JP2020104429A - Barrier film - Google Patents

Abstract

To provide a barrier film excellent in gas barrier properties, light shielding properties and water resistant adhesion.SOLUTION: A barrier film includes a substrate layer, a chemical vapor-deposited layer, a barrier coat layer and a physical vapor-deposited, layer in this order. The chemical vapor-deposited layer is a silicon oxide vapor-deposited film. The physical vapor-deposited layer is an aluminum vapor deposited film.SELECTED DRAWING: Figure 1

Description

The present invention relates to a barrier film, and more particularly to a barrier film including a base material layer, a chemical vapor deposition layer, a barrier coat layer, and a physical vapor deposition layer in this order.

In recent years, as a barrier material against oxygen or water vapor, an inorganic oxide such as silicon oxide or aluminum oxide is formed on a film base material by a vacuum deposition method, a sputtering method, an ion plating method, a chemical vapor deposition method or the like. The transparent gas barrier film has become the focus of attention. In particular, depending on the application of the barrier film, it was necessary to maintain a high gas barrier property. For such a technical problem, for example, a base material made of a plastic material, a first vapor deposition thin film layer formed of an inorganic substance and provided in contact with the base material, and the first vapor deposition thin film layer A gas barrier intermediate layer formed by applying a coating agent containing at least a water-soluble polymer, and a second vapor-deposited thin film layer formed of an inorganic substance and directly vapor-deposited on the intermediate layer. A laminated body provided is proposed (see Patent Document 1).

Further, depending on the use of the barrier film, in addition to the gas barrier property, the light shielding property was required. For such a technical problem, for example, Patent Document 1 proposes a laminated body in which metallic aluminum is vapor-deposited as a second vapor-deposited thin film layer. Further, a vapor deposition thin film layer of an inorganic oxide on at least one surface of a transparent substrate layer, a metal tone printing layer, an adhesive layer, a light shielding sealant layer on the gas barrier coating layer surface of a transparent gas barrier film in which a gas barrier coating layer is laminated. A layered body in which the metal tone printing layer is composed of an ink film mixed with a surface-treated aluminum metal powder for improving adhesion to a binder resin and an antiblocking agent composed of an inorganic powder. Has been proposed (see Patent Document 2).

Japanese Patent No. 4085814 JP 2005-1753 A

In recent years, depending on the use of the barrier film, in addition to the gas barrier property, water resistance, particularly water resistance adhesion is also required. The inventors of the present invention include the biaxially stretched polyethylene terephthalate film/aluminum oxide vapor deposition layer (first vapor deposition thin film layer)/gas barrier intermediate layer/metal aluminum vapor deposition layer (second vapor deposition thin film layer) described in Patent Document 1. We have found a new technical problem that the laminate having a layer structure is inferior in water resistance adhesion. Further, in the light-shielding barrier packaging material described in Patent Document 2, it is necessary to add an inorganic powder to the metal-tone print layer, or to add a light-shielding agent such as carbon black to the light-shielding sealant layer. There are problems such as adhesion between layers and cost.

The present invention has been made in view of the background art and new technical problems described above, and an object of the present invention is to provide a barrier film having excellent gas barrier properties, light shielding properties, and water resistant adhesion.

The present inventors have conducted extensive studies to solve the above problems, and in a barrier film comprising a base material layer, a chemical vapor deposition layer, a barrier coat layer, and a physical vapor deposition layer in this order, By forming a silicon oxide vapor deposition film as a chemical vapor deposition layer and forming an aluminum vapor deposition film as the physical vapor deposition layer, it is possible to provide a barrier film having excellent gas barrier properties, light shielding properties, and water resistant adhesion. I found out. The present invention has been completed based on such findings.

That is, according to one aspect of the present invention,
A barrier film comprising a base material layer, a chemical vapor deposition layer, a barrier coat layer, and a physical vapor deposition layer in this order,
The chemical vapor deposition layer is a silicon oxide vapor deposition film,
A barrier film is provided, wherein the physical vapor deposition layer is an aluminum deposition film.

In the aspect of the present invention, the base film is preferably a biaxially stretched polyethylene terephthalate film.

In the aspect of the present invention, the barrier coat layer is preferably a resin cured film of a metal alkoxide and a water-soluble polymer.

In the aspect of the present invention, it is preferable that the barrier coat layer is a resin cured film containing a reaction product formed by reacting a metal oxide and a phosphorus compound.

In the aspect of the present invention, the barrier coat layer is preferably a resin cured film containing a carboxyl group-containing polymer crosslinked with a polyvalent metal compound.

In the aspect of the present invention, the barrier film has an acidity permeability of 1.0 cc/m ² ·atm·day or less measured in accordance with JIS K7126 method under an environment of a temperature of 23° C. and a humidity of 90% RH. It is preferable to have.

In the aspect of the present invention, the barrier film has a water vapor permeability of 1.0 g/m ² ·day or less measured in accordance with JIS K7129 method under an environment of a temperature of 40° C. and a humidity of 100% RH. Is preferred.

In the aspect of the present invention, the barrier film preferably has a total light transmittance of 10% or less measured according to JIS K7361.

In another aspect of the present invention, there is provided a moisture-proof sheet including the barrier film described above.

In another aspect of the present invention, there is provided a heat insulating material including the barrier film described above.

In another aspect of the present invention, there is provided a packaging material comprising the above barrier film.

According to the present invention, it is possible to provide a barrier film having excellent gas barrier properties, light shielding properties, and water resistant adhesion. Such a barrier film can be suitably used for applications requiring high gas barrier properties, moisture proof properties, light shielding properties, and the like, for example, moisture proof sheets, heat insulating materials, packaging materials and the like.

