JP2002292777A - High gas barrier film and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high gas barrier film having high barrier properties against oxygen gas or the like and useful for packaging various articles, for example, food, medicines, industrial articles or the like. SOLUTION: The high gas barrier film is constituted by providing an inorganic matter layer on a polymeric film and the concentration of oxygen at the interface of the plymeric film with the inorganic matter layer is 5 atm % or more and less than 24 atm %.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inorganic vapor-deposited film having an inorganic layer on a polymer film and a method for producing the same, and more particularly to an aluminum film having an aluminum and / or aluminum oxide layer on a polymer film. The present invention relates to a vapor-deposited film and a method for manufacturing the same. This aluminum vapor-deposited film has excellent barrier properties against oxygen gas and the like, and is useful as a packaging material for packaging various articles such as foods, pharmaceuticals, and industrial supplies.

[0002]

2. Description of the Related Art Conventionally, on the surface of a plastic substrate,
Using an inorganic substance (including an inorganic oxide) such as aluminum, silicon oxide, aluminum, and magnesium oxide, a physical vapor deposition method (PVD method) such as a vacuum deposition method, a sputtering method, and an ion plating method, or a plasma A gas barrier film obtained by forming a vapor-deposited film of an inorganic substance by using a chemical vapor deposition method (CVD method) such as a chemical vapor deposition method, a thermal chemical vapor deposition method, or a photochemical vapor deposition method,
Foods that need to block various gases such as water vapor and oxygen,
It is used to package various articles such as pharmaceuticals and industrial supplies.

[0003] In order to further improve the barrier properties of the gas barrier film against oxygen gas or water vapor, a method of treating the surface of a plastic substrate or a method of coating an anchor coating agent has been proposed. As a method of treating the plastic surface,
For example, there is a method in which the surface of a plastic substrate is preliminarily subjected to a pretreatment such as a corona discharge treatment or a glow discharge treatment to roughen the surface. As a method of coating the anchor coating agent, for example, in advance, a coating film of an urethane-based or ester-based deposition anchor coating agent is formed to form an anchor coating agent layer, and the adhesion between the plastic substrate and the deposited film is improved. There are ways to improve.

[0004]

However, it has been the technical reality that it is technically extremely difficult to produce a gas barrier film having a high barrier property even if the above-mentioned treatment is performed. In addition, there is a problem that the manufacturing cost increases because the number of manufacturing steps increases. In addition, the above-mentioned vapor-deposited film obtained by vapor-depositing an inorganic substance such as aluminum is usually manufactured by heating and evaporating metallic aluminum to form a film by using electron beam heating, resistance heating or a crucible method. A considerable amount of residual gas such as moisture easily exists in the atmosphere, and this residual gas causes a large number of water molecules to be taken into the deposited film, resulting in reduced denseness of the deposited film and reduced gas barrier properties. There is a problem that it is significantly reduced.

An object of the present invention is to provide a gas barrier film which has a high barrier property against oxygen gas and the like and is useful for packaging various articles such as foods, pharmaceuticals and industrial supplies.

[0006]

The objects of the present invention are: 1) A film having an inorganic layer on a polymer film, wherein the oxygen concentration at the interface between the polymer film and the inorganic layer is 5 atm% or more, 24 atm%. 2) a film having an inorganic layer on a polymer film, wherein the density at the interface between the polymer film and the inorganic layer is 1.8 g / cm ³ or more and 4.0 g / cm ³ 3) a film having an inorganic layer on a polymer film, wherein the density of the inorganic layer is 2.5 g / cm ³ or more,
g / cm ³ or less; 4) a film having an inorganic layer on a polymer film, wherein the oxygen concentration at the interface between the polymer film and the inorganic layer is 5 atm% or more; Less than 24 atm% and the density at the interface between the polymer film and the inorganic layer is 1.8 g / c
a high gas barrier film having an m ³ or more and 4.0 g / cm ³ or less; 5) a film having an inorganic layer on a polymer film, wherein an oxygen concentration at an interface between the polymer film and the inorganic layer is 5 atm% or more; A high gas barrier film having a density of less than 24 atm% and an internal density of the inorganic layer of 2.5 g / cm ³ or more and 4.0 g / cm ³ or less; 6) a film having an inorganic layer on a polymer film Wherein the oxygen concentration at the interface between the polymer film and the inorganic layer is 5 atm% or more and less than 24 atm%, and the density at the interface between the polymer film and the inorganic layer is 1.8 g / cm ³ or more and 4.0 g. / cm ³ or less, and the internal density of the inorganic layer is 2.5 g / cm ³ or more and 4.0 g / cm ³ or less. 7) The inorganic substance is aluminum and / or aluminum oxide. Of the above 1) to 6) 8) In producing the high gas barrier film according to any one of the above 1) to 7) by forming an inorganic layer by a vapor deposition method, the moisture partial pressure in the vapor deposition atmosphere is set to 1. 2 × 10
^-8 Torr or less.

