JP2008143103A - Gas barrier laminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas barrier laminated film excellent in gas barrier properties and lamination strength. <P>SOLUTION: The gas barrier laminated film has a base material film 10, a vapor deposition film 20 of an inorganic oxide, a gas barrier coating film 30, an anchor coating layer 40, and a heat sealing layer 50 in this order. The gas barrier coating film 30 comprises a gas barrier composition containing an alkoxide, a polyvinyl alcohol-based resin and/or an ethylene/vinyl alcohol copolymer and obtained by polycondensation with a sol-gel method, and the anchor coating layer 40 comprises an anchor coating composition containing polyethyleneimine. Further, an adhesive resin layer is preferably provided between the anchor coating layer 40 and the heat sealing layer 50 and the heat sealing layer 50 is preferably composed of a thermally weldable polyolefinic resin. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a gas barrier laminate film, and more particularly to a gas barrier laminate film having excellent laminate strength and excellent gas barrier properties that prevent permeation of oxygen, water vapor, and the like.

  Conventionally, as packaging materials for filling and packaging foods, beverages, chemicals, miscellaneous goods, etc., various kinds of materials that block or block the transmission of oxygen gas, water vapor, etc. to prevent alteration, discoloration, etc. of the contents. Barrier laminates having the following form have been developed. In consideration of the fact that the metal foil remains as an incombustible material at the time of disposal, a gas barrier laminate material has been developed that allows the contents to be seen through without using a metal foil such as aluminum.

  For example, an inorganic oxide thin film layer is formed on at least one surface of a plastic film, a layer in which an anchor coating agent is mixed with a crosslinking agent is provided on the inorganic oxide thin film layer, and a heat sealable resin is further formed on the surface of the layer. (Patent Literature 1). The anchor coating agent is a mixture of a crosslinking agent, polyethyleneimine, and an epoxy compound. By mixing the epoxy compound, the anchor coating agent is excellent in gas barrier properties and excellent in laminate strength even when moisture is absorbed.

  Further, an inorganic oxide vapor deposition film is provided on one surface of the base film, and a primer agent layer made of a composition containing polyethyleneimine is further provided on the inorganic oxide vapor deposition film, and the primer agent is further provided. There is also a barrier film in which a heat-adhesive resin layer is provided on the layer (Patent Document 2). The invention prevents the occurrence of cracks or the like in the inorganic oxide vapor deposition film constituting the transparent barrier film, thereby ensuring gas barrier properties, preventing deterioration of contents, etc. and ensuring extremely high laminate strength. Therefore, the primer agent layer by the composition containing polyethyleneimine is provided.

Further, the protective layer surface of the transparent coating film in which the metal or metal compound thin film layer and the protective layer are sequentially formed on at least one surface of the polymer film substrate is bonded to the heat-sealable resin through a barrier adhesive. The protective layer is a coating layer comprising at least a hydrolyzate of metal alkoxide and a water-insoluble binder, and the barrier adhesive includes an unsaturated acid and There is also a barrier laminate using a cured film made of a polyamine derivative (Patent Document 3). According to the invention, gas, water vapor, and the like that pass through cracks and pinholes through the coated thin film layer and the protective layer are absorbed and blocked by the adhesive layer, so that higher barrier properties can be achieved.
JP 2001-138428 A JP 2002-166486 A JP 2000-25145 A

  However, a transparent barrier film in which a vapor deposition film of an inorganic oxide such as silicon oxide or aluminum oxide is provided on one surface of a base film is a non-flexible thin film in which the vapor deposition film of the inorganic oxide is a glassy material. Therefore, it lacks flexibility, and cracks and the like are likely to occur due to heat and pressure, and the barrier property may be lowered. This is the same not only when the film is manufactured, but also when a printed layer is further included at the time of lamination, or when making a bag or can using the gas barrier laminate film, depending on the external force at the time of lamination or bag making, etc. Cracks and the like are generated in the inorganic oxide vapor-deposited film, and the barrier property is lowered. In addition, the vapor deposition film of inorganic oxide is glassy and its surface is extremely inactive, and its wettability is extremely poor. It lacks strength and it is difficult to produce various desirable packaging containers. In this regard, as described in Patent Document 1 and Patent Document 2, when a primer agent layer is provided between the vapor-deposited film of the inorganic oxide and the heat-adhesive resin layer, the laminate strength can be improved. Furthermore, if the laminate strength can be improved and the gas barrier properties can be improved, the contents can be more effectively prevented from being altered.

  In addition, the gas barrier film can be molded into various bags, and the gas barrier property is maintained even when the film is more flexible if the film is flexible. In this regard, the film of Patent Document 3 is a barrier laminate using a cured film made of an unsaturated acid and a polyamine derivative, and the gas barrier properties are further improved if flexibility can be secured.

  Accordingly, an object of the present invention is to provide a gas barrier laminate film that has excellent barrier properties that prevent permeation of oxygen gas, water vapor, and the like, and that is excellent in laminate strength.

  As a result of examining the gas barrier laminate film in detail, the present inventor can impart gas barrier properties by forming an inorganic oxide vapor-deposited film on one surface of the base film, and a polyvinyl alcohol-based resin on the vapor-deposited thin film. When a gas barrier coating film comprising a metal alkoxide, a silane coupling agent or the like is provided, water resistance can be imparted, and an anchor coat comprising an anchor coat composition containing polyethyleneimine between the gas barrier coating film and the heat seal layer When a layer is provided, the adhesiveness can be improved while ensuring the flexibility between the gas barrier coating film and the heat seal layer, thereby finding that the gas barrier property can be further improved together with the improvement of the laminate strength, The present invention has been completed.

  The gas barrier laminated film of the present invention is obtained by laminating a gas barrier coating film on an inorganic oxide vapor-deposited film, and the gas barrier coating film comprises a polyvinyl alcohol resin or an ethylene / vinyl alcohol copolymer. One or more alkoxides chemically react with each other to form a very strong three-dimensional network composite polymer layer, so that it has excellent gas barrier properties and can prevent cracks and pinholes.

  In the gas barrier laminate film of the present invention, an anchor coat layer made of an anchor coat composition containing polyethyleneimine is laminated between the gas barrier coating film and the heat seal layer, and the laminate strength is improved by lamination by a melt extrusion method. The film has excellent flexibility.

The first of the present invention is a gas barrier laminate film having a base film, an inorganic oxide vapor deposition film, a gas barrier coating film, an anchor coat layer and a heat seal layer,
An inorganic oxide vapor deposition film is provided on the surface of the base film, and the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² are C represents an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents the valence of M.) Gas barrier coating with a gas barrier composition obtained by polycondensation by a sol-gel method, which contains at least one alkoxide represented by the formula (1) and a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. A gas barrier property, characterized in that a film is provided, an anchor coat layer comprising an anchor coat composition containing polyethyleneimine is provided on the gas barrier coating film, and a heat seal layer is laminated on the anchor coat layer. It is a layer film. Hereinafter, the present invention will be described in detail.

(1) Layer constitution of film As shown in FIG. 1 (a), the gas barrier laminate film of the present invention comprises a base film (10), an inorganic oxide vapor deposition film (20), and a gas barrier coating film (30). And an anchor coat layer (40) and a heat seal layer (50). Furthermore, as shown in FIG.1 (b), you may have a surface treatment layer (10 ') and (20') on a base film (10) and a vapor deposition film (20), respectively. Moreover, as shown in FIG.1 (c), you may have a printing layer (60) on the anchor coat layer (40) further. The print layer (60) may be full-surface printing or partial printing.

(2) Base film The base film that can be used in the present invention is excellent in chemical or physical strength, withstands the conditions for forming a vapor-deposited film of each inorganic oxide, and the inorganic oxide. It is possible to use a resin film that can be satisfactorily maintained without deteriorating film properties such as the deposited film. Specifically, for example, polyolefin resin such as polyethylene resin or polypropylene resin, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile ruptage-styrene copolymer ( ABS resins), poly (meth) acrylic resins, polycarbonate resins, polyvinyl alcohol resins, saponified ethylene-vinyl ester copolymers, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, and polyamides such as various nylons Various resin films such as resin, polyurethane resin, acetal resin, cellulose resin, and the like can be used. In the present invention, among the above resin films, it is particularly preferable to use a polyester resin, polyolefin resin, or polyamide resin film. As the base film, any of an unstretched film of the resin and a resin film stretched in a uniaxial direction or a biaxial direction can be used.

  In the present invention, as the above-mentioned various resin films, for example, one or more of the above-mentioned various resins are used, and an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method, etc. The above-mentioned film forming method is used to form a film of each of the above-mentioned various resins alone, or to form a multilayer co-extrusion film using two or more kinds of resins, Using the above resins, various resin films are manufactured by a method of forming a film by mixing before forming into a film, and if necessary, for example, a tenter method or a tubular method, etc. Various resin films that are stretched in a uniaxial or biaxial direction using the above can be used.

