JPH11302422A - Gas barrier material, its preparation and package - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier material which is a transparent gas barrier material as a package for food, pharmaceutical products or the like, inhibits the generation of cracks caused by deformation under stress such as stretching, or the like, and maintains the barrier property, and a preparation process thereof. SOLUTION: In a preparation process of a gas barrier material, a gas barrier material 1 is prepared by forming an organic-inorganic composite film 40 wherein an organic compound, comprising an organosilicon monomer molecule, or the like, is distributed in the thickness direction in an inorganic compound film 20 comprising silicon oxide containing pores 22 on one side of a polymer film substrate 10. Here, after the inorganic compound film 20 is formed on the substrate 10 through vacuum metallizing in the presence of an inert gas, an organic compound 30 is distributed in the thickness direction of the iorganic compound film 20 through chemical vapor deposition in the presence of a vapor of an organosilicon compound and oxygen gas to form an organic-inorganic composite film 40.

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 material having a high barrier property against permeation of oxygen and water vapor suitable for packaging of foods and pharmaceuticals, and more particularly to a gas barrier material by deformation. The present invention relates to a gas barrier material with less deterioration in performance and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as a packaging material, gas barrier properties are important for preserving contents, and aluminum foil and polyvinylidene chloride (PVDC) coat are used as packaging materials having a barrier property against oxygen and water vapor. Has been used.
However, although aluminum foil has excellent gas barrier properties, it is opaque so that its contents cannot be confirmed, its contents cannot be inspected with a metal detector, it does not pass microwaves, so it cannot be used for microwave oven food, etc., incineration There were many problems such as the aluminum ingot melted in the process accumulating on the furnace bottom and damaging the furnace.

[0003] On the other hand, PVDC is transparent, but has insufficient gas barrier properties and contains chlorine in its molecules. Therefore, toxic chlorine-based gas is discharged during the incineration process, which is not preferable for environmental hygiene. There was also a problem that the incinerator was corroded by chlorine gas.

[0004] To solve the above two problems,
Recently, a gas barrier film in which an inorganic compound film made of silicon oxide or the like is provided as a gas barrier layer on a polymer base material has been developed. However, although these are transparent as compared with aluminum foil, their gas barrier properties are still insufficient, and they are weak against tensile stress or the like, and their gas barrier properties deteriorate, so that their use as gas barrier materials has been limited.

In a gas barrier material having the above-mentioned inorganic compound film provided on a polymer resin base material, a gas barrier property is deteriorated because a crack (crack) is generated in the inorganic compound film when a stress such as tension is applied. Even in a gas barrier material in which an organic film is laminated on an inorganic compound film provided on a polymer resin substrate, it has been difficult to maintain gas barrier properties due to cracks generated in the inorganic compound film.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and it is an object of the present invention to suppress the generation of cracks even when deformed by stress such as tension. An object of the present invention is to provide a gas barrier material capable of maintaining a barrier property and a method for manufacturing the same.

[0007]

In order to achieve the above object, according to the present invention, first, at least one surface of a substrate made of a polymer resin contains silicon oxide as a main component. A gas barrier material characterized in that an organic compound containing at least one or more carbon atoms in a molecule is formed in an inorganic compound film to form an organic-inorganic composite film distributed in a thickness direction. is there.

According to a second aspect of the present invention, in the gas barrier material according to the first aspect, the organic compound is an organosilicon monomer molecule or a substance obtained from the organosilicon monomer molecule.

Further, in the invention according to claim 3, after the inorganic compound film is provided on one surface of the base material made of the polymer resin by a vacuum deposition method in the presence of an inert gas, A method for producing a gas barrier material, comprising distributing in the thickness direction of the inorganic compound film by a chemical vapor deposition method in the presence of vapor of an organic silicon compound and oxygen gas to form an organic-inorganic composite film. .

According to a fourth aspect of the present invention, there is provided the method for producing a gas barrier material according to the third aspect, wherein the inert gas is helium (He) gas.

According to a fifth aspect of the present invention, the vacuum deposition and the chemical vapor deposition are performed continuously without returning the inside to the atmospheric pressure in the same apparatus. This is a method for producing a gas barrier material.

