetraethoxysilane hydrolyzate (C) were prepared by mixing A-γ / B / C = 30/30/40 (weight ratio). 2. Charge into the container in proportions, followed by a total solids content of 3.
Water was added to a concentration of 5%, and the mixture was stirred while heating to 100 ° C. or lower to prepare a mixture. As in Example 9,
Using a biaxially oriented polypropylene film having a thickness of 20 μm provided with a urethane-based subbing layer as a substrate, the above mixture was applied onto the substrate by a gravure coater, dried through an oven at 100 ° C., and dried. A gas barrier film having a composite coating layer having a thickness of 0.3 μm was formed.

<Example 13> PVA-γ (A-γ), montmorillonite (B) and tetraethoxysilane hydrolyzate (C) were prepared by mixing A-γ / B / C = 23/23/54 (weight ratio). A gas barrier film was prepared in the same manner as in Example 12, except that the gas barrier film was charged at a ratio.

Example 14 PVA-γ (A-γ), montmorillonite (B) and tetraethoxysilane hydrolyzate (C) were prepared by mixing A-γ / B / C = 20/40/40 (weight ratio). A gas barrier film was prepared in the same manner as in Example 12, except that the gas barrier film was charged at a ratio.

Example 15 A polyethylene terephthalate film having a thickness of 12 μm was used as a base material, metal aluminum was used as a vapor deposition material, and an electron beam heating winding type vapor deposition device was used to introduce oxygen onto the substrate while introducing oxygen. Aluminum was deposited in an oxygen atmosphere to prepare an aluminum oxide deposited film. A composite coating layer similar to that of Example 9 was formed on the obtained aluminum oxide vapor-deposited film, and a non-stretched polypropylene (thickness: 30 μm) was adhered thereon using a polyol isocyanate-based adhesive to form a gas barrier film. did.

Example 16 A composite coating layer similar to that of Example 12 was formed on the aluminum oxide vapor-deposited film prepared in Example 15 and further stretched using a polyol isocyanate-based adhesive. Thickness 3
0 μm) to form a gas barrier film.

Comparative Example 1 A gas barrier film was prepared in the same manner as in Example 1 except that general polyvinyl alcohol (hereinafter, PVA-β) was used instead of PVA-α (A-α). That is, PVA-β (A-β) and montmorillonite (B) were charged into a container at a ratio of A-β / B = 40/60 (weight ratio).

Comparative Example 2 The same as Comparative Example 1 except that PVA-β (A-β) and montmorillonite (B) were charged into a container at a ratio of A-β / B = 60/40 (weight ratio). To produce a gas barrier film.

Comparative Example 3 The same as Comparative Example 1 except that PVA-β (A-β) and montmorillonite (B) were charged into a container at a ratio of A-β / B = 80/20 (weight ratio). To produce a gas barrier film.

Comparative Example 4 A gas barrier film was prepared in the same manner as in Example 4 except that general polyvinyl alcohol (hereinafter referred to as PVA-β) was used instead of PVA-α (A-α). That is, PVA-β (A-β), montmorillonite (B), and tetraethoxysilane hydrolyzate (C) were converted to A-β / B / C = 30/30/40 (weight ratio).
Into the container at the rate of

<Comparative Example 5> PVA-β (A-β), montmorillonite (B), and tetraethoxysilane hydrolyzate (C) were mixed with A-β / B / C = 23/23/54 (weight ratio).
A gas barrier film was prepared in the same manner as in Comparative Example 4, except that the mixture was charged into the container at the ratio of

<Comparative Example 6> PVA-β (A-β), montmorillonite (B), and tetraethoxysilane hydrolyzate (C) were mixed with A-β / B / C = 20/20/60 (weight ratio).
A gas barrier film was prepared in the same manner as in Comparative Example 4, except that the mixture was charged into the container at the ratio of

Comparative Example 7 Comparative Example 1 was used as a composite coating layer.
A gas barrier film was prepared in the same manner as in Example 7, except that the composite coating layer was formed.

Comparative Example 8 Comparative Example 4 was used as a composite coating layer.
A gas barrier film was prepared in the same manner as in Example 8, except that the composite coating layer was formed.