  In the present invention, the film thickness of various resin films is preferably about 6 to 2000 μm, more preferably about 9 to 100 μm.

  It should be noted that one or more of the above-mentioned various resins are used, and in forming the film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness Various plastic compounding agents and additives can be added for the purpose of improving and modifying mold release properties, flame retardancy, antifungal properties, electrical properties, strength, etc. Can be optionally added from a very small amount to several tens of percent depending on the purpose.

  In the above, as a general additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, and the like can be used. Furthermore, a modifying resin or the like can also be used.

(3) Surface treatment In this invention, although the vapor deposition film | membrane of an inorganic oxide is formed in one surface of said base film, you may surface-treat a base film previously. As a result, the adhesion with an inorganic oxide vapor deposition film or a gas barrier coating film can be improved. Similarly, surface treatment may be performed on the vapor deposition layer.

  Such surface treatments include corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc., and other pretreatments, etc. is there.

  In addition, a primer coating agent, an undercoat agent, a vapor deposition anchor coating agent, or the like can be optionally applied in advance to the surface of various films used in the present invention. Examples of the coating agent include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, polyolefins such as polyethylene or polypropylene. A resin composition containing a resin or a copolymer or modified resin thereof, a cellulose resin, or the like as a main component of the vehicle can be used.

  Among such surface treatments, it is particularly preferable to perform corona treatment or plasma treatment. For example, as plasma processing, there is plasma processing in which surface modification is performed using a plasma gas generated by ionizing a gas by arc discharge. In addition to the above, an inorganic gas such as oxygen gas, nitrogen gas, argon gas, helium gas can be used as the plasma gas. For example, immediately before forming a vapor-deposited film of an inorganic oxide by chemical vapor deposition, which will be described later, in-line plasma treatment removes moisture and dust from the surface of the base film and smoothes the surface. Surface treatment such as activation, etc. can be made possible. In addition, plasma treatment can be performed after vapor deposition to improve adhesion. In the present invention, as the plasma treatment, it is preferable to perform the plasma discharge treatment in consideration of the plasma output, the type of plasma gas, the supply amount of the plasma gas, the treatment time, and other conditions. Moreover, as a method for generating plasma, DC glow discharge, high frequency discharge, microwave discharge, and other devices can be used. In addition, plasma treatment can be performed by an atmospheric pressure plasma treatment method.

  In the present invention, the surface of the resin film other than the base film is also adhered to an inorganic oxide vapor-deposited film, a gas barrier coating film, a heat seal layer, a printed layer and other layers and films. In order to improve, any of the above surface treatments may be performed. For example, in the present invention, when the gas barrier coating film is formed on the inorganic oxide vapor-deposited film, the inorganic oxide vapor-deposited film is subjected to plasma treatment, and the gas barrier coating film is formed on the plasma-treated surface. Good. Moreover, when forming a printing layer on the said gas-barrier coating film, a plasma process may be previously performed to a gas-barrier coating film, and a printing layer may be formed.

(4) Inorganic oxide vapor-deposited film As the inorganic oxide vapor-deposited film, for example, a chemical vapor deposition method, a physical vapor deposition method, or a combination of these is used to form a single layer of an inorganic oxide vapor-deposited film. It can be produced by forming a layer film or a multilayer film or a composite film composed of two or more layers.

  Examples of the chemical vapor deposition method include chemical vapor deposition methods such as plasma chemical vapor deposition method, low temperature plasma chemical vapor deposition method, thermal chemical vapor deposition method, and photochemical vapor deposition method (Chemical Vapor Deposition method), CVD method). Specifically, a vapor deposition monomer gas such as an organosilicon compound is used as a raw material on one surface of a base film, and an inert gas such as argon gas or helium gas is used as a carrier gas. As described above, a vapor deposition film of an inorganic oxide such as silicon oxide can be formed by using a low temperature plasma chemical vapor deposition method using an oxygen gas or the like and using a low temperature plasma generator or the like.

  In the above, as a low temperature plasma generator, generators, such as high frequency plasma, pulse wave plasma, and microwave plasma, can be used, for example. In view of obtaining highly active and stable plasma, it is preferable to use a high-frequency plasma generator.

  An example of the formation method of the vapor deposition film | membrane of an inorganic oxide by said low temperature plasma chemical vapor deposition method is demonstrated using FIG. 2 which is a schematic block diagram of a low temperature plasma chemical vapor deposition apparatus.

  In the present invention, the base film 201 is fed out from the unwinding roll 223 disposed in the vacuum chamber 222 of the plasma chemical vapor deposition apparatus 221, and the base film 201 is further fed at a predetermined speed via the auxiliary roll 224. Then, it is conveyed onto the circumferential surface of the cooling / electrode drum 225. On the other hand, a gas mixture for vapor deposition is prepared by supplying vapor deposition monomer gas such as oxygen gas, inert gas, organosilicon compound, etc. from the gas supply devices 226, 227 and the raw material volatilization supply device 228, etc. Is introduced into the vacuum chamber 222 through the raw material supply nozzle 229. The vapor deposition mixed gas composition is supplied onto the substrate film 201 transported on the circumferential surface of the cooling / electrode drum 225, and is generated and irradiated with glow discharge plasma 230 to generate an inorganic oxide such as silicon oxide. The deposited film is formed. Next, if the base film 201 on which the inorganic oxide vapor deposition film such as silicon oxide is formed is wound on the take-up roll 234 via the auxiliary roll 233, the inorganic oxide vapor deposition film by the plasma chemical vapor deposition method is used. Can be formed. A predetermined power is applied to the cooling / electrode drum 225 from a power source 231 disposed outside the vacuum chamber 222, and a magnet 232 is disposed in the vicinity of the cooling / electrode drum 225 to promote plasma generation. Has been. Since a predetermined voltage is applied from the power source to the cooling / electrode drum in this way, glow discharge plasma is generated in the vicinity of the opening of the raw material supply nozzle in the vacuum chamber and the cooling / electrode drum. This glow discharge plasma is derived from one or more gas components in the mixed gas. When the substrate film is conveyed at a constant speed in this state, the glow discharge plasma causes the cooling / electrode drum surface to be A deposited film of an inorganic oxide such as silicon oxide can be formed on the base film. In FIG. 2, reference numeral 235 represents a vacuum pump.

In the present invention, the vacuum chamber is depressurized by a vacuum pump and adjusted to a vacuum degree of 1 × 10 ⁻¹ to 1 × 10 ⁻⁸ Torr, preferably a vacuum degree of 1 × 10 ⁻³ to 1 × 10 ⁻⁷ Torr. It is preferable to do.

The raw material volatilization supply device volatilizes the organic silicon compound as the raw material, mixes it with oxygen gas, inert gas, etc. supplied from the gas supply device, and introduces this mixed gas into the vacuum chamber through the raw material supply nozzle. . At this time, the content of the organosilicon compound in the mixed gas is preferably 1 to 40%, the oxygen gas content is 10 to 70%, and the inert gas content is preferably 10 to 60%. For example, the mixing ratio of organosilicon compound: oxygen gas: inert gas can be about 1: 6: 5 to 1:17:14. Note that the degree of vacuum in the vacuum chamber when supplying the organosilicon compound, the inert gas, the oxygen gas, and the like is 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr is preferable, and the conveying speed of the base film is 10 to 300 m / min, preferably 50 to 150 m / min. Formation of a vapor-deposited film of an inorganic oxide such as silicon oxide obtained in this way is formed on a base film in the form of a thin film in the form of SiO _x while oxidizing the plasma source gas with oxygen gas. Therefore, the deposited film of inorganic oxide such as silicon oxide is a continuous layer that is dense, has few gaps, and is flexible. Accordingly, the barrier property of the deposited film of inorganic oxide such as silicon oxide is It is much higher than a vapor deposition film of an inorganic oxide such as silicon oxide formed by a conventional vacuum vapor deposition method, and a sufficient barrier property can be obtained with a thin film thickness. Moreover, since the surface of the base film is cleaned by SiO _x plasma, and polar groups, free radicals, etc. are generated on the surface of the base film, the deposited film of inorganic oxide such as silicon oxide and the base material are formed. The tight adhesion with the film is high. Further, the degree of vacuum when forming a continuous film of an inorganic oxide such as silicon oxide is 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr. Since the vacuum degree when forming a deposited film of an inorganic oxide such as silicon oxide by the conventional vacuum deposition method is lower than 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Torr, It is possible to shorten the vacuum state setting time at the time of replacing the raw material film, and the degree of vacuum is easily stabilized, and the film forming process is also stabilized.