According to a sixth aspect of the present invention, there is provided an apparatus for manufacturing a gas barrier material capable of independently adjusting the degree of vacuum during the vacuum vapor deposition and during the chemical vapor deposition. This is a method for producing a gas barrier material.

According to a seventh aspect of the present invention, there is provided a package comprising a gas-barrier material according to the first or second aspect, which is used as a transparent and gas-barrier packaging material for foods and medicines. It was done.

[0014]

Embodiments of the present invention will be described below. As shown in FIG. 1, the gas barrier material of the present invention comprises, on at least one surface of a base material (10) made of a polymer resin, an inorganic compound film (20) containing silicon oxide as a main component, Organic compounds containing at least one atom (3
0) is an organic-inorganic composite film (4) distributed in the thickness direction.
0) is formed.

Further, the organic compound (30) is characterized by comprising an organosilicon monomer molecule or a substance obtained from the organosilicon monomer molecule.

Further, in the method for producing a gas barrier material according to the present invention, the inorganic compound film (20) may be formed by subjecting the inorganic compound film (20) to a base material (1
0), the organic compound (30) is distributed in the thickness direction of the inorganic compound film (20) by a chemical vapor deposition method in the presence of at least the vapor of an organic silicon compound and oxygen gas. An inorganic composite film (40) is provided.

The inert gas is helium (H
e) A method for producing a gas barrier material comprising gas.

The substrate (10) made of a polymer resin used in the present invention may be used for the purpose of the gas barrier material.
It can be appropriately selected from the physical properties, characteristics, economy and the like of the packaged item. Specific examples include stretched or unstretched resin films such as nylon, polyethylene, polypropylene, polyvinyl chloride, polycarbonate, polyvinyl alcohol, cellulose, polyacrylate, polyurethane, cellophane, polyethylene terephthalate, and ionomer. The thickness of the base material (10) can be appropriately set in accordance with the purpose of use of the gas barrier material, the stability at the time of production, and the like, and can be, for example, about 10 to 100 μm.

The inorganic compound film (20) constituting the gas barrier material (1) is preferably made of silicon oxide. This silicon oxide film is made of SiO
_x (X = 1 to 2), and the film thickness is 10 to 50
00 °, preferably about 200 to 1500 °. If the film thickness is less than 10 °, the inorganic compound film (20) made of silicon oxide is liable to fall out and the barrier property is likely to vary, and if it exceeds 5000 °, the flexibility of the inorganic compound film (20) is impaired, Cracks are likely to occur. From the viewpoint of transparency, silicon oxide is SiO _x (X
= 1.5-2).

The inorganic compound film (20) made of silicon oxide
Is applied on a substrate (10) made of a polymer resin by a vacuum coating method, a sputtering method, a plasma CVD method or the like. Among them, silicon oxide or the like is heated and evaporated in a vacuum. The vacuum deposition method of adhering to a film by using an inorganic compound film (2
This is a method suitable for attaching 0) to a substrate in a dense structure. The heating method in this vacuum deposition method is resistance heating,
There are induction heating, electron beam heating, and the like, which can be appropriately selected depending on the deposition material and purpose.

The inorganic compound film (20) made of silicon oxide or the like is adhered while supplying a gas into the above-mentioned vacuum deposition atmosphere, so that fine voids (hereinafter referred to as pores (22)) are formed in the dense inorganic compound film (20). )) Can be formed. Due to the presence of the pores (22), the organic compound (30) can be easily mixed inside the inorganic compound film (20) to form the organic-inorganic composite film (40).

Further, by appropriately controlling the type and flow rate of the gas to be supplied, the pores (2) in the inorganic compound film (20) are controlled.
The size and number of 2) can be controlled. The supplied gas is an inert gas, especially helium (H) having a small atomic diameter.
e) is suitable for creating the pore (22). If an active gas is supplied during the deposition of silicon oxide, the active gas reacts with the silicon oxide at the pore (22) interface, and the activity of the pore (22) interface in the silicon oxide is lost. Even if the inorganic compound film (20) is coated with the organic compound (30), the inorganic compound film (20) made of silicon oxide and the organic compound (30) do not react or adsorb to each other, so that they are not suitable for mixing.

