JP2013233746A - Gas barrier film and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film that has superior productivity and high transparency, is superior in alkali resistance and chemical resistance, exhibits high gas barrier properties, and has superior adhesion strength between constituent layers, without the occurrence of curl, and to provide a method for producing the gas barrier film.SOLUTION: A gas barrier film has an inorganic layer formed by a vacuum deposition method, an inorganic layer formed by a chemical vapor deposition method, an inorganic layer formed by the vacuum deposition method, and a layer formed by a catalytic chemical vapor deposition method, in this order on at least one surface of a base material. A method for producing the gas barrier film is also provided.

Description

  The present invention relates to packaging materials and packaging sheets for foods, medicines, chemicals, etc., packaging materials for electronic devices and the like, flexible substrates for electronic devices, back sheets and front sheets for solar cells, for electronic paper, and organic electroluminescence (EL). More particularly, the present invention relates to a gas barrier film that is mainly used as a building material such as a device material, a protective film, and a heat insulating material, and a manufacturing method thereof.

Gas barrier films are mainly used as packaging materials for foods and pharmaceuticals to prevent the influence of oxygen and water vapor, which cause changes in the quality of contents, liquid crystal display panels, EL display panels, and electronic paper. In order to avoid deterioration of performance of elements formed in solar cells and the like by contact with oxygen and water vapor, they are used as packaging materials for electronic devices and the like, materials for electronic paper, and solar cells. In recent years, a gas barrier film may be used for reasons such as imparting flexibility and impact resistance to a portion where glass or the like has been conventionally used.
In general, such a gas barrier film has a structure in which a gas barrier layer is formed on one or both sides of a plastic film as a base material. The gas barrier film is formed by various methods such as a chemical vapor deposition method (CVD method) and a physical vapor deposition method (PVD method). Even if any method is used, the conventional gas barrier property is used. The film only has an oxygen transmission rate (OTR) of about ² cc / m ² / day and a water vapor transmission rate of about ² g / m ² / day, and is used for applications that require higher gas barrier properties. It was still inadequate.
Further, such a gas barrier film has been required to have chemical resistance and alkali resistance when used for exposure to chemicals and alkalis or when used outdoors.

  As a gas barrier film as described above, Patent Document 1 discloses that a first layer made of silicon oxide alone and carbon are contained in an amount of 5 to 40 at. A transparent gas barrier material having a laminated structure in which a second layer made of silicon oxide containing 2% is sequentially formed by a PVD method such as vacuum deposition, sputtering, or ion plating or a plasma activated reactive deposition method is disclosed. Patent Document 2 discloses a gas barrier film having a silicon oxide film formed by plasma CVD on one or both sides of a base material, wherein the silicon oxide film has 170 O atoms with respect to 100 Si atoms. A gas barrier film comprising a component ratio of ˜200 and C atoms of 30 or less is disclosed. Patent Document 3 discloses a gas barrier film having a plastic film and a thin film made of a composition mainly composed of an oxide formed on at least one surface of the plastic film, wherein carbon is contained in the thin film. A gas barrier film containing 0.1 to 40 mol% is disclosed. In Patent Document 4, in a barrier film formed by laminating a silicon oxide film (SiOx) as a barrier layer on one side or both sides of a plastic substrate, the barrier layer is composed of at least two silicon oxide films, The thickness per silicon oxide film is 10 nm or more and 50 nm or less, the thickness of the barrier layer composed of the two or more silicon oxide films is 20 nm or more and 200 nm or less, and the carbon in the barrier layer The atomic ratio is 10 at. % Or less, a gas barrier film is disclosed. Patent Document 5 discloses a transparent gas barrier substrate in which a silicon oxynitride layer and a silicon nitride layer are laminated in this order on one surface or both surfaces of a transparent resin substrate.

The gas barrier material described in Patent Document 1 actually contains 5 to 40 at. If the thickness of the second layer made of silicon oxide containing 1% is increased to such an extent that the flexibility of the barrier layer is sufficiently exhibited, there is a problem that coloring becomes excessive. In addition, such a second layer made of silicon oxide containing carbon has low surface energy and thus has poor adhesion, and if it is not thickened to some extent, it may cause delamination between layers. On the other hand, it is preferable to use the plasma CVD method to form the second layer made of silicon oxide containing carbon, but since the plasma CVD method generally has a lower film formation rate than the vacuum evaporation method using physical vapor deposition, In order to form such a thick film, there is a problem that the film forming speed has to be lowered and the productivity is inferior. Further, since silicon oxide has a problem that it is easily eroded by chemicals, particularly alkali, it is unsuitable for flexible substrates for electronic devices, chemicals, chemicals packaging applications, and outdoor applications exposed to rainwater.
In the gas barrier film described in Patent Document 2, the silicon oxide film containing carbon formed by the plasma CVD method is mainly responsible for the barrier property. Since thickness is required, there are coloring and productivity problems.
In the gas barrier film described in Patent Document 3, a thin film composed of a composition mainly composed of an oxide containing carbon is also mainly responsible for barrier properties. Since a certain thickness is required, there are problems of coloring and productivity.
In the gas barrier film described in Patent Document 4, a barrier layer having a low carbon content is formed by laminating the same kind of films formed by the plasma CVD method, but compared with the vacuum vapor deposition method by physical vapor deposition. Then, the film formation rate is overwhelmingly low, and a certain amount of thickness is required to actually exhibit a sufficient barrier property.
In the transparent gas barrier substrate described in Patent Document 5, in the examples, there is a description that the water vapor transmission rate is up to 0.23 (g / m ² / day), but the film deposition rate is 10 nm / min or less, The film thickness was insufficient as a gas barrier layer during high-speed production. In addition, further improvement in gas barrier properties is required.

Japanese Patent No. 3319164 JP 2006-96046 A JP-A-6-210790 JP 2009-101548 A JP 2007-062305 A

  The problem to be solved by the present invention is to solve the above-mentioned problems of the prior art, and in particular, the film can be continuously formed under vacuum, the productivity is good, and the alkali resistance and chemical resistance are good. Another object of the present invention is to provide a gas barrier film that has high transparency, exhibits high gas barrier properties, has excellent adhesion strength between constituent layers and does not cause curling, and a method for producing the film.