In the present invention, a vapor deposition film of silicon oxide formed using a vapor deposition monomer gas such as an organosilicon compound chemically reacts with a vapor deposition monomer gas such as an organosilicon compound and oxygen gas, and the reaction product is It is closely bonded to one surface of a base film to form a dense thin film having high flexibility, and is usually represented by the general formula SiO _x (where X represents a number from 0 to 2). It is a continuous thin film mainly composed of silicon oxide. The silicon oxide vapor deposition film is a silicon oxide vapor deposition represented by the general formula SiO _x (where X represents a number from 1.3 to 1.9) in terms of transparency and barrier properties. A thin film mainly composed of a film is preferable. The value of X varies depending on the molar ratio of vapor deposition monomer gas and oxygen gas, plasma energy, etc. Generally, the gas permeability decreases as the value of X decreases, but the film itself is yellow. The transparency becomes worse.

In the present invention, the silicon oxide vapor-deposited film is mainly composed of silicon oxide, and further contains at least one compound of carbon, hydrogen, silicon or oxygen, or a compound composed of two or more elements by chemical bonding or the like. It consists of a vapor deposition film. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained by a chemical bond or the like. Examples thereof include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl and SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol. In addition to the above, the type, amount, etc. of the compound contained in the silicon oxide vapor deposition film can be varied by changing the conditions of the vapor deposition process. In this case, the content of the above-mentioned compound in the deposited film of silicon oxide is 0.1 to 50% by mass, preferably 5 to 20% by mass. When the content is less than 0.1% by mass, the impact resistance, spreadability, flexibility, etc. of the deposited silicon oxide film are insufficient, and scratches, cracks, etc. are likely to occur due to bending, etc., and high barrier properties. May be difficult to maintain stably, and on the other hand, if it exceeds 50% by mass, the barrier property may be lowered.

  Further, in the present invention, in the silicon oxide vapor-deposited film, it is preferable that the content of the above compound decreases in the depth direction from the surface of the silicon oxide vapor-deposited film. As a result, the impact resistance and the like are enhanced by the above compound on the surface of the silicon oxide vapor deposition film, and on the other hand, since the content of the above compound is small at the interface with the base film, the vapor deposition of the base film and the silicon oxide is performed. The tight adhesion with the film becomes strong.

  In the present invention, the above-described vapor deposition film of silicon oxide uses, for example, a surface analyzer such as an X-ray photoelectron spectrometer (Xray), a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS), or the like. The above-mentioned physical properties can be confirmed by performing analysis such as ion etching in the vertical direction and performing elemental analysis of the deposited film of silicon oxide.

  In the present invention, the thickness of the silicon oxide vapor-deposited film is preferably about 50 to 4000 mm, more preferably 100 to 1000 mm. If it is thicker than 4000 mm, cracks or the like may occur in the film. On the other hand, if it is less than 50 mm, it may be difficult to achieve a barrier effect. The film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Corporation. As a means for changing the film thickness of the silicon oxide vapor deposition film, a method of increasing the volume velocity of the vapor deposition film, that is, a method of increasing the amount of monomer gas and oxygen gas, a method of slowing the vapor deposition rate, etc. be able to.

  In the present invention, the inorganic oxide vapor-deposited film may be not only one layer of the inorganic oxide vapor-deposited film but also a multilayer film in which two or more layers are laminated, and one or two materials are used. It is also possible to form a vapor-deposited film of an inorganic oxide that is used as a mixture of seeds or more and mixed with different materials.

  In the present invention, as a monomer gas for vapor deposition of an organic silicon compound or the like that forms a vapor deposition film of an inorganic oxide such as silicon oxide, for example, 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyl Trimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane , Methyltriethoxysilane, octamethylcyclotetrasiloxane, and the like 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.

  On the other hand, in the present invention, an inorganic oxide vapor-deposited film can also be formed by physical vapor deposition. As such a physical vapor deposition method, for example, an inorganic oxide can be formed by a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum deposition method, a sputtering method, an ion plating method, or an ion cluster beam method. A vapor deposition film can be formed.

  Specifically, a metal or metal oxide is used as a raw material, this is heated and vaporized, and this is vapor-deposited on one of the base films, or a metal or metal oxide as a raw material. Used to oxidize by introducing oxygen and oxidize and deposit on one side of the base film, and further use plasma-assisted oxidation reaction deposition method that promotes oxidation reaction with plasma to form a deposited film can do. In addition, 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. A method of forming a thin film of an inorganic oxide by physical vapor deposition will be described with reference to FIG. 3 showing a schematic configuration diagram showing an example of a take-up vacuum deposition apparatus.

  First, the base film 201 fed out from the unwinding roll 243 is guided to the cooled coating drum 246 through the guide rolls 244 and 245 in the vacuum chamber 242 of the wind-up type vacuum evaporation apparatus 241. The evaporation source 248 heated by the crucible 247, for example, metal aluminum or aluminum oxide is evaporated on the substrate film 201 guided on the cooled coating drum 246, and if necessary, While an oxygen gas or the like is ejected from the oxygen gas outlet 249 and supplied, an inorganic oxide vapor deposition film such as aluminum oxide is formed through the masks 250 and 250. When the base film 201 on which an inorganic oxide vapor deposition film such as aluminum oxide is formed is sent out through the guide rolls 251 and 252 and wound around the take-up roll 253, the inorganic oxide vapor deposition film is formed by physical vapor deposition. Can be formed. In addition, using the above-described winding-type vacuum vapor deposition apparatus, first, a first-layer inorganic oxide vapor-deposited film is formed, and then an inorganic oxide vapor-deposited film is further formed thereon, or A vacuum evaporation apparatus may be connected in series, and an inorganic oxide vapor deposition film may be continuously formed to form an inorganic oxide vapor deposition film composed of a multilayer film of two or more layers.

The vapor deposition film of metal or inorganic oxide may basically be a thin film on which a metal oxide is deposited, for example, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca). , Vapor deposition films of metal oxides such as potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) Can be used. Preferably, a vapor-deposited film of a metal oxide such as silicon (Si) or aluminum (Al) can be used. Therefore, the metal oxide vapor deposition film can be referred to as a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide, and the like, for example, SiO _x , AlO _x , MgO. MO _X (in the formula, M represents a metal element, the value of X is in the range respectively of a metal element different.) as _X, etc. represented by.

  In addition, as the range of the value of X, silicon (Si) exceeds 0 and 2 or less, aluminum (Al) exceeds 0 and 1.5 or less, magnesium (Mg) exceeds 0 and 1 or less, calcium (Ca ) Is greater than 0 and less than or equal to 1, potassium (K) is greater than 0 and less than or equal to 0.5, tin (Sn) is greater than 0 and less than or equal to 2, sodium (Na) is greater than 0 and less than or equal to 0.5, and boron (B) is 0 to 1, 5 or less, Titanium (Ti) is more than 0 to 2 or less, Lead (Pb) is more than 0 to 1 or less, Zirconium (Zr) is more than 0 to 2 or less, Yttrium (Y) is more than 0 to 1 .5 or less. In the above, when X = 0, it is a complete metal, and the upper limit of the range of X is a completely oxidized value. In the present invention, silicon and aluminum are preferable as M, and the values of these X are in the range of 1.0 to 2.0 for silicon (Si) and 0.5 to 1.5 for aluminum (Al). . In addition, although the film thickness of the vapor deposition film | membrane of an inorganic oxide changes with kinds etc. of the metal to be used or a metal oxide, it can select arbitrarily within the range of 50-2000 mm, for example, Preferably, it is 100-1000 mm. it can. In addition, as the inorganic oxide vapor deposition film, the metal or metal oxide to be used is used in one kind or a mixture of two or more kinds to constitute a vapor deposition film of an inorganic oxide mixed with different materials. You can also.

  Further, in the present invention, for example, a composite film composed of two or more vapor-deposited films of different kinds of inorganic oxides can be formed by using both physical vapor deposition and chemical vapor deposition.

  As a composite film composed of two or more layers of the above-mentioned different kinds of inorganic oxide vapor-deposited films, first, a chemical vapor deposition method is used on a base film, and it is dense and flexible, and relatively cracks are generated. An inorganic oxide vapor-deposited film that can prevent the formation of an inorganic oxide, and then an inorganic oxide vapor-deposited film formed by physical vapor deposition on the inorganic oxide vapor-deposited film. It is preferable to constitute an inorganic oxide vapor deposition film. Contrary to the above, on the base film, first, a vapor deposition film of an inorganic oxide is provided by a physical vapor deposition method, and then dense and flexible by a chemical vapor deposition method. It is also possible to provide an inorganic oxide vapor deposition film composed of a composite film composed of two or more layers by providing an inorganic oxide vapor deposition film that can relatively prevent the occurrence of cracks.

(5) Gas barrier coating film The gas barrier coating film used in the present invention has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² are organic having 1 to 8 carbon atoms). Represents a group, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M. Contains the above alkoxide, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, and polycondensation by sol-gel method in the presence of sol-gel method catalyst, acid, water, and organic solvent A coating film made of a gas barrier composition formed by coating the composition on the inorganic oxide vapor-deposited film on the substrate film layer to provide a coating film, 30 seconds to 10 seconds at a temperature below the melting point of the base film layer It can be formed by between heat treatment.