It is a schematic sectional drawing which showed one Embodiment of the barrier film of this invention.

<Barrier film>
The barrier film according to the present invention comprises a base material layer, a chemical vapor deposition layer, a barrier coat layer, and a physical vapor deposition layer in this order.

The barrier film has an acid permeability of preferably 1.00 cc/m ² ·atm·day or less, more preferably 0, measured in accordance with JIS K7126 method under an environment of temperature 23°C and humidity 90%RH. It is 0.50 cc/m ² ·atm·day or less, more preferably 0.20 cc/m ² ·atm·day or less, and even more preferably 0.10 cc/m ² ·atm·day or less. When the oxygen permeability is within the above numerical range, it has suitable oxygen barrier properties, and thus can be used for various applications requiring oxygen barrier properties. The oxygen permeability can be measured using an oxygen permeability meter (MOCON: OX-TRAN).

The barrier film has a water vapor permeability of preferably 1.00 g/m ² ·day or less, more preferably 0.50 g, measured in accordance with JIS K7129 method under an environment of a temperature of 40° C. and a humidity of 100% RH. /M ² ·day or less, more preferably 0.20 g/m ² ·day or less, even more preferably 0.10 g/m ² ·day or less.
When the water vapor permeability is within the above numerical range, it has a suitable water vapor barrier property, and thus it can be used for various applications requiring water vapor barrier property. The water vapor permeability can be measured using a water vapor permeability measuring device (PERCON, manufactured by MOCON).

The total light transmittance of the barrier film measured according to JIS K7361 is preferably 10% or less, more preferably 8% or less, and further preferably 6% or less. When the total light transmittance is within the above numerical range, it has suitable light-shielding properties, and thus can be used in various applications where light-shielding properties are required. The total light transmittance can be measured using a haze meter (HM-150 manufactured by Murakami Lighting Research Laboratory Co., Ltd.).

The layer structure of the barrier film will be described with reference to the drawings. The barrier film 10 shown in FIG. 1 includes a base material layer 11, a chemical vapor deposition layer 12, a barrier coat layer 13, and a physical vapor deposition layer 14 in this order. Hereinafter, each layer constituting the barrier film of the present invention will be described.

(Base material layer)
The substrate layer used in the barrier film of the present invention is not particularly limited, but it has excellent chemical or physical strength, can withstand the conditions for forming a chemical vapor deposition layer into a film, and has its film characteristics. It is possible to use a resin film that can be satisfactorily held without being damaged. Specifically, for example, polyolefin resin such as polyethylene resin or polypropylene resin, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS Resin), poly(meth)acrylic resin, polycarbonate resin, polyvinyl alcohol resin, saponified ethylene-vinyl ester copolymer, polyester resin such as polyethylene terephthalate and polyethylene naphthalate, polyamide resin such as various nylons Films of various resins such as polyurethane resin, acetal resin, and cellulose resin can be used. In the present invention, it is particularly preferable to use a polyester resin film, a polyolefin resin film, or a polyamide resin film among the above resin films. The substrate layer may be any of unstretched films of the above resins and films of uniaxially or biaxially stretched resins.

As the polyester resin film, the following polyester films can be used in addition to polyethylene terephthalate derived from general petrochemical fuel.

(Polybutylene terephthalate film (PBT))
Since polybutylene terephthalate film has a high heat distortion temperature, excellent mechanical strength and electrical characteristics, and good moldability, it can be used in packaging bags that contain contents such as foods when it undergoes retort treatment. It is possible to prevent the packaging bag from being deformed and its strength to be reduced. The polybutylene terephthalate film is a film containing polybutylene terephthalate (hereinafter also referred to as PBT) as a main component, and is preferably a resin film containing 60% by mass or more of PBT.

(Polyester film derived from biomass)
The biomass-derived polyester film is composed of a resin composition containing a polyester composed of a diol unit and a dicarboxylic acid unit as a main component, and the resin composition is such that the diol unit is ethylene glycol derived from the biomass, and the dicarboxylic acid unit is Is a dicarboxylic acid derived from fossil fuel, and is contained in an amount of 50 to 95% by mass, preferably 50 to 90% by mass, based on the entire resin composition.

The biomass-derived ethylene glycol is derived from ethanol (biomass ethanol) produced from biomass such as sugar cane and corn. For example, biomass-derived ethylene glycol can be obtained from biomass ethanol by a conventionally known method and a method of producing ethylene glycol via ethylene oxide. Further, commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycol can be suitably used.

As the dicarboxylic acid unit of polyester, a dicarboxylic acid derived from fossil fuel is used. As the dicarboxylic acid, aromatic dicarboxylic acid, aliphatic dicarboxylic acid, and derivatives thereof can be used. Examples of the aromatic dicarboxylic acid include terephthalic acid and isophthalic acid, and examples of the derivative of the aromatic dicarboxylic acid include lower alkyl ester of aromatic dicarboxylic acid, specifically, methyl ester, ethyl ester, propyl ester and butyl ester. Examples thereof include esters. Among these, terephthalic acid is preferable, and dimethyl terephthalate is preferable as the derivative of the aromatic dicarboxylic acid.

The polyester that may be included in the resin composition forming the biomass-derived polyester film in a proportion of 5 to 45 mass% is a fossil fuel-derived polyester, a recycled polyester of a fossil fuel-derived polyester product, or a biomass-derived polyester product. It is a recycled polyester.