The present invention
(1) An inorganic layer formed by a vacuum vapor deposition method, an inorganic layer formed by a chemical vapor deposition method, an inorganic layer formed by a vacuum vapor deposition method, and a layer formed by a catalytic chemical vapor deposition method in this order on at least one surface of the substrate. And (2) an inorganic layer by vacuum deposition, an inorganic layer by chemical vapor deposition, an inorganic layer by vacuum deposition, and a layer by catalytic chemical vapor deposition in this order on at least one surface of the substrate A method for producing a gas barrier film, wherein the formation of the layer by the catalytic chemical vapor deposition method is performed under a reduced pressure of 1 Pa to 1 × 10 ³ Pa and the formation of the inorganic layer by the vacuum vapor deposition method is 1 × 10 ^−7. performed under reduced pressure of Pa or more 1Pa or less, the chemical vapor deposition formation of the inorganic layer was carried out under a reduced pressure of 1 × 10 ^-2 Pa to 10Pa or below, and the layer by the catalytic chemical vapor deposition method, the vacuum Deposition method performed at a conveying speed 20 m / min or more substrates at the time of forming the inorganic layer by the inorganic layer and the chemical vapor deposition method by a method for producing a gas barrier film,
About.

  The present invention enables continuous film formation under vacuum, good productivity, good alkali resistance and chemical resistance, high transparency, high gas barrier properties, and excellent adhesion strength between constituent layers. A gas barrier film having no curling and a method for producing the film are provided.

Hereinafter, the present invention will be described in detail.
<Gas barrier film>
The gas barrier film of the present invention comprises an inorganic layer formed by vacuum vapor deposition on at least one surface of a substrate (hereinafter sometimes referred to as “PVD inorganic layer (1)”), an inorganic layer formed by chemical vapor deposition. (Hereinafter sometimes referred to as “CVD inorganic layer”), an inorganic layer formed by vacuum deposition (hereinafter sometimes referred to as “PVD inorganic layer (2)”), and catalytic chemical vapor deposition (Cat-CVD). The formed layer (hereinafter, also referred to as “Cat-CVD layer”) is provided in this order.

[Base material]
The base material of the gas barrier film of the present invention is not particularly limited as long as it is a plastic film that can be used for ordinary packaging materials, packaging materials such as electronic devices, solar cell members, electronic paper members, and organic EL members. Although it can be used without any problem, a transparent polymer film is preferred. Specific examples of the resin constituting the plastic film include polyolefins such as homopolymers or copolymers such as ethylene, propylene, and isobutene, amorphous polyolefins such as cyclic polyolefins, polyethylene terephthalate, and polyethylene-2,6. -Polyester such as naphthalate, nylon 6, nylon 66, nylon 12, polyamide such as copolymer nylon, polyvinyl alcohol, ethylene-vinyl acetate copolymer partial hydrolyzate (EVOH), polyimide, polyetherimide, polysulfone, polyether Examples thereof include biodegradable resins such as sulfone, polyether ether ketone, polycarbonate, polyarylate, fluororesin, acrylic resin, and polylactic acid. Furthermore, polyester, polyamide, and polyolefin are preferable from the viewpoint of film strength and cost, and polyethylene terephthalate (PET) and polyethylene-2,6-naphthalate (PEN) are preferable from the viewpoint of surface smoothness, film strength, heat resistance, and the like. Particularly preferred are the polyesters.
The content of the resin in the plastic film is preferably 50 to 100% by mass.
The base material is a known additive, for example, an antistatic agent, a light blocking agent, an ultraviolet absorber, a plasticizer, a lubricant, a filler, a colorant, a stabilizer such as a light stabilizer, a lubricant, a crosslinking agent, An anti-blocking agent, an antioxidant, etc. can be contained.

The plastic film as the substrate is formed by using the above raw materials, but may be unstretched or stretched. Moreover, either a single layer or a multilayer may be sufficient. Such a substrate can be produced by a conventionally known method. For example, an unstretched film that is not substantially oriented by melting raw materials with an extruder, extruding with an annular die or a T-die, and quenching. Can be manufactured. Further, by using a multilayer die, a single layer film made of one kind of resin, a multilayer film made of various kinds of resins, and the like can be produced.
This unstretched film is subjected to a known method such as uniaxial stretching, tenter sequential biaxial stretching, tenter simultaneous biaxial stretching, tubular simultaneous biaxial stretching, or the like in the film flow direction (vertical direction) or the film flow direction. And the film extended | stretched to the uniaxial direction or the biaxial direction can be manufactured by extending | stretching in the direction (horizontal axis direction) orthogonal to it.
The thickness of the substrate is usually in the range of 5 to 500 μm, preferably 10 to 200 μm, depending on its use from the viewpoint of mechanical strength, flexibility, transparency and the like as the substrate of the gas barrier film of the present invention. Selected. The base material includes a thick sheet. Moreover, there is no restriction | limiting in particular about the width | variety and length of a film, It can select according to a use suitably.

[Layer formed by catalytic chemical vapor deposition (Cat-CVD)]
In the present invention, the Cat-CVD layer is formed by heating a metal catalyst wire that is a heating catalyst body under vacuum and bringing one or more material gases into contact with the metal catalyst wire and thermally decomposing them. It is obtained by forming an inorganic and / or organic layer having an element constituting the main source gas as a main skeleton material.

Specifically, in the Cat-CVD method, cooling is performed so that the substrate temperature is preferably maintained at a glass transition temperature (Tg) or lower, more preferably (Tg-10) ° C. or lower. Thereby, the damage of the base material by the radiant heat from a metal catalyst body can be eliminated. Further, the reaction pressure is performed under a reduced pressure of 1 Pa or more and 1 × 10 ³ Pa or less, preferably 10 Pa or more and 700 Pa or less, more preferably 20 Pa, from the viewpoint of preventing impurities in the air from being mixed into the film and the film formation rate. It is 500 Pa or less.
Conventional catalysts such as tungsten, platinum, and nickel can be used as the metal catalyst body as the heating catalyst body. However, the metal catalyst body itself does not melt or volatilize at the temperature at which the material gas is catalytically decomposed, and further silicidation occurs. Tungsten is preferable because it is suppressed and corrosion by halogen is suppressed. The shape of the line of the metal catalyst body may be a straight line, or may be a right cylindrical coil, may be other shapes, and may be a structure other than a line. Further, the total area of the heating catalyst body is exposed to the Cat-CVD film formation tank in terms of the film formation speed, the amount of heat radiation from the heating catalyst body to the base material, the supply power of the heating catalyst body, and the like. 1/1000 to 1/10 of the area of the film is preferable, and 1/100 to 1/10 is more preferable. The temperature of the metal catalyst body is a temperature at which the material gas is catalytically decomposed, and is preferably a temperature that does not cause thermal damage to the substrate, preferably 500 to 2500 ° C, more preferably 1600 to 2000 ° C.