  Further, the gas barrier composition is coated on the inorganic oxide vapor-deposited film on the base film layer, and two or more coating films are stacked, and the base film layer has a temperature of 20 to 180 ° C. A composite polymer layer in which two or more gas barrier coating films are stacked may be formed by heat treatment at a temperature equal to or lower than the melting point of 30 seconds to 10 minutes.

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

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

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

In the present invention, silicon is preferable. In this case, as an alkoxide that can be preferably used in the present invention, when n = 0 in the general formula R ¹ _n M (OR ² ) _m , the general formula Si (ORa) ₄ (wherein Ra is Represents an alkyl group having 1 to 5 carbon atoms). In the above, Ra includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and the like. Specific examples of such an alkoxysilane include tetramethoxysilane Si (OCH ₃ ) ₄ , tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane Si (0C ₃ H ₇ ) ₄ , tetrabutoxysilane Si ( OC ₄ H ₉₎ can be exemplified ₄ like.

In the case where n is 1 or more, the general formula RbnSi (ORc) _4-m (wherein m represents an integer of 1, 2, 3 and Rb and Rc are a methyl group, an ethyl group, An alkylalkoxysilane represented by n-propyl group, n-butyl group, etc.) can be used. Examples of such an alkylalkoxysilane include methyltrimethoxysilane CH ₃ Si (OCH ₃ ) ₃ , methyltriethoxysilane CH ₃ Si (OC ₂ H ₅ ) ₃ , dimethyldimethoxysilane (CH ₃ ) ₂ Si (OCH). _{3) 2,} dimethyl diethoxy silane _{(CH 3) 2 Si (OC} 2 H 5) 2, may use other like. In the present invention, the above alkoxysilane, alkylalkoxysilane and the like may be used alone or in combination of two or more.

  In the present invention, a polycondensation product of the above alkoxysilane can also be used, and specifically, for example, polytetramethoxysilane, polytetraemethoxysilane, and the like 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 general formula R ¹ _n M (OR ² ) _m . For example, tetramethoxy zirconium Zr (OCH _{3) 4,} tetraethoxy zirconium _{Zr (OC 2 H 5) 4} , tetra i propoxy zirconium _{Zr (iso-0C 3 H 7} ) 4, tetra-n-butoxy zirconium Zr (OC ₄ H _{9) 4} , etc. can be exemplified.

Further, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , a titanium alkoxide in which M is Ti can be preferably used. For example, tetramethoxytitanium Ti (OCH ₃ ) ₄ , tetra Examples thereof include ethoxytitanium Ti (OC ₂ H ₅ ) ₄ , tetraisopropoxytitanium Ti (iso-0C ₃ H ₇ ) ₄ , tetra n-butoxytitanium Ti (OC ₄ H ₉ ) ₄ , and the like.

As the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , an aluminum alkoxide in which M is Al can be used. For example, tetramethoxyaluminum Al (OCH ₃ ) ₄ , tetraethoxyaluminum _{Al (OC 2 H 5) 4} , tetraisopropoxy aluminum _{Al (is0-OC 3 H 7} ) 4, tetra-n-butoxy aluminum _{Al (OC 4 H 9) 4} , may use other like.

  In the present invention, two or more of the alkoxides may be used in combination. For example, when alkoxysilane and zirconium alkoxide are mixed and used, the toughness, heat resistance and the like of the resulting gas barrier laminate film can be improved, and a decrease in the retort resistance of the film during stretching can be avoided. Under the present circumstances, the usage-amount of a zirconium alkoxide is the range of 10 mass parts or less with respect to 100 mass parts of said alkoxysilanes. When the amount exceeds 10 parts by mass, the formed gas barrier coating film tends to gel, and the brittleness of the film increases, and the gas barrier coating film tends to peel off when the base film layer is coated. Therefore, it is not preferable.

  In addition, when alkoxysilane and titanium alkoxide are mixed and used, the thermal conductivity of the resulting gas barrier coating film is lowered, and the heat resistance is remarkably improved. Under the present circumstances, the usage-amount of a titanium alkoxide is the range of 5 mass parts or less with respect to 100 mass parts of said alkoxysilane. When the amount exceeds 5 parts by mass, the brittleness of the formed gas barrier coating film increases, and the gas barrier coating film may be easily peeled off when the base film layer is coated.

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

  When the polyvinyl alcohol resin and the ethylene / vinyl alcohol copolymer are used in combination, the blending ratio of each is polyvinyl alcohol resin: ethylene / vinyl alcohol copolymer = 10: 0. It is preferable that the position is from 05 to 10: 6.

  The content of the polyvinyl alcohol resin and / or the ethylene / vinyl alcohol copolymer is in the range of 5 to 500 parts by mass, preferably 20 to 200 parts by mass with respect to 100 parts by mass of the total amount of the alkoxide. The blending ratio of If it exceeds 500 parts by mass, the brittleness of the gas barrier coating film increases, and the water resistance and weather resistance of the resulting gas barrier laminated film may be lowered. On the other hand, if it is less than 5 parts by mass, the gas barrier property may be lowered.

  In the polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, as the polyvinyl alcohol resin, one obtained by saponifying polyvinyl acetate can be generally used. Polyvinyl alcohol resins include partially saponified polyvinyl alcohol resins in which several tens of percent of acetate groups remain, completely saponified polyvinyl alcohols in which no acetate groups remain, and modified polyvinyl alcohol resins in which OH groups have been modified. Well, not particularly limited. Examples of such a polyvinyl alcohol resin include “RS-110 (degree of saponification = 99%, degree of polymerization = 1,000)” manufactured by Kuraray Co., Ltd., and “Kuraray Poval LM-20SO ( “Saponification degree = 40%, polymerization degree = 2,000)”, “GOHSENOL NM-14 (degree of saponification = 99%, polymerization degree = 1,400)” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. Can do.

  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, it is not particularly limited, and includes a partially saponified product in which several tens mol% of acetic acid groups remain to a complete saponified product in which only several mol% of acetic acid groups remain or no acetic acid groups remain. However, it is preferable to use a saponification degree that is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties. In addition, the content of the repeating unit 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. Examples of such an ethylene / vinyl alcohol copolymer include “Eval EP-F101 (ethylene content; 32 mol%)” manufactured by Kuraray Co., Ltd., “Soarnol D2908 (ethylene content; 29 mol) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.” %) "And the like.

The gas barrier composition used in the present invention has 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 is Represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M.) And a polycondensation by a sol-gel method in the presence of a sol-gel method catalyst, acid, water, and an organic solvent. Gas barrier composition. In preparing the gas barrier composition, a silane coupling agent or the like may be added.

  As the silane coupling agent that can be suitably used in the present invention, known organic reactive group-containing organoalkoxysilanes can be widely used. For example, an organoalkoxysilane having an epoxy group is suitable. For example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or β- (3,4-epoxy). (Cyclohexyl) ethyltrimethoxysilane or the like can be used. Such silane coupling agents may be used alone or in combination of two or more. In addition, the usage-amount of a silane coupling agent exists in the range of 1-20 mass parts with respect to 100 mass parts of said alkoxysilanes. If 20 parts by mass or more is used, the gas barrier coating film to be formed has increased rigidity and brittleness, and the insulation and workability of the gas barrier coating film may be lowered.

  The sol-gel catalyst is a catalyst mainly used as a polycondensation catalyst, and a basic substance such as a tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used. . For example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine, etc. can be used. In the present invention, N, N-dimethylbenzylamine is particularly preferred. The usage-amount is 0.01-1.0 mass part per 100 mass parts of total amounts of an alkoxide and a silane coupling agent.

  The “acid” used in the gas barrier composition is mainly used as a catalyst for hydrolysis of an alkoxide, a silane coupling agent or the like in the sol-gel method. For example, mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid, organic acids such as acetic acid and tartaric acid, and the like can be used. The amount of the acid used is preferably 0.001 to 0.05 mol based on the total molar amount of the alkoxide and the alkoxide content of the silane coupling agent (for example, silicate moiety).

  Furthermore, in the gas barrier composition, water can be used in a proportion of 0.1 to 100 mol, preferably 0.8 to 2 mol, relative to 1 mol of the total molar amount of the alkoxide. When the amount of water exceeds 2 mol, the polymer obtained from the alkoxysilane and the metal alkoxide becomes spherical particles, and the spherical particles are three-dimensionally crosslinked to form a porous polymer having a low density, Such a porous polymer cannot improve the gas barrier property of the gas barrier laminate film. Moreover, when the amount of the water is less than 0.8 mol, the hydrolysis reaction may hardly proceed.

  Furthermore, as an organic solvent used in said gas-barrier composition, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol, etc. can be used, for example. The polyvinyl alcohol-based resin and / or the ethylene / vinyl alcohol copolymer is preferably handled in a state of being dissolved in a coating solution containing the alkoxide, silane coupling agent, or the like. It can be selected appropriately. For example, when a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer are used in combination, it is preferable to use n-butanol. An ethylene / vinyl alcohol copolymer solubilized in a solvent can also be used. For example, trade name “Soarnol” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. can be preferably used. The amount of the organic solvent used is usually 30 with respect to 100 mass of the total amount of the alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, acid and sol-gel method catalyst. It is -500 mass parts.