Comparative Example 9 A gas barrier film was prepared in the same manner as in Example 9 except that general polyvinyl alcohol (hereinafter, PVA-β) was used instead of PVA-γ (A-γ). That is, PVA-β (A-β) and montmorillonite (B) were charged into a container at a ratio of A-β / B = 40/60 (weight ratio).

Comparative Example 10 The same as Comparative Example 9 except that PVA-β (A-β) and montmorillonite (B) were charged into a container at a ratio of A-β / B = 60/40 (weight ratio). To produce a gas barrier film.

Comparative Example 11 Same as Comparative Example 9 except that PVA-β (A-β) and montmorillonite (B) were charged into a container at a ratio of A-β / B = 80/20 (weight ratio). To produce a gas barrier film.

<Comparative Example 12> Instead of PVA-γ (A-γ), general polyvinyl alcohol (hereinafter, PVA-β) was used.
A gas barrier film was prepared in the same manner as in Example 12 except that was used. That is, PVA-β (A-β), montmorillonite (B), and tetraethoxysilane hydrolyzate (C) were converted to A-β / B / C = 30/30/40 (weight ratio).
Into the container at the rate of

<Comparative Example 13> PVA-β (A-β), montmorillonite (B), and tetraethoxysilane hydrolyzate (C) were mixed with A-β / B / C = 23/23/54 (weight ratio). A gas barrier film was prepared in the same manner as in Comparative Example 12, except that the mixture was charged into the container at the same ratio.

<Comparative Example 14> PVA-β (A-β), montmorillonite (B), and tetraethoxysilane hydrolyzate (C) were mixed with A-β / B / C = 40/20/40 (weight ratio). A gas barrier film was prepared in the same manner as in Comparative Example 12, except that the mixture was charged into the container at the same ratio.

Comparative Example 15 A gas barrier film was prepared in the same manner as in Example 15 except that the composite coating layer in Comparative Example 9 was formed.

Comparative Example 16 Example 16 was repeated except that the composite coating layer in Comparative Example 12 was formed.
A gas barrier film was prepared in the same manner as described above.

(Evaluation of Performance) Each of the gas barrier films obtained in Examples 1 to 6 and 9 to 14 and Comparative Examples 1 to 6 and 9 to 14 was stored for one month in an atmosphere of 40 ° C. and 90% RH.
Before and after storage, (1) oxygen permeability and (2) water vapor permeability were measured as follows. (1) Oxygen permeability Oxygen permeability measuring device (OXT, OXT
RAN 10 / 40A), 30 ° C, 70% R
H and 30 ° C./100% RH atmosphere. (2) Water vapor permeability Water vapor permeability measuring device (PE, manufactured by Modern Control)
RMATRAN W6) at 40 ° C, 90% R
H and 40 ° C., 100% RH atmosphere. Further, Examples 7 to 8, 15 to 16, and Comparative Examples 7 to 8, 1
Each of the gas barrier films obtained in Nos. 5 to 16 was evaluated for the stretched sample by 2% in length. That is, (1) oxygen permeability and (2) water vapor permeability before and after tension were measured.

Table 1 shows Examples 1 to 3 and Comparative Examples 1 to 3.
And the measurement results of (1) oxygen permeability and (2) water vapor permeability are shown. As can be seen from Table 1, when polyvinyl alcohol and the inorganic layered compound are mixed at a fixed mixing ratio, the gas barrier property is higher when PVA-α is used than when conventional polyvinyl alcohol (PVA-β) is used. Is good.

[0056]

[Table 1]

Table 2 shows Examples 4 to 6 and Comparative Examples 4 to 6.
And the measurement results of (1) oxygen permeability and (2) water vapor permeability are shown. As can be seen from Table 2, when polyvinyl alcohol and the inorganic layered compound are mixed at a fixed compounding ratio, gas barrier properties are higher when PVA-α is used than when conventional polyvinyl alcohol (PVA-β) is used. Is good.