(Recycled polyethylene terephthalate)
A polyethylene terephthalate film containing polyethylene terephthalate recycled by mechanical recycling. Specifically, it contains PET recycled by mechanical recycling of a PET bottle. This PET contains ethylene glycol as the diol component and terephthalic acid as the dicarboxylic acid component. And isophthalic acid. The content of the isophthalic acid component is preferably 0.5 mol% or more and 5 mol% or less, and 1.0 mol% or more and 2.5 mol% or less, based on all dicarboxylic acid components constituting PET. Is more preferable.

Here, mechanical recycling generally means crushing collected polyethylene terephthalate resin products such as PET bottles and washing with alkali to remove dirt and foreign substances on the surface of the PET resin products, and then drying at high temperature and reduced pressure for a certain period of time. Then, the contaminants remaining inside the PET resin are diffused to be decontaminated, the stains of the resin product made of the PET resin are removed, and the PET resin is returned again.

The recycled polyethylene terephthalate preferably contains recycled PET in a proportion of 50% by weight or more and 95% by weight or less, and may contain virgin PET. As virgin PET, a general diol component may be ethylene glycol, a dicarboxylic acid component may be terephthalic acid, and may also include isophthalic acid.

The film thickness of various resin films is preferably about 6 to 2000 μm, more preferably about 9 to 100 μm.

(surface treatment)
In the present invention, the surface treatment may be performed on the base material layer in advance before forming the chemical vapor deposition layer on the base material layer. This can improve the adhesiveness with the chemical vapor deposition layer. Similarly, the vapor deposition layer may be subjected to a surface treatment to improve the adhesiveness with the gas barrier coating film. Examples of such surface treatment include corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, pretreatment such as oxidation treatment using chemicals and the like.

In addition, a primer coating agent, an undercoating agent, a vapor deposition anchor coating agent, or the like can be optionally applied for surface treatment. Examples of the coating agent include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth)acrylic resins, polyvinyl acetate resins, and polyolefin resins such as polyethylene or polypropylene. A resin composition containing a resin, a copolymer or modified resin thereof, a cellulosic resin or the like as a main component of the vehicle can be used.

Among such surface treatments, corona treatment and plasma treatment are particularly preferable. For example, as the plasma treatment, there is plasma treatment in which surface modification is performed by using plasma gas generated by ionizing gas by arc discharge. As the plasma gas, in addition to the above, inorganic gases such as oxygen gas, nitrogen gas, argon gas, and helium gas can be used. For example, by performing in-line plasma treatment, it is possible to remove water, dust, and the like on the surface of the base material layer and enable surface treatment such as smoothing and activation of the surface. Further, plasma treatment may be performed after vapor deposition to improve the adhesiveness. In the present invention, as the plasma treatment, it is preferable to perform plasma discharge treatment in consideration of plasma output, type of plasma gas, supply amount of plasma gas, treatment time, and other conditions. As a method of generating plasma, a device such as direct current glow discharge, high frequency discharge, microwave discharge or the like can be used. Further, plasma treatment can be performed by an atmospheric pressure plasma treatment method.

(Chemical vapor deposition layer)
The chemical vapor deposition layer forming the barrier film according to the present invention is a vapor deposition film formed by a chemical vapor deposition method (CVD method). In the present invention, by forming a silicon oxide vapor deposition film as the chemical vapor deposition layer, it is possible to improve the water barrier adhesion with the base material layer while improving the gas barrier property.

Examples of the chemical vapor deposition method (CVD method) include a plasma chemical vapor deposition method, a low temperature plasma chemical vapor deposition method, a thermochemical vapor deposition method, and a photochemical vapor deposition method. Specifically, on one surface of the base material layer (resin film), a monomer gas for vapor deposition such as an organic silicon compound is used as a raw material, and an inert gas such as argon gas or helium gas is used as a carrier gas. As the oxygen supply gas, oxygen gas or the like is used, and the silicon oxide vapor deposition film can be formed by a low temperature plasma chemical vapor deposition method using a low temperature plasma generator or the like. As the low temperature plasma generator, for example, a generator of high frequency plasma, pulse wave plasma, microwave plasma or the like can be used. It is preferable to use a high-frequency plasma type generator because a highly active and stable plasma can be obtained.

Examples of the vapor deposition monomer gas of the organic silicon compound that forms the silicon oxide vapor deposition film include 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, and the like. Methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane Etc. can be used. Among these, it is particularly preferable to use 1,1,3,3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material because of its handleability and the characteristics of the formed continuous film. In the above, as the inert gas, for example, argon gas, helium gas or the like can be used.

The silicon oxide vapor-deposited film is mainly composed of silicon oxide, and further contains at least one kind of compound consisting of one or more elements of carbon, hydrogen, nitrogen, silicon or oxygen by a chemical bond or the like. You may. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit having a graphite shape, a diamond shape, a fullerene shape, or the like, a raw material organosilicon compound or a derivative thereof is further added. It may be contained by a chemical bond or the like. For example, hydrocarbon having a CH ₃ moiety, hydrosilica such as SiH ₃ silyl and SiH ₂ silylene, and hydroxyl group derivative such as SiH ₂ OH silanol can be exemplified. In addition to the above, the kind, amount, etc. of the compound contained in the silicon oxide vapor deposition film can be changed by changing the conditions of the vapor deposition process and the like.

The film thickness of the silicon oxide vapor deposition film is preferably 3 nm or more and 100 nm or less, more preferably 4 nm or more and 50 nm or less, and more preferably 5 nm or more and 30 nm or less. When the film thickness of the silicon oxide vapor deposition film is within the above range, it is possible to further improve the water-resistant adhesion to the base material layer while exhibiting sufficient gas barrier properties.