  In the present invention, an inorganic oxide vapor deposition layer is provided on a base film, and a gas barrier coating film can be formed by the following method.

  First, an alkoxide such as alkoxysilane, a silane coupling agent, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, a sol-gel method catalyst, an acid, water, an organic solvent, and, if necessary, A metal alkoxide or the like is mixed to prepare a gas barrier composition. By mixing, the gas barrier composition (coating liquid) starts and proceeds with a polycondensation reaction.

  On the inorganic oxide vapor deposition film on the base film layer, the above gas barrier composition is applied and dried by a conventional method. By this drying step, polycondensation of the alkoxide such as alkoxysilane, metal alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer further proceeds, and a coating film is formed. . On the first coating film, the above coating operation may be further repeated to form a plurality of coating films composed of two or more layers.

  Next, the base film layer to which the gas barrier composition is applied is 20 ° C. to 180 ° C. and a temperature not higher than the melting point of the base film layer, preferably at a temperature in the range of 50 ° C. to 160 ° C. for 10 seconds to 10 seconds. Heat for minutes. One or more gas barrier coating films of the gas barrier composition may be formed on the inorganic oxide vapor-deposited film.

  A gas barrier laminate film obtained using an ethylene / vinyl alcohol copolymer alone or both a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer is excellent in gas barrier properties after hydrothermal treatment. On the other hand, when a gas barrier laminate film is produced using only a polyvinyl alcohol-based resin, a first coating film is formed by previously applying a gas barrier composition using a polyvinyl alcohol-based resin, A gas barrier composition containing an ethylene / vinyl alcohol copolymer is applied onto the coating film to form a second coating film, and a composite layer thereof is formed. Can be improved.

  Further, a coating film is formed by the gas barrier composition containing the ethylene / vinyl alcohol copolymer, or the gas barrier composition containing a combination of the polyvinyl alcohol resin and the ethylene / vinyl alcohol copolymer is applied. Even if a film is formed and a plurality of these films are laminated, it becomes an effective means for improving the gas barrier property of the gas barrier laminated film according to the present invention.

  The production method of the gas barrier laminate film used in the present invention will be described in more detail using alkoxysilane as the alkoxide.

  The alkoxysilane and metal alkoxide blended as the gas barrier composition are hydrolyzed by the added water. During the hydrolysis, the acid acts as a hydrolysis catalyst. Next, protons are taken from the hydroxyl groups generated by hydrolysis by the action of the sol-gel method catalyst, and the hydrolyzed products undergo dehydration polycondensation. At this time, the silane coupling agent is simultaneously hydrolyzed by the acid catalyst, and the alkoxy group becomes a hydroxyl group.

  In addition, the opening of the epoxy group also occurs due to the action of the base catalyst, generating a hydroxyl group. In addition, a polycondensation reaction between the hydrolyzed silane coupling agent and the hydrolyzed alkoxide also proceeds. In the reaction system, polyvinyl alcohol resin, ethylene / vinyl alcohol copolymer, or polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer are present, so polyvinyl alcohol resin and ethylene / vinyl alcohol copolymer are present. Reaction with the hydroxyl group of the polymer also occurs. In addition, the polycondensate to be generated includes, for example, an inorganic part composed of a bond such as Si—O—Si, Si—O—Zr, Si—O—Ti, and the like, and an organic part resulting from the silane coupling agent. It is a composite polymer containing.

  In the above reaction, for example, a linear polymer having a partial structural formula represented by the following formula (III) and further having a portion derived from a silane coupling agent is first formed.

このポリマーは、ＯＲ基（エトキシ基などのアルコキシ基）を、直鎖状のポリマーから分岐した形で有する。このＯＲ基は、存在する酸が触媒となって加水分解されてＯＨ基となり、ゾル−ゲル法触媒（塩基触媒）の働きにより、まず、ＯＨ基が、脱プロトン化し、次いで、重縮合が進行する。すなわち、このＯＨ基が、下記の式（Ｉ）に示されるポリビニルアルコール系樹脂、または、下記の式（ＩＩ）に示されるエチレン・ビニルアルコール共重合体と重縮合反応し、Ｓｉ−Ｏ−Ｓｉ結合を有する、例えば、下記の式（ＩＶ）に示される複合ポリマー、あるいは、下記の式（Ｖ）及び（ＶＩ）に示される共重合した複合ポリマーを生じると考えられる。

This polymer has an OR group (an alkoxy group such as an ethoxy group) branched from a linear polymer. This OR group is hydrolyzed to become an OH group using the existing acid as a catalyst. The OH group is first deprotonated by the action of a sol-gel method catalyst (base catalyst), and then polycondensation proceeds. To do. That is, this OH group undergoes a polycondensation reaction with a polyvinyl alcohol-based resin represented by the following formula (I) or an ethylene / vinyl alcohol copolymer represented by the following formula (II) to form Si—O—Si. For example, it is considered that a composite polymer represented by the following formula (IV) or a copolymerized composite polymer represented by the following formulas (V) and (VI) is formed.

上記の反応は常温で進行し、ガスバリア性組成物は、調製中に粘度が増加する。このガスバリア性組成物を、基材フィルム層上の無機酸化物の蒸着膜の上に塗布し、加熱して溶媒および重縮合反応により生成したアルコールを除去すると重縮合反応が完結し、基材フィルム層上の無機酸化物の蒸着膜の上に透明な塗布膜が形成される。なお、上記の塗布膜を複数層積層する場合には、層間の塗布膜中の複合ポリマー同士も縮合し、層と層との間が強固に結合する。

The above reaction proceeds at room temperature, and the viscosity of the gas barrier composition increases during preparation. When this gas barrier composition is applied onto an inorganic oxide vapor-deposited film on a base film layer and heated to remove the solvent and the alcohol produced by the polycondensation reaction, the polycondensation reaction is completed, and the base film A transparent coating film is formed on the inorganic oxide vapor deposition film on the layer. In addition, when laminating | stacking two or more said coating films, the composite polymer in the coating film of an interlayer is also condensed, and a layer couple | bonds firmly between layers.

  Furthermore, the organic reactive group of the silane coupling agent and the hydroxyl group generated by hydrolysis are bonded to the hydroxyl group on the surface of the base film layer, or the deposited film of the inorganic oxide on the base film layer, The adhesion between the base film layer or the surface of the inorganic oxide vapor deposition film and the coating film is also good. Thus, in the present invention, the inorganic oxide vapor-deposited film and the gas barrier coating film form, for example, a chemical bond, a hydrogen bond, or a coordinate bond by hydrolysis / co-condensation reaction. Adhesion between the oxide vapor deposition film and the gas barrier coating film is improved, and a better gas barrier effect can be exhibited by the synergistic effect of the two layers.

In the present invention, when the amount of water added is adjusted to 0.8 to 2 mol, preferably 1.0 to 1.7 mol, relative to 1 mol of alkoxides, the above linear polymer is used. Is formed. Such a linear polymer has crystallinity and has a structure in which a large number of minute crystals are embedded in an amorphous part. Such a crystal structure is the same as that of a crystalline organic polymer (for example, vinylidene chloride or polyvinyl alcohol), and a polar group (OH group) is partially present in the molecule, and the molecular aggregation energy is high. Since the rigidity is also high, it is particularly excellent in gas barrier properties (blocking and blocking permeation of O ₂ , N ₂ , H ₂ O, CO ₂ , etc.). In particular, when used for so-called gas-filled packaging filled with N ₂ , CO ₂ gas or the like, the excellent gas barrier property is extremely effective for holding the filled gas. Thereby, the gas barrier laminate film according to the present invention is excellent in hot water treatment, particularly high pressure hot water treatment (retort treatment), and exhibits extremely excellent gas barrier properties.

  Examples of the method for applying the gas barrier composition of the present invention include, for example, once by a roll coater such as a gravure roll coater, spray coat, spin coat, dipping, brush, bar code, applicator or the like. A coating film having a dry film thickness of 0.01 to 30 μm, preferably about 0.1 to 10 μm, can be formed by applying a plurality of times. Further, under a normal environment, 50 to 300 ° C., preferably The gas barrier coating film of the present invention is formed by performing condensation at a temperature of 70 to 200 ° C. by heating and drying for 0.005 to 60 minutes, preferably 0.01 to 10 minutes. Can do.

(6) Anchor coat layer In the present invention, an anchor coat layer made of an anchor coat composition containing polyethyleneimine is laminated on the gas barrier coating film.