[0007]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A preferred embodiment of the present invention is an aluminum vapor-deposited film having an aluminum vapor-deposited film on a polymer film, wherein the oxygen concentration at the interface between the polymer film and the aluminum vapor-deposited film is 5 atm% to 24 atm.
%, The density at the interface between the polymer film and the aluminum vapor-deposited film is 1.8 g / cm ³ or more and 4.0 g / c.
m ³ or less, and a high gas barrier film that satisfies at least one of the following: the internal density of the aluminum vapor-deposited film is 2.5 g / cm ³ or more and 4.0 g / cm ³ or less; The present invention relates to a method for producing a high gas barrier film in which, when an aluminum vapor deposition film is formed on a molecular film, the moisture partial pressure in the vapor deposition atmosphere is less than 1.2 × 10 ⁻⁸ Torr.

Hereinafter, the present invention will be described in more detail.

First, the high gas barrier film of the present invention has an inorganic layer disposed on the film, and the inorganic substance includes silicon, magnesium, zinc, aluminum, and the like.
These oxides are used, and aluminum and / or aluminum oxide are particularly preferably used. Preferably, aluminum and aluminum oxide are deposited on the film by vapor deposition.

Next, the polymer film constituting the high gas barrier film of the present invention is not particularly limited as long as it is a film made of an organic polymer compound. For example, polyolefin such as polyethylene or polypropylene, polyethylene terephthalate or Polyester such as polyethylene naphthalate, polyamide, polycarbonate, polystyrene, polyvinyl alcohol,
Films made of various polymers such as a saponified ethylene-vinyl acetate copolymer, polyacrylonitrile, polyacetal and the like can be used. The polymer constituting the film may be either a homopolymer or a copolymer, or may be used alone or as a blend. Further, a single-layer film, a film formed by a co-extrusion method of two or more layers, a film stretched uniaxially or biaxially, or the like can be used. The thickness is preferably about 5 to 100 μm, and more preferably 7 to 60 μm, from the viewpoint of the stability at the time of manufacturing the aluminum vapor-deposited film. If necessary, for example, a film to which additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, and a filler are added within a range that does not affect the gas barrier properties can be used.

Next, the thickness of the inorganic layer in the present invention is as follows:
In the case of a deposited film of aluminum or the like, 50 to 2000 mm,
Preferably 100-1000 °, more preferably 2
00-800 ° is good. In the above description, when the thickness of the aluminum vapor-deposited film is greater than 2000 °, the flexibility of the film is reduced, and cracks and the like are easily generated in the film. Also,
If the angle is less than 50 °, the influence of pinholes and the like becomes large, and the permeation of oxygen molecules cannot be sufficiently prevented by the aluminum vapor-deposited film, and the barrier property is reduced.

In the present invention, the above-mentioned aluminum vapor-deposited film is made of a metal such as aluminum, for example, by controlling the water partial pressure of the vapor deposition atmosphere by vacuum vapor deposition, sputtering, ion plating or the like. Can be formed. In the above, as a heating method of the deposition material, for example, an electron beam (E
B) system, high-frequency induction heating system, resistance heating system and the like are used.

Next, the high gas barrier film of the present invention and the method for producing the film will be described in detail, taking as an example the case where an aluminum vapor-deposited film is formed as an inorganic layer.