In the present invention, the layer formed by the Cat-CVD method may be an inorganic layer or an organic layer.
Examples of the inorganic layer include a layer made of an oxidized and / or silicon nitride compound, a silicon carbide compound containing oxygen and / or nitrogen, titanium oxide, aluminum oxide, and the like, and a silicon compound layer is preferable.
Moreover, as an organic layer, the organic layer which has as a main component the polymer obtained by monomer bridge | crosslinking can be used. The monomer is not particularly limited as long as it contains a functional group exhibiting crosslinkability, but it is preferable to use a monomer having an acryloyl group, a methacryloyl group, or an oxirane group. For example, alkyl acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, isocyanuric acid (meth) acrylate, pentaerythritol (meth) acrylate, trimethylolpropane (meth) acrylate, ethylene glycol (meth) acrylate, polyester (meth) Examples include acrylate and glycidyl methacrylate.
Among these, an organic layer using a composition containing a monomer containing an acryloyl group as a main raw material is preferable in terms of reactivity and film formation rate.
Moreover, a radical polymerization initiator can be used with the said monomer, A halogen compound, an azo compound, an organic peroxide etc. are mentioned as a radical initiator.
The radical initiator is decomposed into radical species by contacting the heating catalyst body. By using a radical initiator, the reaction rate of the monomer is improved.
In the present invention, the layer formed by the Cat-CVD method is preferably an inorganic layer made of a silicon compound or an organic layer mainly composed of a composition containing a monomer having a methacryloyl group, an acryloyl group, or an oxirane group.

  The material gas that can be used varies depending on the target layer constituent material, but is preferably composed of at least one kind of gas. For example, in the formation of a silicon compound layer, ammonia, It is preferable to use a rare gas such as nitrogen, oxygen, hydrogen or argon as the second material gas.

  The first material gas containing silicon is monosilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane. Ethoxysilane, diphenyldiethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, etc. alone or 2 It can be used in combination of more than one species. The material gas may be gaseous or liquid at room temperature, and the liquid raw material can be vaporized by a raw material vaporizer and supplied into the apparatus. Among the first material gases, organosilicon compounds are preferable from the viewpoint of gas safety, reactivity, and reaction rate.

When ammonia is used, the main reaction at and near the surface of the heated catalyst body is NH ₃ → NH ₂ + H ·, and NH ₂ · is considered to be the main deposition species. The main reaction of hydrogen is H ₂ → 2H ·, which is considered to be mainly used to assist the gas phase reaction and the surface reaction of the substrate.
Although H. is generated without using hydrogen as a material gas, a large amount of H. can be generated by flowing hydrogen into a vacuum apparatus as a material gas. Demonstrating. And, it is presumed that the silicon-containing active species and NH ₂ · react mainly due to the presence of reaction auxiliary components such as the thermal energy on the substrate surface, the thermal energy of the deposited species, and H · to form a silicon compound film. Detailed gas phase reactions and substrate surface reactions are not known. In addition, in the above, * shows the state of a radical.

The material gas flow ratio is preferably 1 to 100, more preferably 2 to 50, hydrogen is preferably 5 to 400, more preferably 20 to 80, and oxygen is preferably 0.1 to the organosilicon compound 1. It is -2.0, More preferably, it is 0.2-0.8. By doing so, it is possible to form a silicon compound film containing nitrogen and oxygen that has a high ability to block permeation of water vapor, oxygen, and the like and has good adhesion.
That is, if the flow rate ratio of ammonia to the organosilicon compound 1 is in the range of 1 to 100 ammonia relative to the organosilicon compound 1, the silicon compound film is not colored, and the ammonia is on the heating catalyst body. The resulting silicon compound film has good barrier properties against water vapor, oxygen, etc. without significantly hindering the decomposition of hydrogen. In addition, when the flow ratio of hydrogen to the organosilicon compound 1 is within a range of 5 to 400 hydrogen relative to the organosilicon compound 1, barrier properties such as water vapor and oxygen are good. Further, no decrease in the concentration of the deposited species is observed in the vacuum apparatus, and the deposition rate is good.

  The thickness of the Cat-CVD layer is preferably 100 nm or less. The thickness of the Cat-CVD inorganic layer can be measured by a cross-sectional TEM (transmission electron microscope) method. By being in the above range, the production rate by the Cat-CVD method can be increased to the same level as the vacuum deposition method, so that the production efficiency can be improved and the manufacturing equipment can be downsized and simplified. Can be manufactured. From the above viewpoint, the thickness of the Cat-CVD layer is preferably 80 nm or less, more preferably 60 nm or less, and further preferably 50 nm or less.

Further, the lower limit of the thickness of the Cat-CVD layer is preferably 0.1 nm, more preferably 1 nm, and more preferably 5 nm as the minimum layer thickness for exhibiting the effect of improving gas barrier properties. More preferably. A thickness of 0.1 nm or more is preferable because adhesion, denseness, gas barrier properties, and the like are good and surface roughness is small. From the above viewpoint, the thickness of the Cat-CVD layer is preferably from 0.1 nm to 100 nm, more preferably from 1 nm to 80 nm, and even more preferably from 5 nm to 60 nm.
The thickness of the Cat-CVD layer can be measured by a cross-sectional TEM method using a transmission electron microscope (TEM), and specifically by the following method.
(Measurement of the thickness of the inorganic layer formed by catalytic chemical vapor deposition (Cat-CVD))
A sample is prepared by an epoxy resin-embedded ultrathin section method, and measured with a cross-sectional TEM apparatus (JEM-1200EXII) manufactured by JEOL Ltd. under an acceleration voltage of 120 KV. As for the thickness of the Cat-CVD layer of 10 nm or less, since it is difficult to obtain an accurate value even in the measurement by the cross-sectional TEM method, a relatively thick Cat-CVD of 20 nm or more formed under the same film formation conditions. The layer is measured by the cross-sectional TEM method to calculate the film formation rate per unit traveling speed, and the thickness is calculated when the film is formed at a predetermined traveling speed.