  Polyethyleneimine is synthesized, for example, by ring-opening polymerization of ethyleneimine in the presence of an acid catalyst. In general, primary, secondary and tertiary amines are 1: 2: 1 derived from the reactivity of active hydrogen atoms on the nitrogen atoms contained, rather than a perfect linear polymer as shown by the formula Having a branched structure. In the present invention, a polymer compound containing such a branched structure can be preferably used. Thereby, it can couple | bond with the reactive group contained in the said gas-barrier coating film, and can adhere | attach a gas-barrier coating film and a heat seal layer closely | flexibly and closely.

したがって、本発明で使用するポリエチレンイミンとしては、エチレンイミンの重合体であって、反応性に優れる活性水素に、１級、２級、３級アミンが結合し、これによってラミネート強度を高め得るものであれば、その構造に制限はない。また、そのようなポリエチレンイミンであれば、市販品を使用することもできる。このような市販品としては、日本触媒株式会社製、商品名「エポミン（登録商標）」、東洋モートン社製、商品名「ＡＤ３７２ＭＷ」、大日精化社製、商品名「セカダイン４１００」、等がある。本発明において、上記のようなポリエチレンイミンを使用することにより、ガスバリア性塗布膜とヒートシール層との密接着性等を向上させ、ラミネート加工、あるいは、製函加工等の後加工適性を向上させ、後加工時における無機酸化物の蒸着膜のクラック等の発生を防止することができる。

Therefore, the polyethyleneimine used in the present invention is a polymer of ethyleneimine, and primary, secondary, and tertiary amines are bonded to active hydrogen that is excellent in reactivity, thereby increasing the laminate strength. If so, the structure is not limited. Moreover, if it is such a polyethyleneimine, a commercial item can also be used. Examples of such commercially available products include Nippon Shokubai Co., Ltd., trade name “Epomin (registered trademark)”, Toyo Morton, trade name “AD372MW”, Dainichi Seika Co., Ltd., trade name “SECADINE 4100”, and the like. is there. In the present invention, by using the polyethyleneimine as described above, the tight adhesion between the gas barrier coating film and the heat seal layer is improved, and the post-processing suitability such as laminating or box making is improved. Further, it is possible to prevent the occurrence of cracks or the like in the deposited film of the inorganic oxide during post-processing.

  The anchor coating agent may further contain other components as long as it has polyethyleneimine as a main component. As an anchor coating agent, for example, for polyethyleneimine 1 to 30% by mass, an additive such as a stabilizer, a curing agent, a crosslinking agent, a lubricant, an ultraviolet absorber, and the like is optionally added, and a solvent, An aqueous composition may be prepared by adding a diluent and mixing well. Specifically, the main component is polyethyleneimine, and the silane coupling agent is 0.05 to 10% by mass, preferably 0.1% to 5% by mass with respect to 1 to 30% by mass of the polyethyleneimine. %, 0.1 to 20% by weight, preferably 1 to 10% by weight, and, if necessary, stabilizers, curing agents, crosslinking agents, lubricants, ultraviolet absorbers, etc. A solution prepared by adding an additive arbitrarily, adding a solvent, a diluent and the like and mixing them well to prepare an aqueous composition can be suitably used.

  As the silane coupling agent that can be blended in the composition, organic functional silane monomers having binary reactivity can be used. For example, γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxy Silane, vinyl-tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxy Silane, γ-mercaptopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, Bis (β-hydroxy Chill)-.gamma.-aminopropyltriethoxysilane, .gamma.-aminopropyl silicone - can be used one or more of such aqueous emissions.

  Examples of the filler that can be blended include calcium carbonate, barium sulfate, alumina white, silica, talc, glass frit, resin powder, and the like. Thus, the above-mentioned filler adjusts the viscosity of the above-described composition liquid, improves its coating suitability, and binds with polyethyleneimine via a silane coupling agent to improve the cohesive strength of the coating film. Is.

  In the present invention, as an anchor coating agent, if necessary, for example, polyurethane resin, polyester resin, polyamide resin, epoxy resin, phenol resin, (meth) acrylic resin, polyvinyl acetate resin, polyethylene or A composition may be prepared by arbitrarily adding one or more of polyolefin resins such as polypropylene or copolymers or modified resins thereof, cellulose resins, and the like.

  The solvent that dissolves the anchor coating agent may be any solvent that can dissolve the anchor coating agent, and an organic solvent, an aqueous solvent, or the like can be used alone or as a mixed solution.

The composition is coated on the gas barrier coating film by, for example, roll coating, gravure coating, knife coating, dip coating, spray coating, or other coating methods, and then the coating film is dried to form a solvent. The anchor coat layer according to the present invention may be formed by removing the diluent and the like, and further performing an aging treatment if necessary. In the present invention, the thickness of the anchor coat layer is preferably, for example, 0.1 to 5.0 g / m ² (dry state). In the present invention, the anchor coat layer as described above improves the tight adhesion between the gas barrier coating film and the heat seal layer and the like and improves the elongation of the anchor coat layer, for example, laminating, or It is possible to improve post-processing suitability such as box making and to prevent generation of cracks or the like in the deposited film of inorganic oxide during post-processing.

(7) Heat-seal layer As the heat-seal layer, polyolefin resins having various heat-seal properties that can be melted by heat and fused together can be used. Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, ethylene-α / olefin copolymer polymerized using a metallocene catalyst, polypropylene, ethylene-acetic acid Vinyl copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methyl Polyethylene resins such as pentene polymer, polybutene polymer, polyethylene or polypropylene modified with unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, acid-modified polyolefin resin, polyvinyl acetate Resin, poly (medium ) Can be used an acrylic resin, polyvinyl chloride resin, other like resins. In the present invention, one or more of the above resins are used, melt extruded using an extruder or the like, and a melt extruded resin layer is melt extrusion laminated through an anchor coat layer or the like. Alternatively, one or more of the above resins are used, and a resin film or sheet is produced in advance from the resin film or sheet through an adhesive layer for laminating or the like. A heat seal layer can be formed by dry lamination lamination.

  One of the characteristics of the present invention is that a heat seal layer is formed on an anchor coat layer made of an anchor coat composition containing polyethyleneimine. Even when low density polyethylene is used as a heat seal layer, lamination is also possible. Strength can be improved. If this point is described in detail, since low density polyethylene or linear (linear) low density polyethylene is heated to about 330 to 350 ° C. and melt extruded, silicon oxide and oxide constituting the gas barrier laminate film are oxidized. A heating temperature of about 330 to 350 ° C. acts on a vapor deposition film of an inorganic oxide such as aluminum, and a crack or the like is likely to occur in the vapor deposition film of an inorganic oxide such as silicon oxide or aluminum oxide. In some cases, the barrier property to prevent the permeation of light is significantly deteriorated. Therefore, a copolymer with ethylene-unsaturated carboxylic acid or an esterified product thereof that can be melt-extruded and laminated at a lower temperature may be used. However, in the present invention, an inorganic oxide vapor deposition film is provided on the surface of the base film, the gas barrier coating film is provided on the surface of the inorganic oxide vapor deposition film, and an anchor coat composition containing polyethyleneimine thereon. By providing an anchor coat layer made of the above, even when a heat seal layer made of a polyolefin resin having heat sealability is laminated on the anchor coat layer, the laminate strength between the layers can be improved by polyethyleneimine In a gas barrier laminate film, sufficient adhesive strength and gas barrier properties can be ensured.

  In the present invention, the thickness of the heat seal layer is about 5 to 200 μm, preferably about 10 to 100 μm.

(8) Thermal adhesive resin layer In the present invention, a thermal adhesive resin layer can be provided between the anchor coat layer and the heat seal layer. As such a heat-adhesive resin layer, various heat-sealable polyolefin-based resins that can be melted by heat and fused to each other can be used, and the same resin as the heat-seal layer is used. May be. Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene -Ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-α / olefin copolymer polymerized using metallocene catalyst, polypropylene, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer Polyolefin resins such as methylpentene polymer, polybutene polymer, polyethylene or polypropylene modified with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, Vinyl acetate Resins, poly (meth) acrylic resins, one or more resins comprising a resin such as polyvinyl chloride resin. When the resin constituting the heat-adhesive resin layer is formed by melt extrusion, the anchor coat layer and the heat-adhesive resin layer can be bonded with excellent adhesion. Subsequently, the film which consists of resin which comprises the said heat seal layer can be laminated | stacked on the said heat adhesive resin layer, and it can be set as the gas barrier laminated film of this invention.

  As described above, the present invention uses an anchor coat layer containing polyethyleneimine, and laminates a heat seal layer or a heat-adhesive resin layer that can be melted and welded to each other on the anchor coat layer. The laminate strength can be improved without providing an adhesive layer made of a copolymer with ethylene-unsaturated carboxylic acid or its esterified product that melts and adheres at a lower temperature. Therefore, when the heat-adhesive resin layer is laminated on the anchor coat layer by melt extrusion, the heat seal layer laminated on the heat-adhesive resin layer is not limited to melt extrusion, and a laminate adhesive or the like is used. It may be bonded by a dry lamination method.