(Barrier coat layer)
The barrier coat layer formed on the chemical vapor deposition layer is a layer having a gas barrier property, and the coating film applied by coating is a cured resin film cured by drying.

As the first aspect of the barrier coat layer, a cured film of a hydrolysis product of a metal alkoxide and a water-soluble polymer can be used. This barrier coat layer can be formed, for example, by the following gas barrier coating film. Gas barrier coating film is a coating that holds the gas barrier property under high temperature and high humidity environment, the gas barrier coating film is a coating that holds the gas barrier property under high temperature and high humidity environment, the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, and m represents It represents an integer of 1 or more, and n+m represents a valence of M.) at least one metal alkoxide represented by the formula (1) and a water-soluble polymer, and further contains a sol-gel method catalyst, an acid, water, And a coating film comprising a barrier coat composition obtained by polycondensation by a sol-gel method in the presence of an organic solvent.

In the above general formula R ¹ _n M(OR ² ) _m , R ¹ is an optionally branched alkyl group having 1 to 8, preferably 1 to 5 and more preferably 1 to 4 carbon atoms. , For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group and the like. Can be mentioned.

In the general formula R ¹ _n M(OR ² ) _m , R ² is an alkyl group having 1 to 8 carbon atoms, which may have a branch, more preferably 1 to 5, and particularly preferably 1 to 4 carbon atoms. Examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a sec-butyl group. In addition, when a plurality of (OR ² ) are present in the same molecule, the (OR ² ) may be the same or different.

In the above general formula R ¹ _n M(OR ² ) _m , examples of the metal atom represented by M include silicon, zirconium, titanium and aluminum.

As the alkoxide represented by the general formula R ¹ _n M(OR ² ) _m , at least one kind of a partial hydrolyzate of an alkoxide and a hydrolytic condensate of an alkoxide can be used. The partial hydrolyzate is not limited to one in which all of the alkoxy groups are hydrolyzed, and may be one or more in which it is hydrolyzed, or a mixture thereof, and further, a condensate of hydrolysis. As the above, a partially hydrolyzed alkoxide dimer or more, specifically, a dimer to hexamer may be used.

In the present invention, as the alkoxide represented by the general formula R ¹ _n M(OR ² ) _m , an alkoxysilane in which M is Si can be preferably used. Suitable alkoxysilanes, for example, tetramethoxysilane Si _{(OCH 3) 4,} tetraethoxysilane _{Si (OC 2 H 5) 4} , tetrapropoxysilane _{Si (OC 3 H 7) 4} , tetrabutoxysilane Si (OC ₄ H _{9) 4,} methyltrimethoxysilane _{CH 3 Si (OCH 3) 3} , methyltriethoxysilane _{CH 3 Si (OC 2 H 5} ) 3, dimethyldimethoxysilane _{(CH 3) 2 Si (OCH} 3) 2, dimethyldi silane _{(CH 3) 2 Si (OC} 2 H 5) 2 and the like. In the present invention, polycondensation products of these alkoxysilanes can also be used, and specifically, for example, polytetramethoxysilane, polytetraemethoxysilane, etc. can be used.

In the present invention, a zirconium alkoxide in which M is Zr can also be suitably used as the alkoxide represented by the above general formula R ¹ _n M(OR ² ) _m . Suitable zirconium alkoxides, for example, tetramethoxy zirconium Zr _{(OCH 3) 4,} tetraethoxy zirconium _{Zr (OC 2 H 5) 4} , tetra i propoxy zirconium _{Zr (iso-OC 3 H 7} ) 4, tetra-n-butoxy zirconium Zr _{(OC 4} H ₉₎ can be exemplified ₄ like.

Further, as the alkoxide represented by the above general formula R ¹ _n M(OR ² ) _m , a titanium alkoxide in which M is Ti can also be preferably used. Suitable titanium alkoxides, for example, tetramethoxy titanium Ti _{(OCH 3) 4,} tetraethoxy titanium _{Ti (OC 2 H 5) 4} , tetraisopropoxy titanium _{Ti (iso-OC 3 H 7} ) 4, tetra-n-butoxy titanium Ti _{(OC 4} H ₉₎ can be exemplified ₄ like.

Further, as the alkoxide represented by the general formula R ¹ _n M(OR ² ) _m , an aluminum alkoxide in which M is Al can also be suitably used. Suitable aluminum alkoxides such as tetramethoxysilane aluminum Al _{(OCH 3) 4,} tetraethoxy aluminum _{Al (OC 2 H 5) 4} , tetraisopropoxy aluminum _{Al (iso-OC 3 H 7} ) 4, tetra-n-butoxy aluminum al _{(OC 4} H ₉₎ can be exemplified ₄ like.

In the present invention, the above alkoxides may be used in combination of two or more kinds. For example, when an alkoxysilane and a zirconium alkoxide are mixed and used, the toughness and heat resistance of the obtained barrier film can be improved. Further, when the alkoxysilane and the titanium alkoxide are mixed and used, the thermal conductivity of the obtained gas barrier coating film is lowered and the heat resistance is remarkably improved.

As the water-soluble polymer used in the present invention, a polyvinyl alcohol resin or an ethylene/vinyl alcohol copolymer may be used alone, or a polyvinyl alcohol resin and an ethylene/vinyl alcohol copolymer may be used. Combinations can be used in combination. In the present invention, by using the polyvinyl alcohol resin and/or the ethylene/vinyl alcohol copolymer, the physical properties such as gas barrier property, water resistance, weather resistance and the like can be remarkably improved.