Since the layer formed by the Cat-CVD method is a non-plasma CVD method, the formation surface is not exposed to plasma and is not damaged by the plasma. It is formed and has excellent gas barrier properties.
In addition, since a dense film without internal defects is formed, a layer with excellent surface resistance and chemical resistance and a small surface roughness is formed, so the surface area exposed to the outside is small. Corrosion due to is suppressed.
Further, if the source gas used in the Cat-CVD method is, for example, an organic silicon compound, the Cat-CVD layer can be formed at high speed.
By forming such a Cat-CVD layer excellent in alkali resistance and chemical resistance on the outermost surface, the alkali resistance and chemical resistance of the gas barrier film can be enhanced.
Furthermore, by forming a laminated structure in the order of a PVD inorganic layer, a CVD inorganic layer, and a PVD inorganic layer under the Cat-CVD layer, the CVD inorganic layer itself hardly contributes directly to the gas barrier property, but the PVD inorganic layer On the other hand, in order to exert a sealing effect on the lower layer and an anchor effect on the upper layer, compared with the case where the PVD inorganic layer is simply formed thick or when the PVD inorganic layers or the CVD inorganic layers are laminated, The gas barrier properties are dramatically improved.

[Inorganic layer formed by vacuum deposition method (PVD method)]
In the gas barrier film of the present invention, the inorganic substance constituting each of the PVD inorganic layers provided in the upper and lower layers of the CVD inorganic layer is silicon, aluminum, magnesium, zinc, tin, nickel, titanium, carbon, or the like. Oxides, carbides, nitrides or mixtures thereof may be mentioned, and silicon oxide is preferred. In view of gas barrier properties, silicon oxide, aluminum oxide, and carbon (for example, a substance mainly composed of carbon such as diamond-like carbon) are preferable. In particular, silicon oxide and aluminum oxide are preferable in that high gas barrier properties can be stably maintained. Although the said inorganic substance may be used individually by 1 type, you may use it in combination of 2 or more type.
In particular, in the gas barrier film of the present invention, at least one of the inorganic layers (1) or (2) formed by PVD is preferably made of silicon oxide.

For the formation of each of the PVD inorganic layers (1) and (2) on the substrate, a vacuum vapor deposition method is used among physical vapor deposition methods in that a uniform thin film having a high gas barrier property can be obtained.
The thickness of each of the PVD inorganic layers (1) and (2) has a lower limit of generally 0.1 nm, preferably 0.5 nm, more preferably 1 nm, particularly preferably 10 nm, and the upper limit is generally It is 500 nm, preferably 100 nm, more preferably 50 nm. The thickness of the PVD inorganic layer is preferably 0.1 or more and 500 nm or less, more preferably 10 nm or more and 500 nm or less, further preferably 10 nm or more and 100 nm or less, and particularly preferably 10 nm or more from the viewpoint of gas barrier properties and film productivity. 50 nm or less. The thickness of the PVD inorganic layer can be measured using fluorescent X-rays.
(Measurement of the thickness of the inorganic layer formed by the vacuum deposition method (PVD method))
This method uses the phenomenon of emitting fluorescent X-rays peculiar to atoms when they are irradiated with X-rays, and knowing the number (amount) of atoms by measuring the intensity of emitted fluorescent X-rays. I can do it. Specifically, two layers of known thicknesses are formed on the film, the specific fluorescent X-ray intensity emitted for each is measured, and a calibration curve is created from this information. Similarly, the fluorescent X-ray intensity is measured for the measurement sample, and the thickness is measured from the calibration curve.

Each of the PVD inorganic layers (1) and (2) is formed while conveying the film under reduced pressure in order to form a dense layer. The pressure at the time of forming each of the PVD inorganic layer (1) and (2) in terms of evacuation capability and barrier properties, is usually 1 × 10 ^-7 1 Pa or less the range of Pa, preferably 1 × 10 ^{- It is 6} or more and 1 × 10 ⁻¹ Pa or less, more preferably 1 × 10 ⁻⁴ or more and 1 × 10 ⁻² Pa or less. If it is in the range of 1 × 10 ⁻⁷ Pa or more and 1 Pa or less, a sufficient gas barrier property is obtained, and the PVD inorganic layer is excellent in transparency without causing cracks or peeling.

[Inorganic layer formed by chemical vapor deposition (CVD)]
In the present invention, a CVD inorganic layer is formed on the PVD inorganic layer (1). It is considered that defects such as defects generated in the PVD inorganic layer are sealed by the CVD inorganic layer, and gas barrier properties and interlayer adhesion are improved.
As the chemical vapor deposition method, it is necessary to increase the film formation rate to achieve high productivity and to avoid thermal damage to the film substrate. Therefore, the plasma CVD method is preferable, and it is formed by the plasma CVD method. Examples of the layer include at least one layer selected from metals, metal oxides, metal nitrides, and the like obtained by plasma decomposition of organic substances. Among plasma CVD methods, it is preferable to form a CVD inorganic layer by remote plasma CVD method. The remote plasma CVD method is a CVD method in which a plasma generation unit is located at a different location from the substrate. For example, a plasma CVD apparatus “MAPLE” manufactured by Mitsubishi Heavy Industries, Ltd., a SWP-CVD apparatus manufactured by Shimadzu Corporation, etc. Can be mentioned. By forming the CVD inorganic layer by the remote plasma CVD method, the carbon content is further reduced. Further, by forming a CVD inorganic layer by a remote plasma method, a dense inorganic layer having a small surface roughness can be formed without being damaged by heat or plasma.

In the present invention, the CVD inorganic layer has a carbon content measured by X-ray photoelectron spectroscopy (XPS method) of 20 at. % Or less, preferably 10 at. % Or less, more preferably 5 at. % Or less. By setting the carbon content to such a value, the surface energy of the inorganic layer is increased and the adhesion between the inorganic layers is not hindered. Therefore, the bending resistance and peel resistance of the barrier film are improved.
The carbon content of the CVD inorganic layer is 0.5 at. % Or more, preferably 1 at. % Or more, more preferably 2 at. % Or more is more preferable. A slight amount of carbon is contained in the CVD inorganic layer serving as the intermediate layer, so that the stress is efficiently relaxed and the curl of the barrier film is reduced.
From the above points, the carbon content in the CVD inorganic layer is preferably 0.5 at. % Or more and 20 at. % Or less, and more preferably 0.5 at. % Or more and 10 at. % Or less, and more preferably 0.5 at. % Or more and 5 at. % Or less, and more preferably 1 at. % Or more and 5 at. % Or less, and more preferably 2 at. % Or more and 5 at. % Or less. Here, “at.%” Indicates an atomic composition percentage (atomic%).