(9) Printed layer In the present invention, a desired printed pattern layer can be formed between any of the layers forming the gas barrier laminate film. As the printed pattern layer, for example, a normal gravure ink composition, an offset ink composition, a relief ink composition, a screen ink composition, and other ink compositions on a base film or a gas barrier coating film. Use, for example, gravure printing method, offset printing method, letterpress printing method, silk screen printing method, and other printing methods, for example, to form a desired printing pattern consisting of characters, figures, patterns, symbols, etc. Can be configured.

  Regarding the ink composition, examples of the vehicle constituting the ink composition include polyolefin resins such as polyethylene resins and chlorinated polypropylene resins, poly (meth) acrylic resins, polyvinyl chloride resins, and polyvinyl acetate. Resin, vinyl chloride-vinyl acetate copolymer, polystyrene resin, styrene-butadiene copolymer, vinylidene fluoride resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, polybutadiene resin, polyester resin Resins, polyamide resins, alkyd resins, epoxy resins, unsaturated polyester resins, thermosetting poly (meth) acrylic resins, melamine resins, urea resins, polyurethane resins, phenol resins, xylene resins , Maleic resin, Fiber resins such as rocellulose, ethylcellulose, acetylbutylcellulose, ethyloxyethylcellulose, rubber resins such as chlorinated rubber and cyclized rubber, natural resins such as petroleum resins, rosin and casein, linseed oil, soybean oil, etc. A mixture of one or more of fats and oils and other resins can be used. In the present invention, one or more of the above-mentioned vehicles are used as a main component, and one or more of coloring agents such as dyes and pigments are added to this, and if necessary, a filler, Light stabilizers such as additives, plasticizers, antioxidants, UV absorbers, dispersants, thickeners, drying agents, lubricants, antistatic agents, cross-linking agents, and other additives are optionally added, solvent, dilution Ink compositions having various forms obtained by sufficiently kneading with an agent or the like can be used.

  The print layer may be printed by surface printing or reverse printing of a desired printing pattern such as a character, a figure, a symbol, a pattern, or a pattern, and may be full surface printing or partial printing.

(10) Other laminated materials In the present invention, the gas barrier laminated film may be subjected to severe physical and chemical conditions during its use, and has a deformation prevention strength, a drop impact strength, Various conditions such as pinhole property, heat resistance, sealing property, quality maintenance, workability, hygiene, etc. are required. For this reason, in this invention, the material which satisfies the said various conditions can further be selected arbitrarily and laminated | stacked on the said gas-barrier laminated | multilayer film further. Examples of such a laminated material include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene- Ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride Polymer, poly (meth) acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin , Polyamide series Oil, polycarbonate resin, polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, fluorine resin, diene resin, polyacetal resin, polyurethane resin, nitrocellulose, and other known resin films There is. Any of these films, such as unstretched films and films stretched in a uniaxial or biaxial direction, can be used. Moreover, although the thickness is arbitrary, it can select and use from the range of several micrometers-about 300 micrometers according to a use. These films may be films having any properties such as extrusion film formation, inflation film formation, and coating film. In addition, for example, a film such as cellophane, various paper base materials, synthetic paper, and the like can be used.

  In this invention, when laminating | stacking another laminated material, it can laminate | stack using the adhesive agent for lamination, for example, using the dry lamination lamination method. The adhesive for laminating comprises a polyvinyl acetate adhesive, a homopolymer such as ethyl acrylate, butyl, 2-ethylhexyl ester or a copolymer of these with methyl methacrylate, acrylonitrile, styrene, etc. Polyacrylate adhesives, cyanoacrylate adhesives, ethylene copolymer adhesives made of copolymers of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, etc., cellulose adhesives Polyester adhesive, polyamide adhesive, polyimide adhesive, amino resin adhesive made of urea resin or melamine resin, phenol resin adhesive, epoxy adhesive, polyurethane adhesive, reactive type (meta ) Acrylic acid adhesive, chloroprene rubber, nitrile Beam, styrene - inorganic adhesive made of butadiene rubber, a silicone-based adhesive, an alkali metal silicate, inorganic adhesive made of low-melting glass, it is possible to use other adhesives.

  More preferably, for example, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, or aliphatic polyisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, etc. Mainly used are polyether polyurethane resins, polyester polyurethane resins, and polyacrylate polyurethane resins obtained by reacting polyfunctional isocyanates with polyether polyols, polyester polyols, polyacrylate polyols, and other hydroxyl group-containing compounds. Ingredients. According to these, it is possible to form a thin film rich in flexibility and flexibility, improve its tensile elongation, and as a film having flexibility, flexibility, etc. against a barrier thin film layer made of an inorganic oxide It can act and improve processing aptitude, such as lamination processing and printing processing, and can avoid generation of a crack etc. to a barrier thin film layer which consists of inorganic oxides.

The composition system of these adhesives may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the property may be any of a film, a sheet, a powder, a solid, and the like. Furthermore, the reaction mechanism may be any of a chemical reaction type, a solvent volatilization type, a heat welding type, a hot pressure type, and the like. The amount of the laminating adhesive is not particularly limited, but is generally 0.1 to 10 g / m ² (dry state). The laminating adhesive can be applied by roll coating, gravure coating, kiss coating or other coating methods or printing methods.

(11) Gas barrier laminated film The gas barrier laminated film of the present invention is produced by a method of laminating an ordinary laminated material, for example, a wet lamination method, a dry lamination, in order to produce a gas barrier laminated film using the above-described materials. For example, a solvent-free dry lamination method, an extrusion lamination method, a T-die extrusion molding method, a coextrusion lamination method, an inflation method, a coextrusion inflation method, and the like.

  In the present invention, a packaging container can be produced using the barrier laminate film as described above. For example, if the packaging container is a flexible packaging bag made of plastic film, etc., use the laminated material manufactured by the method described above, and fold it up with the inner surface of the heat-sealable film facing each other. Alternatively, the two sheets can be overlapped, and the peripheral edge can be heat sealed to provide a seal portion to form a bag. As the bag making method, the above-mentioned laminated material is bent with the inner layer faces facing each other, or the two sheets are overlapped, and the peripheral edge of the outer periphery is, for example, a side seal type, two-side seal Heat seal by heat seal form such as mold, three-side seal type, four-side seal type, envelope sticker seal type, palm seal sticker type (pillow seal type), pleated seal type, flat bottom seal type, square bottom seal type, etc. Various types of packaging containers according to the present invention can be manufactured. In addition, for example, a self-supporting packaging bag (standing pouch) or the like can be manufactured. Further, in the present invention, a tube container or the like can be manufactured using the laminated film.

  In the above, the heat sealing method can be performed by a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal, and the like. In the present invention, a spout such as a one-piece type, a two-piece type, or the like, or an opening / closing zipper can be arbitrarily attached to the packaging container as described above. Further, the shape can be any of a rectangular container, a cylindrical paper can such as a round shape, and the like.

  In the present invention, the packaging container produced as described above is filled with various foods and drinks, chemicals such as adhesives and adhesives, cosmetics, pharmaceuticals, miscellaneous goods such as chemical warmers, and other various articles. It is used for packaging. In the present invention, for example, a liquid sachet for filling and packaging soy sauce, sauce, soup, etc., a soft packaging bag for filling and packaging fresh confectionery, etc., or a soft packaging bag for filling and packaging boiled or retort food, etc. It is useful as a packaging container for filling and packaging foods and drinks or foods and drinks containing moisture.

  EXAMPLES Next, although an Example is given and this invention is demonstrated concretely, these Examples do not restrict | limit this invention at all.

Example 1
(1) A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm having a corona-treated surface on one side is used, and this film is attached to a delivery roll of a plasma chemical vapor deposition apparatus. A deposited silicon oxide film having a thickness of 120 mm was formed on the corona-treated surface of the axially stretched polyethylene terephthalate film.

That is, the raw material hexamethyldisiloxane (hereinafter referred to as HMDSO) is introduced into the corona-treated surface; the amount of introduced gas; hexamethyldisiloxane: oxygen gas: helium = 1.0: 3.0: 3.0 (units) Slm), degree of vacuum in the vacuum chamber; 2-6 × 10 ⁻⁶ mBar, degree of vacuum in the deposition chamber; 2-5 × 10 ⁻³ mBar, cooling and electrode drum power supply: 10 kW, line speed: 100 m / supplied in min.

Next, immediately after the silicon oxide vapor deposition film having a thickness of 120 mm was formed, a glow discharge plasma generator was used on the silicon oxide vapor deposition film surface, and the power was 9 kw, oxygen gas (O ₂ ): argon gas (Ar). = 7.0: 2.5 (unit: slm) is used, and oxygen / argon mixed gas plasma treatment is performed at a mixed gas pressure of 6 × 10 ⁻⁵ Torr and a processing speed of 420 m / min. The surface tension of the deposited film surface was improved by 54 dyn / cm or more to form a plasma treated surface.

  (2) Next, a preliminarily prepared hydrolyzate of composition b was added to the mixed solution of composition a prepared according to the composition shown in Table 1 and stirred to obtain a colorless and transparent barrier coating solution.