Here, by supplying an inert gas into the vapor deposition atmosphere, a silicon oxide vapor deposition film (inorganic compound film (2)
0)), an inert gas is taken in, but does not react with silicon oxide.
2) can be made. At this time, by using helium (He) having a small atomic diameter, the size and number of the pores (22) can be easily controlled, which is more preferable. However, it is not always necessary to limit to helium. As an inert gas supplied during vacuum deposition, besides helium, neon,
Argon or the like can be used, and can be appropriately selected from the physical properties and characteristics of the organic substance to be coated after the vapor deposition, stable vapor deposition conditions, and the like.

In the present invention, in order to form an organic / inorganic composite film (40) by mixing an organic compound (30) into an inorganic compound film (20) formed by a vacuum deposition method under a high vacuum condition, This is a process in which the organic compound (30) is continuously (in-line) deposited in the same apparatus as the vacuum deposition by a chemical vapor deposition method.

By this process, the organic compound (30)
Is not only laminated on the inorganic compound film (20) made of silicon oxide or the like, but also enters the pores (22) in the silicon oxide film and reacts or adsorbs with the silicon oxide forming the pores (22) to form silicon oxide or the like. The organic / inorganic composite film (40) can be obtained by mixing the organic compound (30) in the inorganic compound film (20) composed of

In addition, by performing this process in-line without releasing the atmospheric pressure, it is possible to prevent a problem that the pore (22) reacts or adsorbs with an unintended substance, so that the pore (22) cannot react with or adsorb to an intended organic substance. And the manufacturing efficiency is improved.

As a method of mixing the organic compound (30) into an inorganic compound film (20) made of silicon oxide or the like formed on a substrate (10) made of a polymer resin, plasma CVD as a chemical vapor deposition method is used. Method, a sputtering method, etc., the raw material of the organic compound (30), the state of the inorganic compound film (20) made of silicon oxide or the like, the number and size of the pores (22), and the number of the target organic compound (30). It can be appropriately selected from physical properties and the like. For example, by using a plasma CVD method, a raw material gas is supplied in the vicinity of the inorganic compound film (20) made of silicon oxide or the like, and plasma is generated there to mix the organic compound (30) with the inorganic compound film (20). Let it. Organic compound (3) mixed with inorganic compound film (20)
As the raw material 0), for example, an organic silicon compound can be used. The use of the organosilicon compound facilitates the reaction or adhesion with the pores (22) of the inorganic compound film (20) made of silicon oxide because it already has a bond between carbon and silicon.

Examples of the organic silicon compound as a raw material of the organic compound (30) include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane,
Methyl triethoxy silane, dimethyl ethoxy silane, trimethyl ethoxy silane, tetramethoxy silane, tetra ethoxy silane, ethyl trimethoxy silane, ethyl triethoxy silane, normal propyl trimethoxy silane, normal butyl trimethoxy silane,
Isoptyltrimethoxysilane, normal hexyltrimethoxysilane, vinyltrimethoxysilane, tetramethyldisiloxane, hexamethyldisiloxane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, getylsilane, propylsilane, phenylsilane, vinyl Examples include trimethylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, and phenyltrimethoxysilane. Among them, tetramethyldisiloxane and hexamethyldisiloxane are preferable.

By supplying oxygen together with the organic silicon compound, the degree of oxidation of the organic compound (30) component formed by the plasma CVD method and the oxidation of the inorganic compound film (20) made of silicon oxide formed by the vacuum evaporation method are increased. The degree can be adjusted arbitrarily. In order to stabilize the plasma CVD atmosphere, an inert gas such as argon or helium can be added to the source gas supply system, but it is not always necessary.