As the polyvinyl alcohol-based resin, those obtained by saponifying polyvinyl acetate can be generally used. The polyvinyl alcohol-based resin may be a partially saponified polyvinyl alcohol-based resin in which an acetic acid group remains tens of percent, a completely saponified polyvinyl alcohol in which an acetic acid group does not remain, or a modified polyvinyl alcohol-based resin in which an OH group is modified. Well, it is not particularly limited.

As the ethylene/vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer can be used. For example, partial saponification products in which several tens mol% of acetic acid groups remain, to complete saponification products in which only several mol% of acetic acid groups remain or acetic acid groups do not remain, are not particularly limited. However, from the viewpoint of gas barrier properties, the saponification degree is preferably 80 mol% or more, more preferably 90 mol% or more, and further preferably 95 mol% or more. The content of repeating units derived from ethylene in the ethylene/vinyl alcohol copolymer (hereinafter also referred to as "ethylene content") is usually 0 to 50 mol%, preferably 20 to 45 mol%. It is preferable.

A silane coupling agent may be added to the barrier coat layer. For example, a silane coupling agent having a reactive group such as an alkoxy group such as a methoxy group and an ethoxy group, an acetoxy group, an amino group, an epoxy group can be used. Specifically, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxy Propylmethyldiethoxysilane, γ-glycidoxypropyldimethylethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, or the like can be used.

Furthermore, as the organic solvent used in the above barrier coat composition, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol and the like can be used. The polyvinyl alcohol-based resin and/or the ethylene/vinyl alcohol copolymer are preferably handled in a state of being dissolved in a coating liquid containing the alkoxide, the silane coupling agent, or the like. It can be appropriately selected. For example, when a polyvinyl alcohol-based resin and an ethylene/vinyl alcohol copolymer are used in combination, it is preferable to use n-butanol.

The barrier coat layer can be manufactured by the following method. First, the metal alkoxide, if necessary, a silane coupling agent, a water-soluble polymer, a sol-gel method catalyst, an acid, water, an organic solvent and the like are mixed to prepare a barrier coat composition (barrier coat liquid).

Then, the barrier coat composition is applied onto the chemical vapor deposition layer. As a method for applying the barrier coat composition, for example, a roll coater such as a gravure roll coater, a spray coater, a spin coater, a dipping coat, a brush, a bar code, an applicator or the like may be applied to the barrier coat composition once or a plurality of times. It is possible to form a coating film having a dry film thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm.

Then, the film coated with the above barrier coat composition is 120°C to 200°C, and a temperature not higher than the melting point of the resin film of the substrate film of the barrier film, preferably 130°C to 180°C, more preferably 140°C to 160°C. Heat and dry for 3 seconds to 10 minutes at a temperature in the range. Thereby, polycondensation is performed and a barrier coat layer can be formed. Further, the barrier coat composition is overlaid on the chemical vapor deposition layer to form two or more coating films, and the temperature is 120° C. to 200° C. and the melting point of the resin substrate is lower than or equal to 3 seconds. You may heat-dry for 10 minutes and form the composite polymer layer which laminated two or more barrier coat layers. As described above, one or more barrier coat layers can be formed from the above barrier coat composition.

The thickness of the barrier coat layer is not particularly limited, but is preferably 10 nm or more and 5000 nm or less, more preferably 50 nm or more and 1000 nm or less, further preferably 100 nm or more and 500 nm or less, and still more preferably 150 nm or more and 400 nm or less. Is. When the thickness of the barrier coat layer is about the above range, the surface of the chemical vapor deposition layer can be coated as a layer that can exhibit gas barrier properties and has flexibility.

As the second aspect of the barrier coat layer, a resin cured film containing a reaction product formed by reacting a metal oxide and a phosphorus compound can be used. This cured resin film has a gas barrier property, and has a wave number in the infrared absorption spectrum in the range of 800 to 1400 cm -1 at which the maximum infrared absorption is in the range of 1080 to 1130 cm -1.

In the reaction product, when a metal atom (M) forming a metal oxide and a phosphorus atom (P) are bonded via an oxygen atom (O) to form a bond represented by M-O-P, M It is considered that the absorption peak based on the -O-P bond appears as the absorption peak of the maximum absorption wave number in the range of 800 to 1400 cm-1 in the range of 1080 to 1130 cm-1.

This infrared absorption spectrum can be obtained by measuring the surface of the barrier coat layer by a total reflection measuring method, or by measuring the infrared absorption spectrum of a component scraped off the barrier coat layer by a KBr method.

The metal oxide is an oxide of magnesium, calcium, aluminum, silicon, titanium, zirconium or the like.

The metal oxide can be obtained by hydrolyzing a compound containing the metal atom, and examples of the compound that can be produced by hydrolyzing the metal oxide include aluminum chloride, aluminum triethoxide, and aluminum trinormal. Propoxide, aluminum triisopropoxide, aluminum trinormalbutoxide, aluminum tris-butoxide, aluminum trit-butoxide, aluminum triacetate, aluminum acetylacetonate, aluminum nitrate, titanium tetraisopropoxide, titanium tetranormalbutoxide, titanium tetra. (2-ethylhexoxide), titanium tetramethoxide, titanium tetraethoxide, titanium acetylacetonate, zirconium tetranormal propoxide, zirconium tetrabutoxide, zirconium tetraacetylacetonate, etc. even if used alone Good, or two or more kinds may be used in combination.

As the phosphorus compound, one having a structure in which a halogen atom or an oxygen atom is directly bonded to a phosphorus atom can be used. Specific examples thereof include phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid and derivatives thereof, and examples of the polyphosphoric acid include pyrophosphoric acid, triphosphoric acid, polyphosphoric acid in which four or more phosphoric acids are condensed, and the like. Examples of the derivatives include salts of phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, (partial) ester compounds, halides (chlorides, etc.), dehydrated products (niline pentoxide, etc.), and the like.