FIG. 1 is a schematic diagram showing an example of a roll-up type vacuum evaporation apparatus for carrying out the method for producing a high gas barrier film of the present invention. First, in the take-up chamber 2 of the take-up type vacuum evaporation apparatus 1, the polymer film 15 is set on the take-out roll 6, and the cooling drum 1 is taken out via the guide rolls 8, 9, and 10.
Pass through 6. Since a wire such as aluminum is introduced on the boat 5 and the aluminum is evaporated from the boat 5, an aluminum vapor-deposited film is formed on the surface of the polymer film 15 at a position on the cooling drum 16. Then, the polymer film 15 on which the aluminum vapor-deposited film is formed is transferred to the guide rolls 11, 12, 1
3 and is taken up on a take-up roll 7. At this time, an inert gas introduction pipe 14 for introducing an inert gas such as an argon gas or a nitrogen gas is installed in a gap between the winding chamber 2 and the vapor deposition chamber 3 and between the partition walls 4. Introduce an inert gas. The introduction of the inert gas reduces the moisture partial pressure in the vapor deposition atmosphere to a predetermined level, so that the aluminum vapor deposited film of the present invention can be manufactured. Quadrupole mass spectrometer 1
By measuring at 7, the moisture partial pressure in the vapor deposition atmosphere can be grasped. The above example is merely an example, and the present invention is not limited thereto.

In the above description, as a method of introducing an inert gas, specifically, for example, a method of supplying an inert gas from a gas introduction pipe or the like machined into a slit shape or the like can be mentioned. Further, the supply amount of the above-mentioned inert gas is preferably, for example, 50 to 2000 cc / min.

The partial pressure of water in the vapor deposition atmosphere refers to the partial pressure of water in the vapor deposition chamber, and can be calculated from the following equation using a quadrupole mass spectrometer.

The water partial pressure in the vapor deposition atmosphere = (water partial pressure in the quadrupole mass spectrometer / total pressure in the quadrupole mass spectrometer) × pressure in the vapor deposition chamber The quadrupole mass spectrometer is placed in a vacuum chamber. Is a device for measuring the types of elements present in the vapor deposition and their abundances. In order to measure the gas abundance in the vapor deposition atmosphere, measurement is performed at a pressure lower than the actual pressure in the vapor deposition chamber. As an example of the apparatus, there is MASSMATE100 manufactured by Japan Vacuum Engineering Co., Ltd.

The water partial pressure in the above-mentioned vapor deposition atmosphere is as follows.
It is preferably less than 1.2 × 10 ⁻⁸ Torr, more preferably 8 × 10 ⁻⁹ Torr. Moisture partial pressure is 1.2 × 10
^{If the} pressure is higher than ^-8 Torr, a good vapor-deposited film is not formed when aluminum is vapor-deposited, and an aluminum vapor-deposited film having high barrier properties cannot be obtained.

The oxygen concentration of the aluminum deposited film obtained by such a production method can be measured by the following method.

The oxygen concentration of the aluminum deposited film can be determined by X-ray photoelectron spectroscopy using ion gun etching described in “X-ray photoelectron spectroscopy” (edited by The Surface Science Society of Japan, published by Maruzen Co., Ltd.), page 179. Can be measured. When this method is used, composition analysis in the depth direction from the surface of the aluminum-deposited film to the interface between the polymer film and the aluminum-deposited film is possible. Specifically, convergence (150-1,000 μm) was obtained by dispersing a curved single crystal on the surface of an aluminum-deposited film placed in an ultra-high vacuum.
m) Irradiate soft X-rays and detect photoelectrons emitted from the surface (up to several nm) with an analyzer. The element information on the surface can be obtained from the binding energy value of the bound electrons in the substance, and the information on the valence and the bonding state can be obtained from the energy shift of each peak. In addition, it can be quantified using the peak area.

The measuring device was SSX-100 manufactured by US SSI.
Is measured under the following analysis conditions. X-ray source: single connection
Crystal spectroscopy AlKα ray, X-ray spot: 300 × 520 μm
Oval, output 10kV 7mA, analyzer mode
C: Constant Analyzer Energ
y (CAE) Mode, Pass Energy: Re
s. 4 = 150 eV, resolution: Au4f7FWHM =
1.65 eV, degree of vacuum: 1 × 10^-9Torr, Geomet
Lee: θ = 35 ° (θ: tilt of the detector with respect to the sample surface
G), data processing: Smoothing 3 points
s, peak area measurement, b
Acquisition subtraction, pe
ak synthesis, Ar etching: 3 keV
 1.5 × 10 ^-7Torr, 4 × 2 mm raster,
Sputter rate: 4.9 nm / min (SiO_TwoConversion
value).

The measurement was performed under the above-mentioned apparatus and analysis conditions, and Al,
A depth direction analysis of each element of C and O is performed.