Next, a method for manufacturing the gas barrier material of the present invention will be described with reference to the drawings. As shown in FIG. 2, vacuum deposition and plasma CV used in the method of manufacturing a gas barrier material of the present invention.
FIG. 2 shows an example of the in-line deposition apparatus (200) of D.
As shown in FIG. 5, the apparatus comprises an unwinding and winding chamber (90), a vacuum evaporation chamber (80), a plasma CVD chamber (62), and a peripheral raw material gas supply unit.
1) and an unwinding roll (52), a take-up roll (53), a cooling / electrode roll (54), an auxiliary roll (55), a shielding plate (5) disposed in a vacuum chamber (51).
6), crucible (57), electron beam generator (58), deflection coil (59), inert gas supply pipe for vacuum evaporation (60), plasma CVD chamber (62), magnet (7)
1), a raw material supply pipe for plasma CVD (63), an inert gas supply device (61) disposed around a vacuum chamber (51), a flow regulator (64), a gas mixer (65), an oxygen gas Supply device (66), raw material heating device (67), vacuum pump for the winding section (68), vacuum pump for the vapor deposition section (69), vacuum pump for plasma CVD (7)
0) and a vacuum gauge (72).

The vacuum chamber (51) is divided into an unwinding-winding chamber (90) and a vacuum evaporation chamber (80) by a shielding plate (56). A predetermined vacuum degree can be set by the vacuum pump (69). The plasma CVD chamber (62) is also provided with a vacuum pump (70) for the plasma CVD chamber to perform plasma CVD at a different vacuum level from the vacuum deposition chamber (80) and the unwinding and winding chamber (90). Control. These degrees of vacuum can be controlled by unique values, but may be the same degree of vacuum.

The in-line vapor deposition apparatus (20)
A roll of the base material (10) made of a polymer resin is mounted on the unwinding roll (52) of (0), and is wound via the auxiliary roll (55), the cooling / electrode roll (54), and the auxiliary roll (55). A material transport path leading to the take-up roll (53) is formed.
The inside of the vacuum chamber (51) is depressurized by the vacuum pump (68) for the winding section and the vacuum pump (69) for the vapor deposition section, and the unwinding chamber (90) and the vacuum vapor deposition chamber (8)
0) In both cases, the degree of vacuum is 10-2 Torr or more, preferably ^10-4 or more.

Next, an inert gas such as helium is supplied into the vacuum chamber (51) through an inert gas supply device (61), a flow controller (64), and an inert gas supply pipe (60) for vacuum evaporation. The vacuum deposition inert gas supply pipe (60) is provided between the crucible (57) and the cooling / electrode roll (54) so that the inert gas is taken into the silicon oxide deposition. Helium is supplied as an example of an inert gas into the vacuum chamber (51) through an inert gas supply pipe (60) for vacuum deposition. The type and flow rate of the inert gas differ depending on the number and size of the target pores and the apparatus used for vapor deposition. It is desirable that the inflow rate of the inert gas is 0.07 to 1.0 in terms of molar ratio with respect to the evaporation rate of silicon oxide in the vacuum chamber (51).

The properties of the inorganic compound film (20) made of silicon oxide in the gas barrier material (1) produced according to the present invention are determined by the value of X in the composition SiO _X of silicon oxide and the film thickness. By setting the transport speed of (10), the power of the electron beam used for evaporation, and the flow rate of the inert gas to appropriate values, it is possible to form a good deposited inorganic compound film (20) made of silicon oxide.

The above-mentioned deposited inorganic compound film (2) made of silicon oxide
In the plasma CVD for distributing the organic compound (30) to the pores (22) in (0), an organic silicon compound and oxygen gas are mixed and supplied. Although the oxygen content contained in the plasma CVD source gas can be changed depending on the properties of the target film, the oxygen gas can be reduced to about 1 to 17 with respect to the organic silicon compound 1. Plasma C
The blowing of the raw material gas from the VD raw material supply pipe (63) is carried out by cooling and cooling so that the whole of the substrate (10) film made of the polymer resin is conveyed by the plasma and the organic compound (30) is spread over the entire surface. The magnet (71) is uniformly blown out toward the electrode roll (54). Further, under the mixing conditions, the conditions may be such that a film is formed by plasma CVD alone, or the condition may not be a film. Plasma C
The inside of the VD chamber (62) is required to have a degree of vacuum of 10-1 Torr or more, and is adjusted to a degree of vacuum suitable for supplying the organic compound (30). The electric power at the time of plasma generation by plasma CVD can be arbitrarily set depending on the thickness of the deposited inorganic compound film (20) made of silicon oxide, the number and size of the pores (22), and the like.

