JP2008143585A - Paper container for liquid - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a paper container for liquid having excellent laminate strength and gas barrier properties. <P>SOLUTION: The paper container for liquid is formed by folding a laminated material composed of an outermost layer, a paper substrate, a laminate film layer having gas barrier properties, and an innermost layer. In the laminate film layer having gas barrier properties, an vapor-deposited film of an inorganic oxide is provided on a film surface of the substrate, a primer coat layer is provided on a surface of the vapor-deposited film of the inorganic oxide, an anchor coat layer consisting of an anchor coat composition containing polyethylene imine is provided on the primer coat layer, and a heat-bonded layer is laminated on the anchor coat layer. The paper container for liquid has the excellent laminate strength and gas barrier properties. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a liquid paper container. More specifically, the present invention is excellent in barrier properties that prevent permeation of oxygen gas, water vapor, etc., further eliminates the occurrence of pinholes, avoids poor sealing, liquid leakage, etc. The present invention relates to a liquid paper container that prevents deterioration and the like and is excellent in storability and storage.

  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 a metal or metal compound thin film layer and a 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 as the barrier adhesive, 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 coating thin film layer and the protective layer are absorbed and blocked by the adhesive layer, so that higher barrier properties can be achieved.

In addition, a paper substrate can be further laminated on the gas barrier film to produce a liquid paper container, for example, an outermost layer, a paper substrate, an adhesive layer, a barrier layer including a vapor deposition film of an inorganic difference product, In addition, there is a liquid paper container in which the innermost layer is sequentially laminated to form a laminated material (Patent Document 4). The liquid paper container described in Patent Document 4 has the above-described configuration, thereby preventing cracks and the like from being generated in the vapor-deposited film of the inorganic oxide, and preventing the occurrence of twisted pinholes and the like. Can be maintained.
JP 2001-138428 A JP 2002-166486 A JP 2000-25145 A JP 2002-154524 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 a variety of desirable liquid paper 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 liquid paper container having excellent barrier properties for preventing permeation of oxygen gas, water vapor and the like.

  As a result of detailed examination of the gas barrier laminated film constituting the liquid paper container, the present inventor can impart gas barrier properties by forming an inorganic oxide vapor-deposited film on one surface of the substrate film. If a gas barrier coating film made of a polyvinyl alcohol resin, a metal alkoxide, a silane coupling agent, or the like is provided, water resistance can be imparted, and an anchor containing polyethyleneimine is provided between the gas barrier coating film and the heat fusion layer. When an anchor coat layer made of a coating composition is provided, adhesion can be improved while ensuring flexibility between the gas barrier coating film and the heat-sealing layer, thereby improving gas barrier properties as well as improving laminate strength. If a liquid paper container containing such a gas barrier laminate film is manufactured, the flavor is impaired. It found that excellent storage stability, such as easy-liquor, has led to the completion of the present invention.

  Since the liquid paper container of the present invention includes a gas barrier laminate film layer having excellent laminate strength and gas barrier properties, it is excellent in storage of contents.

  Since the liquid paper container of the present invention can be molded into a legislative body, it is easy to store the product.

The first of the present invention is a liquid paper container formed by boxing a laminated material in which an outermost layer, a paper base material, a gas barrier laminated film layer, and an innermost layer are laminated in this order,
The gas barrier laminate film layer is provided with an inorganic oxide vapor-deposited film on the base film surface, a gas barrier coating film made of a gas barrier composition on the surface of the inorganic oxide vapor-deposited film, and the gas barrier property This is a liquid paper container in which an anchor coat layer made of an anchor coat composition containing polyethyleneimine is provided on a coating film, and a heat fusion layer is laminated on the anchor coat layer. Hereinafter, the present invention will be described in detail.