There is no restriction | limiting in particular as a method of achieving the carbon content measured by the said X ray photoelectron spectroscopy (XPS method) in this invention, For example, the method achieved by selecting the raw material in CVD method, a raw material, and reaction Examples thereof include a method of adjusting by the flow rate and ratio of gas (oxygen, nitrogen, etc.), a method of adjusting by the pressure during film formation and input power, and the like.
A specific method for measuring the carbon content by X-ray photoelectron spectroscopy (XPS method) is as follows.
(Measurement of carbon content of CVD inorganic film layer)
Using an XPS analyzer K-Alpha manufactured by Thermo Fisher Scientific Co., Ltd., the binding energy is measured by XPS (X-ray photoelectron spectroscopy), and converted from the peak area corresponding to Si2P, C1S, N1S, O1S, etc. By doing so, the elemental composition (at.%) Can be calculated. The carbon content of the CVD inorganic layer can be evaluated by reading the value of the CVD inorganic layer portion of the XPS chart.

  Examples of the inorganic substance constituting the CVD inorganic layer include silicon, aluminum, magnesium, zinc, tin, nickel, titanium, diamond-like carbon, and oxides, carbides, nitrides, or mixtures thereof. In view of gas barrier properties and adhesion, silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbide, silicon oxycarbonitride, aluminum oxide, aluminum nitride, aluminum oxynitride, aluminum oxide carbide, titanium oxide, diamond-like carbon Etc. Among these, silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbonitride, and aluminum oxide are more preferable because high gas barrier properties can be stably maintained. The CVD inorganic layer may contain one kind of the inorganic substance or two or more kinds.

As a raw material for forming a CVD inorganic layer made of silicon oxide or the like, for example, a silicon compound can be cited. Moreover, a titanium compound is mentioned as a raw material for CVD inorganic layer formation which consists of titanium oxide etc. If it is a compound such as a silicon compound or a titanium compound, it can be used in a gas, liquid, or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation. Moreover, you may dilute and use with a solvent and organic solvents, such as methanol, ethanol, n-hexane, and these mixed solvents can be used for a solvent.
In the present invention, the raw material for forming the CVD inorganic layer is preferably a gas (gas), and the raw material gas is preferably an organometallic compound.

  Examples of the silicon compound include silane, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetra t-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane, bis (dimethylamino) dimethylsilane Bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) carbodiimide, die Ruaminotrimethylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, tetramethyldisilazane , Tris (dimethylamino) silane, triethoxyfluorosilane, allyldimethylsilane, allyltrimethylsilane, benzyltrimethylsilane, bis (trimethylsilyl) acetylene, 1,4-bistrimethylsilyl-1,3-butadiyne, di-t-butylsilane, 1,3-disilabutane, bis (trimethylsilyl) methane, cyclopentadienyltrimethylsilane, phenyldimethylsilane, phenyltrimethylsilane, pro Rugyltrimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetramethyl Examples thereof include cyclotetrasiloxane, hexamethyldisiloxane, hexamethylcyclotetrasiloxane, M silicate 51, and the like.

  Examples of the titanium compound include titanium inorganic compounds such as titanium oxide and titanium chloride, titanium alkoxides such as titanium tetrabutoxide, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate and tetramethyl titanate, Examples thereof include titanium chelates such as titanium lactate, titanium acetylacetonate, titanium tetraacetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium ethylacetoacetate and titanium triethanolaminate.

In order to ensure the sealing effect on the PVD inorganic layer, the CVD inorganic layer is preferably composed of two or more layers, more preferably 2 to 5 layers.
The thickness of the CVD inorganic layer is preferably 20 nm or less. The thickness of the CVD inorganic layer can be measured by a cross-sectional TEM method. Adhesiveness improves more because the intermolecular force of PVD inorganic layers acts effectively because it is 20 nm or less. At the same time, since the production rate by the chemical vapor deposition method can be increased to the same level as that of the vacuum vapor deposition method, the production efficiency can be improved and the production equipment can be downsized and simplified, so that an inexpensive barrier film can be produced. From the above viewpoint, the thickness of the CVD inorganic layer is preferably 10 nm or less, more preferably 5 nm or less, and further preferably 3 nm or less.

  Further, the lower limit of the thickness of the CVD inorganic layer is preferably 0.01 nm, more preferably 0.1 nm as the minimum layer thickness for exhibiting a sealing effect on the PVD inorganic layer. Preferably, 0.5 nm is more preferable. A thickness of 0.01 nm or more is preferable because of good adhesion and gas barrier properties. From the above viewpoint, the thickness of the CVD inorganic layer is preferably 0.01 nm or more and 20 nm or less, more preferably 0.1 nm or more and 20 nm or less, and more preferably 0.1 nm or more and 10 nm or less, It is still more preferably 0.1 nm or more and 5 nm or less, and even more preferably 0.1 nm or more and 3 nm or less.

  In the present invention, in the adjacent CVD inorganic layer and PVD inorganic layer, the thickness ratio (CVD inorganic layer thickness / PVD inorganic layer thickness) is preferably 0.0001 to 1, more preferably. Is 0.0005 to 0.5, and more preferably 0.001 to 0.2. If the CVD inorganic layer thickness is 0.0001 or more compared to the PVD inorganic layer thickness, the ratio of the CVD inorganic layer to the entire inorganic layer is not too small, and the CVD inorganic layer cannot be obtained only by the PVD inorganic layer. It is possible to obtain a sealing effect by the layer and effects such as stress relaxation. Further, if the CVD inorganic layer thickness is 1 or less compared to the PVD inorganic layer thickness, the film formation rate of the CVD method does not become extremely low as compared with the PVD method, and the PVD inorganic layer is formed by the Roll to Roll process. When the layer and the CVD inorganic layer are continuously formed, productivity is improved without lowering the transport speed even if the transport speed of the substrate is matched with the film formation rate of the CVD inorganic layer.

The surface roughness (AFM: measured with an atomic force microscope) of the PVD inorganic layer is preferably about 5 nm or less, because vapor deposition particles are densely deposited, which is preferable for the development of barrier properties. At this time, by setting the thickness of the CVD inorganic layer to be equal to or less than the above value, the crest portion of the vapor deposition particles is covered only very thinly while filling open vacancies existing in the valleys between the vapor deposition particles (or partially). Therefore, the adhesion between the PVD inorganic layers can be further enhanced. Further, by setting the thickness of the CVD inorganic layer to 0.1 nm or more, the effect of sealing the open pores of the above-described lower PVD inorganic thin curtain layer is exhibited, and at the same time the surface becomes smooth, and the upper PVD inorganic layer is formed. When vapor deposition is performed, the surface diffusion of the vapor-deposited particles becomes good and the particles are deposited more densely, so that the barrier property is further improved.
The measurement of the thickness of the CVD inorganic layer by a cross-sectional TEM method is performed using a transmission electron microscope (TEM), and specifically, can be performed by the following method.
(Measurement of the thickness of inorganic layers formed by chemical vapor deposition (CVD))
A sample is prepared by an epoxy resin-embedded ultrathin section method, and measured with a cross-sectional TEM apparatus (JEM-1200EXII) manufactured by JEOL Ltd. under an acceleration voltage of 120 KV. As for the thickness of the CVD inorganic layer of 10 nm or less, since it is difficult to obtain an accurate value even in the measurement by the cross-sectional TEM method, a relatively thick CVD inorganic layer of 20 nm or more formed under the same film formation conditions is used. Then, the film formation rate per unit traveling speed is calculated by measuring by the cross-sectional TEM method, and the thickness when the film is formed at a predetermined traveling speed is set as the calculated value.