Here, the oxygen concentration at the interface between the polymer film and the aluminum film is defined as the oxygen concentration at the interface between the polymer film and the aluminum film where the atomic ratio of the Al element is 50% of the peak top. Oxygen atomic ratio. For example, when the peak top of the aluminum atomic ratio is 96 atm%, a portion where the aluminum atomic ratio is 96/2 = 48 atm% is regarded as an interface, and the oxygen atomic ratio in this portion is determined to be the oxygen concentration. The interface portion between the polymer film and the aluminum vapor-deposited film is the first portion formed when the aluminum vapor-deposited film is formed, and is a very important portion. If impurities such as moisture are mixed in when the interface between the polymer film and the aluminum deposited film is formed, it will affect the entire aluminum deposited film accumulated on the interface during the deposition. Therefore, by lowering the moisture partial pressure in the vapor deposition atmosphere at the time of vapor deposition, the oxygen concentration at the interface between the polymer film and the aluminum vapor deposited film can be lowered, and an aluminum vapor deposited film having high oxygen barrier properties can be obtained.

[0024] The density of the aluminum deposition film is "PYSI
CAL REVIEW "Vol. 95, p. 359, N
member2 (JULY 15, 1954) or “Applications of radiat”
ion to Materials analysis
s "(publisher: elsevier) p. 142 (199
It can be measured by the X-ray reflectance measurement method described in 6). Specifically, incident X-ray wavelength: 0.1540 n
m (CuKα1 line), measurement range (0.05 to 2 °),
The X-ray reflectivity is measured in 0.01 ° steps. Reflectance is a function of refractive index and angle of incidence. The refractive index can be determined by determining the angle of incidence and irradiating X-rays to determine the reflectance. The refractive index is a function of the composition and density, and the density can be determined by fitting. If the substance has a thin film, reflected X-rays from each interface will interfere with each other, and an interference effect in which the reflectance reflects the thickness of each layer will appear. Furthermore, when there is micro roughness (micro unevenness) on the surface or interface, it affects the reflectance. "REVIEW PYSICAL APPL
ICATION "Vol. 15, p. 761 (198
By the method described in (0), the roughness can be taken into the reflectance, and the density of the aluminum vapor-deposited film including the influence of the roughness can be obtained by performing fitting under the conditions including the roughness. .

The density at the interface refers to the density of the thickness portion obtained by multiplying the sputtering time by the sputtering time when it corresponds to the interface as measured by the above-mentioned X-ray photoelectron spectroscopy. The internal density means that the atomic ratio of the aluminum element obtained by the above-mentioned X-ray photoelectron spectroscopy is 90% of the peak top.
The density in the range of the thickness obtained by multiplying the sputtering time corresponding to the above portion by the sputtering speed. For example, when the sputtering speed is 4.9 nm / min and the sputtering time corresponding to the interface is 10 min, the thickness from the surface of the aluminum deposited film to the interface is 4.9 nm / min ×
10 min = 49 nm, and the density of the portion 49 nm from the surface of the aluminum vapor-deposited film is referred to as the interface density. In addition, when the sputtering rate is 4.9 nm / min and the sputtering time corresponding to the portion where the atomic ratio of aluminum element is 90% or more of the peak top is 2 to 8 min, 4.9 nm
/Min×2min=9.8 nm, 4.9 nm / min
× 8min = 39.2 nm, and the density in the range of 9.8 to 39.2 nm from the surface of the aluminum vapor-deposited film is referred to as the internal density.

As shown by the above X-ray photoelectron spectroscopy,
The state of the interface between the polymer film and the deposited aluminum film is very important. Therefore, the higher the density at the interface between the polymer film and the aluminum deposited film, the higher the density of the aluminum deposited film deposited thereon,
As a result, an aluminum vapor-deposited film having high gas barrier properties is obtained.

The aluminum-deposited film of the present invention produced as described above is, for example, a resin film, a paper base material, a metal material, synthetic paper, cellophane, a packaging material constituting a packaging container, and the like. And arbitrarily combined with each other to produce various laminates, thereby making it possible to produce suitable packaging materials for packaging various articles.