The reaction product can be formed by mixing and reacting the metal oxide and the phosphorus compound. At this time, the phosphorus compound to be mixed may be in the form of itself or in the form of a composition containing the phosphorus compound and the added resin.

Such added resins include polyvinyl alcohol, partially saponified polyvinyl acetate, polyethylene glycol, polyhydroxyethyl (meth)acrylate, polyacrylic acid, polymethacrylic acid, poly(acrylic acid/methacrylic acid) and salts thereof, Ethylene-vinyl alcohol copolymer, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride alternating copolymer, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer Examples include saponified products of polymers.

In the present invention, this barrier coat layer can be laminated by coating a chemical vapor deposition layer with a coating liquid in which a metal oxide and a phosphorus compound are mixed, and drying the coating liquid. ˜1 μm.

The coating solution is prepared by first dispersing an aqueous solution in which a metal oxide is produced by dispersing/dissolving a compound capable of producing a metal oxide by hydrolysis, with a solvent in which a phosphorus compound is dispersed/dissolved, or a phosphorus compound. It can be prepared by adding a composition containing an additive resin to a solvent in which the resin is dispersed and dissolved.

As the third aspect of the barrier coat layer, a resin cured film containing a carboxyl group-containing polymer crosslinked with a polyvalent metal compound can be used. This cured resin film has gas barrier properties.

The carboxyl group-containing polymer is a polymer containing two or more carboxyl groups, and specifically, polyacrylic acid, polymethacrylic acid, a copolymer of acrylic acid and methacrylic acid, or two kinds of these. It is a mixture of the above.

The polyvalent metal compound is a metal compound of beryllium, magnesium, calcium, titanium, zirconium, chromium, manganese, iron, cobalt, nickel, copper, zinc, aluminum and oxides, carbonates, and organic acid salts thereof. These oxides and carbonates include oxides such as zinc oxide, magnesium oxide, copper oxide, nickel oxide and cobalt oxide; carbonates such as calcium carbonate; organic acid salts such as calcium lactate, zinc lactate and calcium acrylate. is there. The resin film containing the carboxyl group-containing polymer crosslinked with the polyvalent metal compound can be prepared as a resin cured film in which the carboxyl group-containing polymer and the polyvalent metal compound are mixed.

Further, another form of this resin film can be made by forming a two-layer structure in which a layer containing a polyvalent metal compound is laminated adjacent to a resin layer containing a carboxyl group-containing polymer. The resin layer containing the carboxyl group-containing polymer is ionically cross-linked by the polyvalent metal ions transferred from the separated layer containing the polyvalent metal compound to form a cured resin film.

The resin layer containing the carboxyl group-containing polymer can contain a polyalcohol such as polyvinyl alcohol or glycerin, in addition to the polymer containing two or more carboxyl groups. Then, the polymer containing two or more carboxyl groups and polyvinyl alcohol are mixed in a weight ratio of 99:1 to 20:80.

The layer containing a polyvalent metal compound, the above-mentioned metal compound, alkyd resin of mixing resin, melamine resin, acrylic resin, urethane resin, nitrocellulose, epoxy resin, polyester resin, phenol resin, amino resin, fluororesin, isocyanate It is a layer mixed with at least one resin selected from the group. The weight ratio of the polyvalent metal compound and the resin (metal compound/resin) is 0.01 to 1000. The polyvalent metal compound is mixed in the resin layer in the form of particles having an average particle size of 15 nm to 500 nm.

In the present invention, the barrier coat layer is a chemical vapor deposition layer and a resin prepared by mixing a carboxyl group-containing polymer and a polyvalent metal compound with water, alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; -By coating and drying the coating liquid dispersed or dissolved in a single substance or a mixed liquid of dimethyl sulfoxide, N,N-dimethylformamide, dimethylacetamide, acetone, methyl ethyl ketone, diethyl ether, dioxane, tetrahydrofuran, ethyl acetate and butyl acetate, It can be laminated, and its thickness is 0.1 to 10 μm.

As another method, first, a layer containing a carboxyl group-containing polymer is laminated on the chemical vapor deposition layer. In this lamination, a carboxyl group-containing polymer and other necessary additives are added to alcohols such as water, methyl alcohol, ethyl alcohol and isopropyl alcohol; N,N-dimethylsulfoxide, N,N-dimethylformamide, dimethylacetamide and the like. It is made by coating a coating solution dissolved or dispersed in a solvent and drying it, and its thickness is 0.1 to 10 μm.

Next, a polyvalent metal compound and a resin are dissolved or dispersed in a solvent such as acetone, methyl ethyl ketone, diethyl ether, dioxane, tetrahydrofuran, ethyl acetate, or butyl acetate, in addition to the above-mentioned solvent, to prepare a carboxyl group-containing compound. By coating a resin layer containing a polymer and drying it, a layer containing a polyvalent metal compound is laminated to a thickness of 0.1 to 10 μm.

By laminating a layer containing a polyvalent metal compound on a resin layer containing a carboxyl group-containing polymer in this manner, the carboxyl group-containing polymer ion is cross-linked by polyvalent metal ions transferred from the layer containing a polyvalent metal compound. And becomes a resin cured film. In order to promote migration of polyvalent metal ions, aging may be performed in a heating environment of 30 to 130 degrees after forming the two layers.

(Physical vapor deposition layer)
The physical vapor deposition layer constituting the barrier film according to the present invention is a vapor deposition film formed by a physical vapor deposition method (PVD method). In the present invention, by forming an aluminum vapor deposition film as the physical vapor deposition layer, it is possible to improve the light shielding property while improving the gas barrier property.