[0058]

[Table 2]

Table 3 shows Examples 7 to 8 and Comparative Examples 7 to 8.
2 shows the measurement results of (1) oxygen permeability and (2) water vapor permeability. As can be seen from Table 3, even after the tension is applied, the gas barrier film using PVA-α maintains a higher gas barrier property than the gas barrier film using conventional polyvinyl alcohol (PVA-β), and is suitable for processing. It can be said to be excellent.

[0060]

[Table 3]

Table 4 shows Examples 9 to 11 and Comparative Examples 9 to
The measurement results of (1) oxygen permeability and (2) water vapor permeability are shown below. As can be seen from Table 4, when polyvinyl alcohol and the inorganic layered compound are mixed at a fixed mixing ratio, the gas barrier property is higher when PVA-γ is used than when conventional polyvinyl alcohol (PVA-β) is used. Is good.

[0062]

[Table 4]

Table 5 shows Examples 12 to 14 and Comparative Example 1.
The measurement results of (1) oxygen permeability and (2) water vapor permeability are shown below. As can be seen from Table 5, when the polyvinyl alcohol and the inorganic layered compound are mixed at a fixed blending ratio, the PVA- is compared with the case where the conventional polyvinyl alcohol (PVA-β) is used.
The gas barrier property is better when γ is used.

[0064]

[Table 5]

Table 6 shows Examples 15 and 16 and Comparative Example 1.
The measurement results of (1) oxygen permeability and (2) water vapor permeability at 5 to 16 are shown. As can be seen from Table 6, even after the tension is applied, the gas barrier film using PVA-γ maintains a higher gas barrier property than the gas barrier film using conventional polyvinyl alcohol (PVA-β), and is suitable for processing. It can be said to be excellent.

[0066]

[Table 6]

[0067]

According to the present invention, at least one side of a substrate is provided.
A gas barrier film provided with a composite coating layer formed from a mixture containing polyvinyl alcohol having a 1,2-glycol bond content of 0.01% or more and 1.9% or less and an inorganic layered compound as main components. As a result, a gas barrier film having excellent barrier properties, which maintains higher barrier properties than conventional gas barrier films even under high humidity conditions.

Further, according to the present invention, a polyvinyl alcohol having a 1,4-glycol bond content of 0.01% or more and 2.0% or less and an inorganic layered compound as main components are provided on at least one surface of a substrate. Since it is a gas barrier film provided with a composite coating layer formed from the mixture described above, a gas barrier film excellent in barrier properties that maintains higher barrier properties than conventional gas barrier films even under high humidity conditions.

Continued on the front page F term (reference) 4F100 AA00C AA00D AA19A AA20A AA21A AB10D AB11D AB12D AC10D AD00A AH08D AK01A AK07 AK21B AK21D AT00A BA04 BA05 BA06 BA07 BA10A BA10D BA13 EH66A JD01YYB00

Claims (8)

[Claims] 1. A mixture comprising, as a main component, a polyvinyl alcohol having a 1,2-glycol bond content of 0.01% or more and 1.9% or less and at least one surface of a substrate. A gas barrier film provided with a formed composite coating layer. 2. A mixture comprising, as a main component, a polyvinyl alcohol having a 1,4-glycol bond content of 0.01% or more and 2.0% or less and at least one surface of a base material. A gas barrier film provided with a formed composite coating layer. 3. The weight ratio of polyvinyl alcohol (A) and inorganic layered compound (B) in the composite coating layer is A / B = 1.
The gas barrier film according to claim 1, wherein the gas barrier film has a ratio of 0/90 to 99/1. 4. The gas barrier film according to claim 1, wherein the substrate is a plastic film or a ceramic vapor deposited film provided with a ceramic vapor deposited layer. 5. The gas barrier film according to claim 4, wherein the ceramic of the ceramic vapor-deposited layer is a silicon oxide-based, aluminum oxide-based, or titanium oxide-based ceramic. 6. The gas barrier film according to claim 1, wherein the composite coating layer further contains a hydrolyzate of a metal alkoxide as a component. 7. The gas barrier film according to claim 6, wherein the metal forming the metal alkoxide is silicon, aluminum, or titanium. 8. The method according to claim 1, wherein said inorganic layered compound is montmorillonite.
The gas barrier film according to the above item.