As the resin film, unstretched,
Any of those stretched in uniaxial or biaxial directions can be used. The thickness is several μm
Can be selected from the range of about 200 μm to about 200 μm.
Any film such as an inflation film or a coating film may be used. Specific materials include, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene propylene copolymer, ethylene vinyl acetate copolymer, ionomer resin, ethylene ethyl acrylate copolymer. Polymer, ethylene acrylic acid or methacrylic acid copolymer, acid-modified polyolefin resin, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinylidene chloride resin Polymer, poly (meth) acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile styrene copolymer (AS resin), acrylonitrile butadiene styrene copolymer (ABS resin), polyester resin, poly Any resin selected from amide resin, polycarbonate resin, polyvinyl alcohol resin, saponified ethylene vinyl acetate copolymer, fluorine resin, diene resin, polyacetal resin, polyurethane resin, nitrocellulose, etc. can do.

[0029] As the paper substrate constituting the paper layer, those having a basis weight of about 80~600g / m ^2, preferably, it is desirable to use a basis weight of about 10~450g / m ^2-position, A strongly sized bleached or unbleached paper substrate, or a paper substrate such as pure white roll paper, kraft paper, paperboard, or processed paper, or the like can be used. In addition, as the above-mentioned metal material, for example, an aluminum foil, a resin film having an aluminum vapor-deposited film, or the like can be used.

Next, the laminate using the above-mentioned materials is subjected to a pretreatment such as a corona treatment, an ozone treatment and a frame treatment on the film surface of the present invention, if necessary. , Isocyanate-based (urethane-based), polyethyleneimine-based, polybutadiene-based, organic titanium-based anchor coating agents, or polyurethane-based, polyacryl-based, polyester-based, epoxy-, polyvinyl acetate-based, cellulose-based, and other laminates A method of laminating a usual packaging material using a known anchor coat agent such as an adhesive for adhesives, an adhesive or the like, for example, a wet lamination method, a dry lamination method, a solventless dry lamination method, an extrusion lamination method, Die extrusion, co-extrusion lamination, inflation Deployment method, can be produced by co-extrusion inflation method, other methods such as.

Next, a method of making a bag or making a box using the above-described laminate will be described. For example, when the packaging container is a soft packaging bag made of a polymer film or the like, a laminate manufactured by the above-described method is used, and the heat-sealable resin layer of the inner layer is opposed to the laminate and folded. The bag body can be formed by overlapping or by overlapping the two sheets, and further, by heat-sealing the peripheral end thereof to provide a seal portion. In addition, as the bag making method, the above-mentioned laminate is folded with its inner layer facing the surface, or the two sheets are overlapped, and the peripheral end of the outer periphery is further
For example, side seal type, two side seal type, three side seal type,
Four-sided seal type, envelope pasted seal type, Gassho pasted seal type (pillow seal type), pleated seal type, flat bottom seal type,
Various types of packaging containers can be manufactured by heat sealing using a heat sealing mode such as a square bottom sealing type. In addition, for example, a self-supporting packaging bag (standing pouch) or the like can be manufactured, and a tube container or the like can be manufactured using the above-described laminated material. In the above, as a method of heat sealing, for example, a known method such as a bar seal, a rotating roll seal, a belt seal, an impulse seal, a high-frequency seal, and an ultrasonic seal can be used. It should be noted that a spout such as a one-piece type, a two-piece type, etc., or a zipper for opening and closing can be arbitrarily attached to the packaging container as described above.

In the case of a liquid-filled paper container containing a paper base as the packaging container, for example, as a lamination material, a laminated material obtained by laminating a paper base is manufactured, and a blank plate for manufacturing a desired paper container from the manufactured laminate. After the production, the blank, the bottom, the head and the like are made into a box using this blank plate to produce, for example, a liquid paper container of a brick type, a flat type or a goebel top type. Moreover, the shape can be manufactured by any of a rectangular container, a circular or other cylindrical paper can, and the like.

The packaging container manufactured as described above has excellent gas barrier properties against oxygen gas and the like, impact resistance, and the like, and further has a suitable post-processing property such as laminating, printing, bag making or box making. Having, also, to prevent the peeling of the deposited thin film as a barrier film, and to prevent the occurrence of thermal cracks, to prevent its deterioration, to exhibit excellent resistance as a barrier film, for example, It is excellent in packaging suitability and storage suitability of various articles such as foods, medicines, detergents, shampoos, oils, toothpastes, chemicals and cosmetics such as adhesives and adhesives, and others.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. The properties of the manufactured aluminum-deposited film were measured under the following conditions.