Examples of the physical vapor deposition method (PVD method) include a vacuum vapor deposition method, a sputtering method, an ion plating method, and an ion cluster beam method. Specifically, for example, it is possible to form a vapor deposition film using a vacuum vapor deposition method or the like in which aluminum is used as a raw material, which is heated to be vaporized and vaporized on one side of the base material layer (resin film). it can. As a heating method of the vapor deposition material, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method (EB) or the like can be used.

The film thickness of the aluminum vapor deposition film is preferably 20 nm or more and 500 nm or less, more preferably 30 nm or more and 500 nm or less, and more preferably 40 nm or more and 500 nm or less. When the film thickness of the aluminum vapor deposition film is within the above range, the light shielding property can be further improved while exhibiting sufficient gas barrier property.

<Use>
The barrier film according to the present invention can be applied to products in various fields in which high gas barrier properties, light shielding properties, water-resistant adhesion properties, etc. are required. Examples include products such as moisture-proof sheets, heat insulating materials, packaging materials, and medical instruments. When used in these products, the gas barrier property, the light-shielding property, and the water-resistant adhesive property can be improved by providing the barrier layer made of the barrier film of the present invention.

<Manufacture of barrier film>
[Example 1]
A biaxially stretched polyethylene terephthalate (PET) film having a thickness of 12 μm was prepared as a base material layer. Subsequently, the PET film was mounted on a delivery roll of a plasma enhanced chemical vapor deposition apparatus, and then hexamethyldisiloxane as a raw material was introduced on one surface of the film to introduce hexamethyldisiloxane:oxygen gas:oxygen gas: Helium=1.0:1.5:1.0 (unit: slm), degree of vacuum in vacuum chamber 2 to 6×10 ⁻⁶ mBar, degree of vacuum in vapor deposition chamber 2 to 5×10 ⁻³ mBar, cooling An electrode drum power was supplied at 10 kW to form a silicon oxide vapor deposition film (chemical vapor deposition layer) having a thickness of 10 nm.

Further, in accordance with the composition shown in Table 1, a hydrolyzed solution of composition B prepared in advance was added to the prepared mixed solution of composition A and stirred to obtain a colorless and transparent barrier coat composition.

Next, the barrier coat composition prepared above was coated on the silicon oxide deposited film by the direct gravure method. After that, heat treatment was performed at 140° C. for 60 seconds to form a barrier coat layer having a thickness of 0.3 μm (dry state).

Subsequently, a glow discharge plasma generator was used on the barrier coat layer to apply argon of 1.0 slm and current of 20 A to perform plasma treatment. Then, using aluminum as a raw material on the plasma-treated surface, the degree of vacuum in the vacuum chamber was set to 2×10 ⁻⁴ mbar and the degree of vacuum in the vapor deposition chamber was set to 2.0 by an electron beam heating vacuum deposition method. A 40 nm thick aluminum vapor deposition film (physical vapor deposition layer) is formed under the condition of ×10 ⁻² mbar to form a barrier film (layer structure: PET/silicon oxide vapor deposition film (chemical vapor deposition layer)/barrier coat). Layer/aluminum vapor deposition film (physical vapor deposition layer) was obtained.

[Example 2]
A barrier film (layer structure: PET/silicon oxide vapor deposition film (chemical vapor deposition layer)/) was formed in the same manner as in Example 1 except that the thickness of the silicon oxide vapor deposition film (chemical vapor deposition layer) was changed to 16 nm. A barrier coat layer/aluminum vapor deposition film (physical vapor deposition layer) was obtained.

[Example 3]
A barrier film (layer structure: PET/silicon oxide vapor deposition film (chemical vapor deposition layer)/barrier) was formed in the same manner as in Example 1 except that the thickness of the aluminum vapor deposition film (physical vapor deposition layer) was changed to 70 nm. A coat layer/aluminum vapor deposition film (physical vapor deposition layer) was obtained.

[Comparative Example 1]
A biaxially stretched polyethylene terephthalate (PET) film having a thickness of 12 μm was prepared as a base material layer. Subsequently, a glow discharge plasma generator was used on the PET film, and 1.0 slm of argon and a current of 20 A were applied to perform plasma treatment. Then, using aluminum as a raw material on the plasma-treated surface, the degree of vacuum in the vacuum chamber was set to 2×10 ⁻⁴ mbar and the degree of vacuum in the vapor deposition chamber was set to 2.0 by an electron beam heating vacuum deposition method. A 40 nm thick aluminum vapor deposition film (physical vapor deposition layer) was formed under the condition of ×10 ⁻² mbar to obtain a barrier film (layer structure: PET/aluminum vapor deposition film (physical vapor deposition layer)). ..

[Comparative example 2]
A biaxially stretched polyethylene terephthalate (PET) film having a thickness of 12 μm was prepared as a base material layer. Subsequently, a glow discharge plasma generator was used on the PET film, and 1.0 slm of argon and a current of 20 A were applied to perform plasma treatment. After that, aluminum is used as a raw material on the plasma-treated surface, and the degree of vacuum in the vacuum chamber is set to 2×10 ⁻⁴ mbar and the degree of vacuum in the vapor deposition chamber is set to 2. by an electron beam heating vacuum deposition method. Sublimation was performed under the condition of 0×10 ⁻² mbar and mixed with oxygen gas of 10 slm to form an aluminum oxide vapor deposition film (physical vapor deposition layer) having a thickness of 20 nm.

Next, a barrier coat layer was formed on the aluminum oxide vapor deposition film in the same manner as in Example 1.