In the present invention, the CVD inorganic layer is formed in a reduced pressure environment of 1 × 10 ⁻² or more and 10 Pa or less.
That is, the pressure when forming a layer by chemical vapor deposition (CVD) is preferably performed under reduced pressure in order to form a dense layer, and is usually 1 × 10 ⁻² from the viewpoint of film formation speed and barrier properties. 10 Pa, and preferably 1 × 10 ^{−1 to 1} Pa. This CVD inorganic layer can be subjected to a crosslinking treatment by electron beam irradiation in order to improve water resistance and durability.

The CVD inorganic layer is formed by evaporating the raw material compound and introducing it into a vacuum apparatus as a raw material gas, and direct current (DC) plasma, low frequency plasma, high frequency (RF) plasma, pulse wave plasma, tripolar structure. It can be performed by converting into plasma with a low-temperature plasma generator such as plasma, microwave plasma, downstream plasma, columnar plasma, plasma assisted epitaxy or the like. From the viewpoint of plasma stability, a radio frequency (RF) plasma apparatus is more preferable.
In addition to the plasma CVD method, known methods such as a thermal CVD method, a Cat-CVD method (catalytic chemical vapor deposition method), a photo CVD method, and an MOCVD method can be used. Among these, the thermal CVD method and the Cat-CVD method are preferable because they are excellent in mass productivity and film formation quality.

[Film formation method]
In the present invention, it is preferable that the PVD inorganic layer (1), the CVD inorganic layer, the PVD inorganic layer (2), and the Cat-CVD layer are continuously formed under reduced pressure from the viewpoint of gas barrier properties and productivity. That is, in the present invention, after the formation of each layer is completed, the pressure in the vacuum chamber is returned to the vicinity of atmospheric pressure, and the vacuum is re-evacuated to perform the post-process, but the film is continuously formed in a vacuum state. It is preferable.
Moreover, as for the film of this invention, the conveyance speed of the base material of the said Cat-CVD layer, PVD inorganic layer (1), CVD inorganic layer, and PVD inorganic layer (2) is 20 m / min or more from a viewpoint of productivity improvement. It is more preferable that it is 100 m / min or more. Although there is no upper limit in particular regarding the said conveyance speed, 1000 m / min or less is preferable from a viewpoint of stability of film conveyance.

  Thus, by forming the Cat-CVD layer, the PVD inorganic layer, and the CVD inorganic layer in the same vacuum chamber, extremely good gas barrier properties can be exhibited. Although the principle is not clear, Cat-CVD layer formation and PVD inorganic layer formation and CVD inorganic layer are formed in the same vacuum apparatus to form a dense Cat- with a small surface roughness on the PVD inorganic layer (1). A CVD inorganic layer is obtained. Further, by forming a CVD inorganic layer on the PVD inorganic layer (1), minute defects generated in the PVD inorganic layer (1) can be evenly spotted, and further, the gas barrier property of the PVD inorganic layer (2) is further increased. It is thought that it can be improved.

In the present invention, the PVD inorganic layer (1), the CVD inorganic layer, and the PVD inorganic layer (2) are formed before the Cat-CVD layer is formed. Further, it may be repeated once or more. That is, in the present invention, from the viewpoint of quality stability, one or a plurality of structural units composed of a CVD inorganic layer and a PVD inorganic layer are further formed on the PVD inorganic layer (1), the CVD inorganic layer and the PVD inorganic layer (2). Preferably, it has 1 to 3 units, more preferably 1 or 2 units.
In addition, when repeating formation of each said inorganic layer, it is preferable to carry out continuously under reduced pressure within the same apparatus.

[Anchor coat layer]
In this invention, in order to improve the adhesiveness of the said base material and PVD inorganic layer, it is preferable to provide an anchor coat layer by apply | coating an anchor coating agent etc. between a base material and a PVD inorganic layer. As an anchor coat agent, from the point of productivity, polyester resin, urethane resin, acrylic resin, nitrocellulose resin, silicone resin, vinyl alcohol resin such as polyvinyl alcohol resin and ethylene vinyl alcohol resin, A resin containing one or more of vinyl ester resins, isocyanate group-containing resins, carbodiimide resins, alkoxyl group-containing resins, epoxy resins, oxazoline group-containing resins and styrene resins is preferred.
In addition, the anchor coat layer is optionally provided with a silane coupling agent, a titanium coupling agent, an alkyl titanate, inorganic particles, an ultraviolet absorber, a weathering stabilizer and other stabilizers, a lubricant, an anti-blocking agent and an antioxidant. Etc. can be contained.

The thickness of the anchor coat layer provided on the substrate is usually 0.1 to 5000 nm, preferably 1 to 2000 nm, more preferably 1 to 1000 nm. If it is within the above range, the slipperiness is good, there is almost no peeling from the base material due to the internal stress of the anchor coat layer itself, and a uniform thickness can be maintained, and also in the adhesion between layers Are better.
Moreover, in order to improve the applicability | paintability and adhesiveness of the anchor coating agent to a base material, you may perform surface treatments, such as normal chemical treatment and electrical discharge treatment, before a base material's application | coating.

[Protective layer]
Moreover, it is preferable that the gas barrier film of this invention has a protective layer in the uppermost layer in the side in which each said layer was formed. As the resin for forming the protective layer, both solvent-based and water-based resins can be used. Specifically, polyester resins, urethane resins, acrylic resins, polyvinyl alcohol resins, ethylene Unsaturated carboxylic acid copolymer resin, ethylene vinyl alcohol resin, vinyl modified resin, nitrocellulose resin, silicone resin, isocyanate resin, epoxy resin, oxazoline group-containing resin, modified styrene resin, modified silicone resin, Alkyl titanates can be used alone or in combination of two or more. As the protective layer, one or more kinds of inorganic particles selected from silica sol, alumina sol, particulate inorganic filler, and layered inorganic filler are mixed with the one or more kinds of resins in order to improve barrier properties, wearability, and slipperiness. It is preferable to use a layer made of an inorganic particle-containing resin formed by polymerizing the resin raw material in the presence of the inorganic particles.