[0036]

Next, the present invention will be described more specifically with reference to examples. Example 1 A 12 μm-thick raw material of a polyethylene terephthalate film was used as a substrate (10) made of a polymer resin, and was attached to an unwinding roll (52) of an inline vapor deposition device (200). Next, the unwinding and winding chamber (90) in the vacuum chamber (51) of the in-line evaporation apparatus (200), the vacuum evaporation chamber (80), and the plasma C
The pressure in the VD chamber (62) was reduced to 1 × 10 −5 Torr.

Subsequently, 30K is applied to the electron beam generator (58).
An electric power of W was supplied to generate an electron beam, and the electron beam was irradiated to silicon oxide in the crucible (57) using the deflection coil (59) and evaporated. At this time, helium gas was supplied through an inert gas supply pipe (60) for vacuum evaporation at a rate of 0.15 with respect to the silicon oxide evaporation rate. Subsequently, the polyethylene terephthalate film, which is the substrate (10), is transported from the unwinding roll (52) at a speed of 2 m / sec, and is exposed to this vapor deposition atmosphere, whereby an inorganic compound made of silicon oxide containing pores (22) is formed. A gas barrier material provided with the film (20) was obtained.

The gas barrier material obtained as described above is conveyed to a plasma CVD chamber (62) which is continuous with the vacuum evaporation chamber (80). In the plasma CVD chamber (62), an organic silicon compound is used as a source gas. 50 sccm of xamethylene disiloxane is passed through a raw material heating device (67) and a flow rate regulator (64), and 100 sccm is passed through an oxygen gas supply device (66) and a flow rate regulator (64).
And mixed in a mixed state through a raw material supply pipe for plasma CVD (63) and a magnet (71).
It was supplied to the VD chamber (62). On the other hand, cooling / electrode roll (5
In 4), a power of 250 W was supplied, and glow discharge plasma was generated by the raw material gas. At this time, the plasma CVD chamber (6
The pressure in 2) was kept at 10-2 Torr.

As described above, the organic compound (30) is mixed into the gas barrier material provided with the inorganic compound film (20) made of silicon oxide by plasma CVD to form the organic / inorganic composite film (40). Material (1) was obtained.

Example 2 A gas barrier material (1) was obtained under the same conditions as in Example 1 except that the supply amount of helium gas was set to 0.5 as a ratio to the evaporation rate of silicon oxide.

<Comparative Example 1> A gas barrier material (1) was obtained under the same conditions as in Example 1 except that the supply amount of helium gas was 2.0 in terms of the ratio to the evaporation rate of silicon oxide.

Comparative Example 2 A gas barrier material (1) was obtained under the same conditions as in Example 1 except that silicon oxide was vapor-deposited without supplying helium gas.

With respect to the gas barrier materials (1) obtained in Examples 1 and 2 and Comparative Examples 1 and 2, the gas barrier materials before applying the organic compound (30) by plasma CVD were compared with Comparative Samples 3, 4, 5 and 5, respectively. 6.

As described above, the silicon oxide is vacuum-deposited with the pores (22) on the substrate (10) made of a polyethylene terephthalate film, and then the gas barrier material (30) in which the organic compound (30) is mixed by plasma CVD. For 1), oxygen barrier properties, water vapor barrier properties, and tensile resistance were measured by the following evaluation methods, and are shown in Table 1. [Evaluation method] (1) Oxygen barrier property: Measured with a MOCONOXTRAN 10 / 50A oxygen gas permeability measuring device (manufactured by Modern Control Co., Ltd.) in an atmosphere of a temperature of 30 ° C. and a humidity of 70% RH to obtain an oxygen permeation amount. (2) Water vapor barrier property: temperature 40 ° C, humidity 90% RH
Was measured by the cup method of JISZ-0208 under the atmosphere described in (1) to determine the amount of water vapor permeation. (3) Tensile resistance: The material of the gas barrier material (1) is cut out to a length of 60 cm and a width of 14 cm, pulled at a constant speed in the length direction to a predetermined strain (3%, 6%), and then restored. The oxygen barrier property and the water vapor barrier property were measured as the permeation amount.