(Measurement Conditions of Oxygen Concentration) Measuring device: SSX-100 manufactured by SSI, USA, X-ray source: single crystal spectral AlKα ray, X-ray spot: 300 × 520 μm
m ellipse, output 10 kV 7 mA, analyzer mode: Constant Analyzer Energ
y (CAE) Mode, Pass Energy: Re
s. 4 = 150 eV, resolution: Au4f7FWHM =
1.65 eV, degree of vacuum: 1 × 10 ⁻⁹ Torr, geometry: θ = 35 ° (θ: inclination of the detector with respect to the sample surface), data processing: Smoothing 3 point
s, peak area measurement, b
Acquisition subtraction, pe
ak synthesis, Ar etching: 3 keV
1.5 × 10 ⁻⁷ Torr, 4 × 2 mm raster,
Sputter rate: 4.9 nm / min (SiO ₂ equivalent value).

(Measurement conditions of density) Measuring device: X-ray reflectance measuring device manufactured by Rigaku Denki, Incident X-ray wavelength: 0.1540 nm (CuKα1 line) Measuring range (0.05 to 2 °), 0.01 ° step .

(Oxygen permeability measurement) Temperature 23 ° C., Humidity 0%
Under the condition of RH, an oxygen transmittance measuring device [model name, OXTRAN (OXTRAN) manufactured by MOCON, USA]
2/20)].

(Moisture Partial Pressure in Vapor Deposition Atmosphere) The water partial pressure in the deposition chamber is measured by a quadrupole mass spectrometer (MA
SSMAATE100), a turbo-molecular pump (UTM50 of Nippon Vacuum Engineering Co., Ltd.) and a rotary pump (GLD-050 of Nippon Vacuum Engineering Co., Ltd.) are connected, and the total pressure, moisture partial pressure and pressure in the evaporation chamber of the quadrupole mass spectrometer are connected. The water partial pressure in the vapor deposition atmosphere was calculated as follows: (water partial pressure of the quadrupole mass spectrometer / total pressure of the quadrupole mass spectrometer) × pressure in the vapor deposition chamber.

[0039]

(Example 1) A roll-up type vacuum evaporation apparatus having an apparatus structure shown in FIG. 1 was used, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as a base material, and aluminum was deposited on one side of the film. Then, an aluminum vapor-deposited film having a thickness of 400 ° was formed by a vacuum vapor deposition method using a resistance heating method to produce an aluminum vapor-deposited film.
At this time, an inert gas introduction pipe was installed in the gap between the cooling drum and the partition wall between the winding chamber and the vapor deposition chamber, and N ₂ gas was introduced.
Since deposition was performed while introducing 300 cc / min,
The water partial pressure in the vapor deposition atmosphere was 1.0 × 10 ⁻⁸ Torr.

When the oxygen transmission rate of the obtained aluminum vapor-deposited film was measured, it was found to be 0.9 cc / m ² · atm ·
24 hours. The oxygen concentration at the interface between the aluminum vapor-deposited film and the base film was measured by X-ray photoelectron spectroscopy, and was found to be 23 atm%. When the density at the interface between the aluminum vapor-deposited film and the base film and the internal density of the vapor-deposited film were measured using an X-ray reflectivity measurement method, they were 1.8 g / cm ³ and 2.5 g / c, respectively.
m ³ .

Example 2 Example 2 was repeated except that the amount of N ₂ gas introduced from the inert gas introduction pipe provided in the gap between the partition wall between the winding chamber and the vapor deposition chamber and the cooling drum was changed to 500 cc / min. In the same manner as in Example 1, an aluminum vapor-deposited film was produced. At this time, the moisture partial pressure in the deposition atmosphere was 3.2 × 10 ⁻¹² Torr.

The oxygen vapor transmission rate of the obtained aluminum vapor-deposited film was 0.3 cc / m ² · atm · 24 h. Further, oxygen at the interface between the aluminum vapor-deposited film and the substrate film was 8 atm%. The density at the interface between the aluminum vapor-deposited film and the substrate film and the density inside the vapor-deposited film were 2.6 g / cm ³ and 2.7, respectively.
g / cm ³ .

(Example 3) Example 3 was repeated except that the amount of N ₂ gas introduced from the inert gas introduction pipe provided in the gap between the partition wall between the winding chamber and the vapor deposition chamber and the cooling drum was changed to 400 cc / min. In the same manner as in Example 1, an aluminum vapor-deposited film was produced. At this time, the moisture partial pressure in the deposition atmosphere was 1.5 × 10 ⁻¹⁰ Torr.