Subsequently, a glow discharge plasma generator was used on the barrier coat layer to apply argon of 1.0 slm and current of 20 A to perform plasma treatment. After that, aluminum oxide was used as a raw material on the plasma-treated surface, and the degree of vacuum in the vacuum chamber was set to 2×10 ⁻⁴ mbar by the vacuum deposition method of the electron beam heating system, and the degree of vacuum in the deposition chamber was set to 2. It is sublimated under the condition of 0×10 ⁻² mbar and mixed with oxygen gas 10 slm to form a 20 nm thick aluminum oxide vapor deposition film (physical vapor deposition layer), and a barrier film (layer structure: PET/aluminum oxide). A vapor deposition film (physical vapor deposition layer)/barrier coat layer/aluminum oxide vapor deposition film (physical vapor deposition layer) was obtained.

[Comparative Example 3]
As the physical vapor deposition layer, a barrier film (layer structure: PET/silicon oxide vapor deposition film (chemical vapor deposition layer)) was formed in the same manner as in Example 1 except that an aluminum oxide vapor deposition film was formed instead of the aluminum vapor deposition film. /Barrier coat layer/aluminum oxide vapor deposition film (physical vapor deposition layer).

[Comparative Example 4]
As the physical vapor deposition layer, a barrier film (layer structure: PET/aluminum oxide vapor deposition film (physical vapor deposition layer)) was prepared in the same manner as in Comparative Example 2 except that an aluminum vapor deposition film was formed instead of the aluminum oxide vapor deposition film. /Barrier coat layer/aluminum vapor deposition film (physical vapor deposition layer).

<Performance evaluation of barrier film>
The following measurements were performed on the barrier films produced in the above Examples and Comparative Examples.

(Measurement of oxygen permeability)
Regarding the barrier film, under an environment of a temperature of 23° C. and a humidity of 90% RH, an oxygen permeability (cc/m ² ) was used in accordance with JIS K7126 using an oxygen permeability measuring device (MOCON: OX-TRAN). *Atm*day) was measured. The measurement results are shown in Table 2.

(Measurement of water vapor permeability)
Regarding the barrier film, under a temperature of 40° C. and a humidity of 100% RH, using a water vapor transmission rate measuring instrument (PERCON, manufactured by MOCON), in accordance with JIS K7129, the hot water vapor transmission rate (g/m ² · The day) was measured. The measurement results are shown in Table 2.

(Measurement of total light transmittance)
For the barrier film, the total light transmittance (%) was measured using a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K7361-1. The measurement results are shown in Table 2.

<Production of laminated film>
First, a main agent containing polyester as a main component, a curing agent containing an aliphatic polyisocyanate, and ethyl acetate are mixed so that a weight compounding ratio is main agent:curing agent:ethyl acetate=10:1:14. A liquid-curable polyester urethane adhesive was prepared.

Subsequently, the polyester urethane adhesive was used to bond the physical vapor deposition layer surface of the barrier film and the adherend (unstretched polypropylene film 70MC) to obtain a laminated film.

Further, the laminated film obtained above was stored for 120 hours in an environment of a temperature of 60° C. and a humidity of 90% RH.

(Evaluation of water resistant adhesion)
With respect to the laminated film obtained above and the laminated film stored in a high-humidity environment, sample pieces that were partially peeled off at the barrier film/adherent interface were prepared, respectively, and immersed in tap water for 1 minute. Then, using a tensile tester (Tensilon universal tester RTC1310A, manufactured by Orientec Co., Ltd.), T-shaped peeling was performed at a measurement speed of 50 mm/min to measure the water resistant adhesive strength (N/15 mm). The measurement results are shown in Table 2.

(Evaluation of laminated film)
The oxygen permeability, the water vapor permeability, and the total light transmittance of the laminate film obtained above and the laminate film after storage in a high humidity environment were measured in the same manner as the performance evaluation of the barrier film. The measurement results are shown in Table 2.

10 Barrier Film 11 Base Layer 12 Chemical Vapor Deposition Layer 13 Barrier Coat Layer 14 Physical Vapor Deposition Layer

Claims (11)

A barrier film comprising a base material layer, a chemical vapor deposition layer, a barrier coat layer, and a physical vapor deposition layer in this order,
The chemical vapor deposition layer is a silicon oxide vapor deposition film,
A barrier film in which the physical vapor deposition layer is an aluminum deposition film. The barrier film according to claim 1, wherein the base film is a biaxially stretched polyethylene terephthalate film. The barrier film according to claim 1, wherein the barrier coat layer is a resin cured film of a metal alkoxide and a water-soluble polymer. The barrier film according to claim 1 or 2, wherein the barrier coat layer is a cured resin film containing a reaction product obtained by reacting a metal oxide and a phosphorus compound. The barrier film according to claim 1, wherein the barrier coat layer is a resin cured film containing a carboxyl group-containing polymer crosslinked with a polyvalent metal compound. The acidity permeability measured in accordance with JIS K7126 method in an environment of a temperature of 23° C. and a humidity of 90% RH is 1.0 cc/m ² ·atm·day or less, and the method according to claim 1. The barrier film described in. The water vapor permeability measured in accordance with JIS K7129 method under an environment of a temperature of 40° C. and a humidity of 100% RH is 1.0 g/m ² ·day or less, according to claim 1. Barrier Fim. The barrier film according to any one of claims 1 to 7, which has a total light transmittance of 10% or less measured in accordance with JIS K7361. A moisture-proof sheet, comprising the barrier film according to claim 1. A heat insulating material comprising the barrier film according to claim 1. A packaging material comprising the barrier film according to claim 1.

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