The unit of the amount of oxygen permeation in the following table is:
The unit of cc / m ² · day · atm and water vapor permeability is
g / m ² · day.

[0046]

[Table 1]

According to Table 1, the oxygen barrier property is a gas permeation amount of 140 cc / m ² · day · atm for a 12 μm thick polyethylene terephthalate film made of a polymer resin, but the silicon oxide is supplied without supplying an inert gas. Gas barrier material (Comparative Sample 6) on which silicon oxide is deposited has a thickness of about 5
At 00 °, the oxygen gas permeation amount is 1.3 cc / m ² · da
y · atm. In the case of a polyethylene terephthalate film having a thickness of 12 μm, the water vapor transmission rate is 55 g / m ² · day, but the water vapor transmission rate is 2.5 g / m ² by depositing silicon oxide.
-It becomes less as day.

A film (comparative sample 2) obtained by laminating an organic compound (30) by in-line plasma CVD on the inorganic compound film (20) deposited film (comparative sample 6) has further improved gas barrier properties. That is, with respect to the oxygen barrier property, by laminating the organic compound (30) film, the oxygen gas permeation amount is 0.9 cc / m ² · day.
· Atm, and the water vapor permeability is reduced to 1.6 g / m ² · day by laminating the organic compound (30) film on the water vapor barrier property.

Helium is supplied as an inert gas for vapor deposition
In the case of the inorganic compound film (20) (Comparative samples 3, 4,
5) Due to the presence of the pore (22), both oxygen and water vapor are transparent.
Overdose increases. The lowest helium flow rate
In the case (Comparative Sample 3), the oxygen permeation amount was 5.9 cc.
/ M^Two・ Day ・ atm, water vapor transmission rate is 3.4g / m
^Two-Silicon oxide deposited without supply of day and helium
(Comparative Sample 6). These inorganic compound films
(20) Organizing the deposited film by plasma CVD
Compounding compound (30) improves gas barrier properties
You. Supply helium to deposit silicon oxide, and then
In the case of Example 1 in which Zuma CVD was performed, both oxygen and water vapor were used.
The amount of transmission decreases. However, the oxygen gas permeation amount is 2.0cc
/ M^Two・ Day ・ atm, water vapor transmission rate 2.7g / m^Two
・ Deposit silicon oxide densely without supplying day and helium
After performing plasma CVD (Comparative Sample 2)
The transmission amount also increases.

When the film is pulled, the amount of gas permeation increases for both oxygen and water vapor. In the case of a vapor-deposited film (Comparative Sample 2) in which an organic compound (30) film is laminated on an inorganic compound film (20), the oxygen gas permeation amount is 4.1 cc / m when the film length is stretched by 3% at a constant speed. ²・ day ・
atm, the amount of water vapor permeated is 8.9 g / m ² · day, and when pulled 6% with respect to the film length, the amount of permeated oxygen gas is 121.1 cc / m ² · day · atm, and the amount of water vapor permeated 52.2 g / m ^2. Day and gas barrier properties are significantly degraded. On the other hand, an organic / inorganic composite film in which an inorganic compound film (20) containing pores (22) is coated with an organic compound (30) film by vapor deposition of silicon oxide in an atmosphere containing an inert gas. In the case of (40), when the ratio between the helium flow rate and the silicon oxide evaporation amount was 0.15 (Example 1), the oxygen gas permeation amount was 2.2 cc / m ² ··· when the film length was pulled by 3%. day.atm, water vapor transmission amount: 3.1 g / m ² .day, 6% based on film length
Even when pulled, the oxygen gas permeation amount is ^2.5 cc / m ² · da
y · atm and the amount of water vapor permeation were 5.3 g / m ² · day, and it was possible to suppress deterioration of gas barrier properties due to tension.