The resulting aluminum vapor-deposited film had an oxygen permeability of 0.7 cc / m ² · atm · 24 h. The oxygen concentration at the interface between the aluminum vapor deposition film and the base film was 20 atm%. The density at the interface between the aluminum vapor-deposited film and the substrate film and the density of the vapor-deposited film were 2.0 g / cm ³ and 2.6, respectively.
g / cm ³ .

Comparative Example 1 Example 1 was repeated except that no inert gas introduction pipe was installed in the gap between the cooling drum and the partition wall between the winding chamber and the vapor deposition chamber, and no N ₂ gas was introduced.
In the same manner as in the above, an aluminum vapor-deposited film was produced. At this time, the moisture partial pressure in the deposition atmosphere is 1.2 × 10 ⁻⁸ To.
rr.

The oxygen transmission rate of the obtained aluminum vapor-deposited film was 1.5 cc / m ² · atm · 24 h. The oxygen concentration at the interface between the aluminum vapor deposition film and the substrate film was 24 atm%. The density at the interface between the aluminum vapor-deposited film and the base film and the density inside the vapor-deposited film were 1.7 g / c, respectively.
m ³ , 2.4 g / cm ³ .

Comparative Example 2 Comparative Example 1 was conducted except that water was supplied to the vapor deposition chamber by a mass flow meter at 100 cc / min.
In the same manner as in the above, an aluminum vapor-deposited film was produced.
At this time, the moisture partial pressure in the deposition atmosphere is 1.3 × 10 ⁻⁷ T
orr.

The oxygen permeability of the obtained aluminum vapor-deposited film was 8.0 cc / m ² · atm · 24 h. The oxygen concentration at the interface between the aluminum vapor deposition film and the base film was 30 atm%. The density at the interface between the aluminum deposited film and the substrate film, and the density inside the deposited film were 0.9 g / cm ³ ,
1.1 g / cm ³ .

Table 1 summarizes the results of the above Examples and Comparative Examples.

[0050]

[Table 1]

[0051]

According to the present invention, it is possible to obtain a high gas barrier film having a high barrier property against oxygen gas and the like, and useful for packaging various articles such as foods, pharmaceuticals and industrial supplies.

[Brief description of the drawings]

FIG. 1 is an apparatus configuration diagram schematically showing an example of a roll-up type vacuum evaporation apparatus for carrying out a method for producing a high gas barrier film of the present invention.

[Explanation of symbols]

1: wind-up type vacuum evaporation apparatus, 2: wind-up chamber,
3: vapor deposition chamber, 4: partition wall, 5: boat, 6: unwinding roll, 7: winding roll, 8, 9, 10: unwinding side guide roll, 11, 12, 13: winding side guide roll , 14: Inert gas introduction pipe, 1
5: Polymer film (base film), 16: Cooling drum, 17: Quadrupole mass spectrometer

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AA00B AA19B AB10B AK01A AK42 BA02 BA07 EH66 GB15 JA13B JD02 JD03 YY00B 4K029 AA11 AA25 BA03 BA44 BD00 CA01 EA03 JA10 KA03

Claims (7)

[Claims] 1. A high gas barrier film having an inorganic layer on a polymer film, wherein an oxygen concentration at an interface between the polymer film and the inorganic layer is 5 atm% or more and less than 24 atm%. . 2. A film having an inorganic layer on a polymer film, wherein the density at the interface between the polymer film and the inorganic layer is 1.8 g / cm ³ or more and 4.0 g / cm ³ or less. Characteristic high gas barrier film 3. A film having an inorganic layer on a polymer film, wherein the density inside the inorganic layer is 2.5 g / cm ^3.
As described above, the high gas barrier film has a weight of 4.0 g / cm ³ or less. 4. The high gas barrier film according to claim 1, wherein the density at the interface between the polymer film and the inorganic layer is 1.8 g / cm ³ or more and 4.0 g / cm ³ or less. 5. The high gas barrier film according to claim 1, wherein the density inside the inorganic layer is 2.5 g / cm ³ or more and 4.0 g / cm ³ or less. 6. The high gas barrier film according to claim 1, wherein the inorganic substance is aluminum and / or aluminum oxide. 7. In producing the high gas barrier film according to claim 1 by forming an inorganic layer by a vapor deposition method, the water partial pressure in the vapor deposition atmosphere is set to 1.
A method for producing a high gas barrier film, wherein the pressure is less than 2 × 10 ⁻⁸ Torr.