As the resin for forming the protective layer, the aqueous resin is preferable from the viewpoint of improving the gas barrier property. Further, as the aqueous resin, a polyvinyl alcohol resin, an ethylene vinyl alcohol resin, or an ethylene-unsaturated carboxylic acid copolymer resin is preferable.
In the present invention, the protective layer may be composed of one kind of the resin, but may be used in combination of two or more kinds.
In addition, inorganic particles can be added to the protective layer in order to improve barrier properties and adhesion.
There is no restriction | limiting in particular in the inorganic particle used for this invention, For example, all well-known things, such as an inorganic filler, an inorganic layered compound, a metal oxide sol, can be used.

  The thickness of the protective layer is preferably 0.05 to 10 μm, more preferably 0.1 to 3 μm, from the viewpoints of printability and processability. A known coating method is appropriately adopted as the formation method. For example, any method such as a reverse roll coater, a gravure coater, a rod coater, an air doctor coater, a spray or a coating method using a brush can be used. Moreover, you may immerse a vapor deposition film in the resin liquid for protective layers. After coating, moisture can be evaporated using a known drying method such as hot drying such as hot air drying or hot roll drying at a temperature of about 80 to 200 ° C. or infrared drying. Thereby, a laminated film having a uniform coating layer is obtained.

[Configuration of gas barrier film]
As the gas barrier film of the present invention, the following embodiments can be preferably used from the viewpoint of gas barrier properties and adhesion.
In the following, for example, the notation of A / B / C indicates that layers are stacked in the order of A, B, and C from the bottom (or from the top).
(1) Base material / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / Cat-CVD layer (2) Base material / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / CVD inorganic layer / PVD inorganic Layer / Cat-CVD layer (3) substrate / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / Cat-CVD layer (4) group Material / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / Cat-CVD layer / protective layer (5) Substrate / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / Cat-CVD layer / Protective layer (6) Base material / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / Cat-CVD layer / protection layer

(7) Base material / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / Cat-CVD layer (8) Base material / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / Cat− CVD layer (9) substrate / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / Cat-CVD layer (10) substrate / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / Cat-CVD layer / protective layer (11) substrate / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / Cat-CVD layer / protective layer (12 ) Substrate / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / Cat-CVD layer / protective layer (in the above embodiment, AC is an anchor coat) Refers to the layer )

In the present invention, after forming an anchor coat layer, or after forming a Cat-CVD layer, PVD inorganic layer or CVD inorganic layer, or after forming a protective layer, gas barrier properties, adhesion, and stabilization of constituent layers It is preferable to perform heat treatment from such points.
However, in the case where there is an anchor coat layer on the substrate, if there is no protective layer, the structural unit layer from the top of the substrate to the uppermost PVD inorganic layer, or if there is a protective layer, the substrate When two or more structural unit layers from the top to the PVD inorganic layer below the protective layer are provided, from the viewpoint of the adhesion between the PVD inorganic layer and the anchor coat layer formed thereunder, the heat treatment as a post-treatment is It is preferable to carry out after forming all the layers constituting the gas barrier film.

  The conditions for the heat treatment vary depending on the types of components constituting the constituent layers of the gas barrier film, the thickness of the layers, and the like, but the method is not particularly limited as long as the necessary temperature and time can be maintained. For example, a method of storing in an oven or temperature-controlled room set to the required temperature, a method of blowing hot air, a method of heating with an infrared heater, a method of irradiating light with a lamp, or heating directly by contact with a hot roll or hot plate A method for imparting a microwave, a method for irradiating with a microwave, and the like can be used. Moreover, even if it heat-processes, after cutting a film into the magnitude | size which is easy to handle, it may heat-process with a film roll. Furthermore, as long as necessary time and temperature can be obtained, a heating device can be incorporated in a part of a film production apparatus such as a coater or a slitter, and heating can be performed in the production process.

  The temperature of the heat treatment is not particularly limited as long as it is a temperature not higher than the heat resistance temperature of the base material, plastic film, etc. used, but it is 60 ° C. or higher because the treatment time required for the effect of heat treatment can be set appropriately. It is preferable that the temperature is 70 ° C. or higher. The upper limit of the heat treatment temperature is usually 200 ° C. or less, preferably 160 ° C. or less, from the viewpoint of preventing the gas barrier property from being lowered due to thermal decomposition of the components constituting the gas barrier film. The treatment time depends on the heat treatment temperature, and is preferably shorter as the treatment temperature is higher. For example, when the heat treatment temperature is 60 ° C., the treatment time is about 3 days to 6 months, when it is 80 ° C., the treatment time is about 3 hours to 10 days, and when it is 120 ° C., the treatment time is about 1 hour to 1 day. In the case of 150 ° C., the treatment time is about 3 to 60 minutes, but these are merely guidelines and can be appropriately adjusted depending on the type of components constituting the gas barrier film, the thickness of the constituent layers, and the like.

In the present invention, various gas barrier films obtained by further laminating additional constituent layers as necessary on the constituent layers can be used according to applications.
As a normal embodiment, a gas barrier film in which a plastic film is provided on the Cat-CVD layer or the protective layer is used for various applications. The thickness of the plastic film is usually 5 to 500 μm, preferably 10 to 200 μm, depending on the application, from the viewpoints of mechanical strength, flexibility, transparency as a substrate of the laminated structure. . In addition, the width and length of the film are not particularly limited and can be appropriately selected according to the application. However, when manufacturing an industrial product using a barrier film, a long product can be manufactured. From the viewpoint of productivity and cost advantages, such as the ability to produce a large number of products in a single process, it is desirable that the width and length of the film be long. The film width is preferably 0.6 m or more, more preferably 0.8 m or more, more preferably 1.0 m or more, and the film length is preferably 1000 m or more, more preferably 3000 m or more, more preferably 5000 m or more. Further, for example, by using a resin capable of heat sealing on the surface of the Cat-CVD layer or the protective layer, heat sealing becomes possible, and it can be used as various containers. Examples of the resin that can be heat sealed include known resins such as polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer, ionomer resin, acrylic resin, and biodegradable resin.