[0051]

As described above, the present invention has the following effects. That is, on at least one surface of a substrate made of a polymer resin, an inorganic compound film containing silicon oxide as a main component, an organosilicon monomer molecule containing at least one or more carbon atoms in a molecule, or an organosilicon monomer molecule is used. Organic compound,
As a gas barrier material formed by forming an organic-inorganic composite film distributed in the thickness direction, the inorganic compound film, on one side of the base material made of the polymer resin by a vacuum deposition method in the presence of an inert gas After providing, a method for producing a gas barrier material in which the organic compound is distributed in the thickness direction of the inorganic compound film by a chemical vapor deposition method in the presence of at least vapor of an organic silicon compound and oxygen gas to form an organic-inorganic composite film. Therefore, it is possible to provide a gas barrier material that can suppress the generation of cracks even when deformed due to stress such as tension and maintain the barrier properties.

Further, since the above-mentioned vacuum deposition and the above-mentioned chemical vapor deposition are carried out continuously in-line without returning the inside of the apparatus to the atmospheric pressure in the same apparatus, the inorganic compound film is made of oxygen in the atmosphere. In addition to preventing contamination by water and water vapor, it can contribute to simplification of the process and improvement of manufacturing efficiency.

Accordingly, the present invention exerts excellent practical effects in use as a package having a transparent and gas-barrier property for foods and pharmaceuticals, and as a package superior in waste disposal after use. .

[Brief description of the drawings]

FIG. 1 is an explanatory view schematically showing a gas barrier material according to an embodiment of the present invention in a side sectional view.

FIG. 2 is a schematic view of an in-line vapor deposition apparatus for explaining production of a gas barrier material according to one embodiment of the present invention.

[Explanation of symbols]

 1 Gas barrier material 10 Base material made of polymer resin 20 Inorganic compound film 22 Pore 30 Organic compound 40 Organic-inorganic composite film 51 Vacuum chamber 52 Unwinding roll 53 ‥‥ Take-up roll 54 ‥‥ Cooling / electrode roll 55 ‥‥ Auxiliary roll 56 ‥‥ Shielding plate 57 ‥‥ Crucible 58 ‥‥ Electron beam generator 59 ‥‥ Deflection coil 60 ‥‥ Inert gas supply pipe for vacuum evaporation 61 << Inert gas supply device 62 >> Plasma CVD chamber 63 >> Raw material supply pipe for plasma CVD 64 >> Flow regulator 65 >> Gas mixer 66 >> Oxygen gas supply device 67 >> Raw material heating device 68 >> Vacuum pump for winding unit 69 Vacuum pump for vapor deposition unit 70 Vacuum pump for plasma CVD 71 Magnet 72 Vacuum gauge 80 Vacuum vapor deposition chamber 0 ‥‥ unwinding winding chamber 200 ‥‥-line vapor deposition apparatus

Claims (7)

[Claims] 1. An organic compound containing at least one carbon atom in a molecule in an inorganic compound film containing silicon oxide as a main component on at least one surface of a substrate made of a polymer resin.
A gas barrier material formed by forming an organic / inorganic composite film distributed in a thickness direction. 2. The gas barrier material according to claim 1, wherein the organic compound is an organosilicon monomer molecule or a substance obtained from the organosilicon monomer molecule. 3. The method according to claim 1, wherein the inorganic compound film is provided on one side of a base material made of the polymer resin by a vacuum deposition method in the presence of an inert gas, and then the organic compound is converted into at least vapor of an organic silicon compound and oxygen. A method for producing a gas barrier material, wherein an organic / inorganic composite film is formed by distributing in the thickness direction of the inorganic compound film by a chemical vapor deposition method in the presence of a gas. 4. The method for producing a gas barrier material according to claim 3, wherein said inert gas is helium (He) gas. 5. The method for producing a gas barrier material according to claim 3, wherein the vacuum deposition and the chemical vapor deposition are continuously performed in the same apparatus without returning the inside to atmospheric pressure. 6. The method for producing a gas barrier material according to claim 3, wherein the apparatus for producing a gas barrier material is capable of independently adjusting the degree of vacuum during the vacuum deposition and during the chemical vapor deposition. 7. A package using the gas barrier material according to claim 1 or 2 as a transparent and gas-barrier packaging material for foods, medicines and the like.