上記で製造したバリア性塗工液を使用し、これをグラビアロールコート法により前記（１）のプラズマ処理面上にコーティングし、次いで、１４０℃で６０秒間、加熱処理して、厚さ０．３μｍ（乾操状態）のガスバリア性塗布膜を形成した。

Using the barrier coating solution produced above, this was coated on the plasma-treated surface of (1) by the gravure roll coating method, and then heat-treated at 140 ° C. for 60 seconds to obtain a thickness of 0. A gas barrier coating film of 3 μm (dry operation state) was formed.

(3) Next, the gas barrier coating film formed in the above (2) is coated with a polyethyleneimine anchor coating agent by a gravure roll coating method so that the film thickness becomes 0.1 g / m ² (dry state). It dried and the anchor coat layer was formed.

  (4) On the surface of the anchor coat layer formed above using an extrusion laminator, low-density polyethylene is extruded and laminated at an extrusion temperature of 310 ° C. and an extrusion film thickness of 30 μm to form a melt-extruded resin layer. A gas barrier laminate film was produced by aging treatment at 40 ° C. for 3 days.

Example 2
A biaxially stretched nylon film having a corona-treated surface on one side and having a thickness of 15 μm was used as the base film, and the vapor deposition conditions were as follows: reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 11: 10 ( (Unit: slm), degree of vacuum in the vacuum chamber: 5.2 × 10 ⁻⁶ mbar, degree of vacuum in the deposition chamber: 5.1 × 10 ⁻² mbar, cooling / electrode drum power supply: 18 kW, film transport speed : A gas barrier laminate film was produced in the same manner as in Example 1 except that a vapor-deposited silicon oxide film having a thickness of 150 mm was formed on the corona-treated surface of the biaxially stretched nylon film at 70 m / min.

Example 3
A biaxially stretched polyethylene terephthalate film with a thickness of 12 μm that has a corona-treated surface on one side is used as a base film, and this film is attached to a take-up roll of a take-up type vacuum vapor deposition apparatus. The vacuum degree in the deposition chamber is 2 × 10 ⁻⁴ mbar, the vacuum degree in the take-up chamber is 2 × 10 ⁻² mbar, by the electron beam (EB) heating method while supplying oxygen gas A gas barrier laminate film is produced in the same manner as in Example 1 except that a vapor deposition film of aluminum oxide having a thickness of 200 mm is formed on the corona-treated surface with a beam power of 25 kW and a film conveyance speed of 240 m / min. did.

Example 4
A biaxially stretched nylon film with a thickness of 15 μm having a corona-treated surface on one side is used as a base film, and this is attached to a delivery roll of a take-up vacuum deposition apparatus, and as a deposition condition, aluminum is used as a deposition source. While supplying oxygen gas, the degree of vacuum in the deposition chamber is 7.2 × 10 ⁻⁶ mbar and the degree of vacuum in the take-up chamber is 1.0 × 10 ⁻⁶ by the vacuum deposition method using an electron beam (EB) heating method. Gas barrier lamination was carried out in the same manner as in Example 1 except that a vapor deposition film of 200 mm thick aluminum oxide was formed on the corona-treated surface at mbar, electron beam power: 40 kW, and film transport speed: 500 m / min. A film was produced.

Example 5
In the same manner as in Examples (1) to (3), a base film (a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm having a corona-treated surface on one side) is deposited on a silicon oxide film, a plasma-treated surface, and a gas barrier property. A film in which a coating film and an anchor coat layer were laminated was produced.

  Next, the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm made to face is opposed to each other, and the low-density polyethylene is laminated by extrusion lamination at an extrusion temperature of 310 ° C. and an extrusion film thickness of 15 μm. A gas barrier laminate film having a 30 μm polyethylene film was prepared.

Comparative Example 1
In the same manner as in (1) to (3) of Example 1, a film was produced by laminating a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm with a deposited silicon oxide film, a plasma-treated surface, and a gas barrier coating film.

  Next, low density polyethylene is extruded on the gas barrier coating film at an extrusion temperature of 310 ° C. and an extrusion film thickness of 30 μm to form a melt-extruded resin layer, and then subjected to aging treatment at 40 ° C. for 3 days for comparison. A gas barrier laminate film was produced.

Comparative Example 2
In the same manner as in (1) to (3) of Example 1, a film was produced by laminating a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm with a deposited silicon oxide film, a plasma-treated surface, and a gas barrier coating film.

  Next, an ethylene-methacrylic acid copolymer is extrusion laminated at an extrusion temperature of 280 ° C. and an extrusion film thickness of 30 μm on the gas barrier coating film to form a melt-extruded resin layer, and then an aging treatment at 40 ° C. for 3 days. A comparative gas barrier laminate film was produced.

Comparative Example 3
In the same manner as in Example 5 (1), a silicon oxide vapor-deposited film and a plasma-treated surface were formed on a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm.

Next, a polyethyleneimine-based primer coating agent was coated and dried on the plasma-treated surface by a gravure roll coating method so as to have a film thickness of 0.1 g / m ² (dry state) to form a primer coating layer.

  Next, low-density polyethylene is extruded and laminated to the primer coat layer at an extrusion temperature of 310 ° C. and an extrusion film thickness of 30 μm to form a melt-extruded resin layer, and then subjected to an aging treatment at 40 ° C. for 3 days for comparative gas barrier properties. A laminated film was produced.

Evaluation method About the film manufactured in Examples 1-5 and Comparative Examples 1-3, gas-barrier property and laminate strength were evaluated. The results are shown in Table 2.

(1) Gas barrier properties (i) Measurement of oxygen permeability:
The measurement was performed with a measuring instrument (model name, OX-TRAN 2/20) manufactured by MOCON, USA under the conditions of a temperature of 23 ° C. and a humidity of 90% RH. The results are shown in Table 2.

(Ii) Measurement of water vapor permeability:
Measurement was performed with a measuring instrument (model name, PERMATRAN 3/31) manufactured by MOCON, USA under the conditions of a temperature of 40 ° C. and a humidity of 90% RH. The results are shown in Table 2. In Table 2, the unit of oxygen permeability is [cc / m ² / day · 23 ° C./90% RH], and the unit of water vapor permeability is [g / m ² / day · 40 ° C. · 90 % RH].

(2) Laminate strength Using a peel tester (Orientec Co., Ltd., model name, Tensilon Universal Tester STA-1150), cut the material to a width of 15 mm so that the peel interface has a T-shaped peel. The peel strength was measured. The unit is [N / 15 mm].

  The gas barrier laminate film according to the present invention is excellent in laminate strength and gas barrier properties and is useful.

Fig.1 (a)-(e) is a cross-sectional view explaining the gas-barrier laminated | multilayer film of this invention. It is a schematic block diagram which shows an example of a low temperature plasma chemical vapor deposition apparatus. It is a schematic block diagram which shows an example of a winding-type vacuum deposition apparatus.

Explanation of symbols

10 ... base film,
10 '... plasma surface treatment surface 20 ... deposited film of inorganic oxide,
20 '... corona surface treatment surface 30 ... gas barrier coating film,
40: Anchor coat layer,
50 ... heat seal layer,
60: Print layer.

Claims (8)

A gas barrier laminated film having a base film, an inorganic oxide vapor deposition film, a gas barrier coating film, an anchor coat layer and a heat seal layer,
An inorganic oxide vapor deposition film is provided on the surface of the base film, and the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² are C represents an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents the valence of M.) Gas barrier coating with a gas barrier composition obtained by polycondensation by a sol-gel method, which contains at least one alkoxide represented by the formula (1) and a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. A gas barrier property, characterized in that a film is provided, an anchor coat layer comprising an anchor coat composition containing polyethyleneimine is provided on the gas barrier coating film, and a heat seal layer is laminated on the anchor coat layer. Layer film.   The gas barrier laminate film according to claim 1, further comprising an adhesive resin layer between the anchor coat layer and the heat seal layer.   The gas barrier laminate film according to claim 1 or 2, wherein the heat seal layer is made of a heat-fusible polyolefin resin.   The gas barrier laminate film according to claim 1 or 2, wherein the heat seal layer and / or the heat-adhesive resin layer is laminated by melt extrusion lamination of a heat-fusible polyolefin resin.   The gas barrier laminate film according to any one of claims 1 to 4, wherein the base film is a biaxially stretched resin film.   6. The gas barrier laminated film according to claim 1, wherein the inorganic oxide vapor-deposited film comprises an inorganic oxide vapor-deposited film formed by chemical vapor deposition or physical vapor deposition.   6. The gas barrier laminate film according to claim 1, wherein the inorganic oxide vapor-deposited film is an organic silicon compound vapor-deposited film formed by chemical vapor deposition.   6. The gas barrier laminate film according to claim 1, wherein the inorganic oxide vapor-deposited film comprises an aluminum oxide vapor-deposited film formed by physical vapor deposition.

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