  Another embodiment of the gas barrier film is one in which a printing layer is formed on the application surface of the Cat-CVD layer or the protective layer, and a heat seal layer is further laminated thereon. As the printing ink for forming the printing layer, aqueous and solvent-based resin-containing printing inks can be used. Here, examples of the resin used in the printing ink include acrylic resins, urethane resins, polyester resins, vinyl chloride resins, vinyl acetate copolymer resins, and mixtures thereof. Furthermore, for printing inks, antistatic agents, light shielding agents, ultraviolet absorbers, plasticizers, lubricants, fillers, colorants, stabilizers, lubricants, antifoaming agents, crosslinking agents, antiblocking agents, antioxidants, etc. These known additives may be added.

Although it does not specifically limit as a printing method for providing a printing layer, Well-known printing methods, such as an offset printing method, a gravure printing method, and a screen printing method, can be used. For drying the solvent after printing, a known drying method such as hot air drying, hot roll drying, or infrared drying can be used.
It is also possible to laminate at least one paper or plastic film between the printing layer and the heat seal layer. As a plastic film, the thing similar to the plastic film as a base material used for the gas barrier film of this invention can be used. Among these, paper, polyester resin, polyamide resin or biodegradable resin is preferable from the viewpoint of obtaining sufficient rigidity and strength of the laminate.

The gas barrier film of the present invention exhibits a high gas barrier property, and has a water vapor permeability of 5 × 10 ⁻³ g / m ² / day or less, preferably 2 × 10 ⁻³ g / m ² / day or less. Is obtained.
The water vapor transmission rate can be measured as follows.
<Measurement of water vapor transmission rate>
According to the conditions of JIS Z0222 “moisture-proof packaging container moisture permeability test method” and JIS Z0208 “moisture-proof packaging material amount moisture permeability test method (cup method)”, the following method is used for evaluation.
Using two gas barrier films each having a moisture permeable area of 10.0 cm × 10.0 cm square, a bag was prepared in which about 20 g of anhydrous calcium chloride was added as a hygroscopic agent and sealed on all sides, and the bag was heated to 40 ° C. and 90% relative humidity. In a constant temperature and humidity device, mass measurement (in units of 0.1 mg) is performed for up to 14 days as a guideline that the weight increase becomes almost constant at intervals of 48 hours or more, and the water vapor transmission rate is calculated from the following formula.
Water vapor transmission rate [g / m ² / day] = (m / s) / t
m: Mass increase in the last two weighing intervals (g)
s; Moisture permeable area (m ² )
t: Time of last two weighing intervals (h) / 24 (h)

<Explanation of terms>
In the present specification, the expression “X to Y” (X and Y are arbitrary numbers) means “X or more and Y or less” unless otherwise specified.

  The gas barrier film of the present invention is used for packaging of articles that need to block various gases such as water vapor and oxygen, for example, packaging materials such as foods, chemicals and chemicals, packaging sheets, packaging materials such as electronic devices, and electronic devices. It can be suitably used as a flexible substrate, a back sheet and a front sheet for solar cells, electronic paper, materials such as an organic EL device, a protective film, and a building material such as a heat insulating material. Moreover, the gas barrier film of the present invention has good productivity and can be industrially produced.

Claims (18)

  A gas barrier having an inorganic layer formed by vacuum deposition, an inorganic layer formed by chemical vapor deposition, an inorganic layer formed by vacuum vapor deposition, and a layer formed by catalytic chemical vapor deposition in this order on at least one surface of the substrate Sex film.   The gas barrier film according to claim 1, wherein the chemical vapor deposition method is a plasma CVD method.   The gas barrier film according to claim 1 or 2, wherein the inorganic layer formed by the vacuum deposition method has a thickness of 0.1 nm or more and 500 nm or less.   The carbon content of the inorganic layer formed by the chemical vapor deposition method is 0.5 at. % Or more, 20 at. The gas barrier film according to any one of claims 1 to 3, wherein the film thickness is 20 nm or less formed by the chemical vapor deposition method.   The gas barrier film according to any one of claims 1 to 4, wherein a thickness of the layer formed by the catalytic chemical vapor deposition method is 0.1 nm or more and 100 nm or less.   The gas barrier film according to any one of claims 1 to 5, wherein the inorganic layer formed by the chemical vapor deposition method comprises two or more layers.   The gas barrier film according to claim 1, wherein the layer formed by the catalytic chemical vapor deposition method is an inorganic layer made of a silicon compound.   The gas barrier property according to any one of claims 1 to 6, wherein the layer formed by the catalytic chemical vapor deposition method is an organic layer mainly composed of a composition containing a monomer having a methacryloyl group, an acryloyl group, or an oxirane group. the film.   The gas barrier film according to any one of claims 1 to 8, wherein at least one of the inorganic layers formed by vacuum deposition is made of silicon oxide.   The gas barrier film according to any one of claims 1 to 9, wherein an anchor coat layer is formed between the substrate and the inorganic layer formed by a vacuum deposition method.   The gas barrier film according to any one of claims 1 to 10, wherein the substrate is a transparent polymer film.   The protective film for electronic paper comprised from the gas barrier film in any one of Claims 1-11.   The protective film for solar cells comprised from the gas barrier film in any one of Claims 1-11.   The packaging material of the chemical | medical agent or chemical | medical solution comprised from the gas barrier film in any one of Claims 1-11.   The protective film for organic electroluminescent devices comprised from the gas barrier film in any one of Claims 1-11 This is a method for producing a gas barrier film in which an inorganic layer by vacuum deposition, an inorganic layer by chemical vapor deposition, an inorganic layer by vacuum vapor deposition, and a layer by catalytic chemical vapor deposition are formed in this order on at least one surface of the substrate. Then, the formation of the layer by the catalytic chemical vapor deposition method is performed under a reduced pressure of 1 Pa to 1 × 10 ³ Pa, and the formation of the inorganic layer by the vacuum evaporation method is performed under a reduced pressure of 1 × 10 ⁻⁷ Pa to 1 Pa. The formation of the inorganic layer by the chemical vapor deposition method is performed under a reduced pressure of 1 × 10 ⁻² Pa to 10 Pa, and the layer by the catalytic chemical vapor deposition method, the inorganic layer by the vacuum vapor deposition method, and the inorganic layer by the chemical vapor deposition method The manufacturing method of the gas-barrier film performed by the conveyance speed of the base material at the time of formation of 20 m / min or more.   The formation of an inorganic layer by a vacuum vapor deposition method, formation of an inorganic layer by a chemical vapor deposition method, formation of an inorganic layer by a vacuum vapor deposition method and a layer by a catalytic chemical vapor deposition method are continuously performed in the same vacuum chamber under reduced pressure. The manufacturing method of the gas barrier film of description.   The method for producing a gas barrier film according to claim 16 or 17, wherein the gas barrier film is one according to any one of claims 2 to 11.