(1) Laminate As shown in FIG. 1 (a), the laminate constituting the liquid paper container of the present invention comprises an outermost layer (A), a paper substrate (B), a gas barrier laminate film layer (C), Consisting of the innermost layer (D), the gas barrier laminated film layer comprises a base film (10), an inorganic oxide vapor deposition film (20), a gas barrier coating film (30), an anchor coat layer (40), and heat fusion. 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. In addition, as shown in FIG. 2A, the laminated material constituting the liquid paper container of the present invention includes an outermost layer (A), an adhesive resin layer (E), a paper base material (B), and a gas barrier laminated film. The gas barrier laminated film layer is composed of a base film (10), an inorganic oxide vapor deposition film (20), a gas barrier coating film (30), an anchor coat layer (40). ) And a thermal fusion layer (50). Furthermore, as shown in FIG.2 (b), you may have a surface treatment layer (10 ') and (20') on a base film (10) and a vapor deposition film (20), respectively.

  In the present invention, as shown in FIG. 1, the heat-sealing layer (50) of the gas barrier laminate film layer (C) and the paper substrate (B) are preferably laminated to face each other. As shown in FIG. 2, the heat-sealing layer (50) of the gas barrier laminate film layer (C) may be laminated to face the paper substrate (B) through the adhesive resin layer (E). preferable.

  The innermost layer (D) may be bonded to the base film (10) of the gas barrier laminate film layer (C) via a laminating adhesive, and by melt extrusion through an adhesive resin layer. It may be formed.

  Moreover, although not shown in figure, you may have a printing layer in any layer, and the said printing layer may be whole surface printing or partial printing.

(2) Outermost layer As the outermost layer, polyolefin resins having various heat sealability that can be melted by heat and fused to each other, and the like can be used. Specifically, for example, 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 -Vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, 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 resin, Can be used Li (meth) acrylic resin, polyvinyl chloride resin, a resin other like. 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. The outermost layer can be formed by dry lamination. In the present invention, the thickness of the outermost layer is about 5 to 200 μm, preferably about 10 to 100 μm.

(3) Paper base material As the paper base material constituting the liquid paper container, since it is a basic material constituting the paper container, a material having formability, flex resistance, rigidity, waist, strength, etc. is used. For example, it is possible to use various types of paper base materials such as a strongly sized bleached or unbleached paper base, or pure white roll paper, kraft paper, paperboard, processed paper, and the like. In the present invention, as the paper substrate, those having a basis weight of about 80 to 600 g / m ² , preferably those having a basis weight of about 100 to 450 g / m ² can be used.

(4) Base film The base film constituting the gas barrier laminate film layer that can be used in the present invention is excellent in chemical or physical strength, and under conditions for forming a deposited film of each inorganic oxide. It is possible to use a resin film that can endure and can be satisfactorily maintained without impairing film properties such as a vapor-deposited film of the inorganic oxide. 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.

(5) 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 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, 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, as described above, the surface of the resin film other than the substrate film, that is, a paper substrate, an inorganic oxide vapor-deposited film, a gas barrier coating film, a heat fusion layer, a printing layer. In order to improve adhesion with other layers and films, 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.

(6) 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 a method for forming a vapor-deposited film of an inorganic oxide by the low temperature plasma chemical vapor deposition method will be described with reference to FIG. 3 which is a schematic configuration 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. 3, 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 for forming a thin film of an inorganic oxide by physical vapor deposition will be described with reference to FIG. 4 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.

(7) 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 and heat resistance of the resulting gas barrier laminate film layer 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 the amount 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 layer 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 layer. 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 this invention, in order to form the vapor deposition layer of an inorganic oxide in a base film, and to form a gas barrier coating film, it can manufacture with 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.

  Next, the above gas barrier composition is applied onto the inorganic oxide vapor-deposited film on the base film layer by a conventional method and dried. 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. Accordingly, one or more gas barrier coating films of the gas barrier composition can be formed on the inorganic oxide vapor-deposited film.

  In addition, the gas barrier property laminated film layer obtained using the ethylene / vinyl alcohol copolymer alone or both of the polyvinyl alcohol resin and the ethylene / vinyl alcohol copolymer is excellent in the gas barrier property after the hot water treatment. On the other hand, when the gas barrier coating film is formed using only the polyvinyl alcohol-based resin, the first coating film is formed by previously applying the gas barrier composition using the 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. Forming a film and laminating a plurality of these are effective means for improving the gas barrier property of the gas barrier laminated film layer according to the present invention.

  Next, the case where alkoxysilane is used as the alkoxide will be described in more detail.

  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. Furthermore, the gas barrier laminate film layer 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.

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

  The anchor coat composition comprises polyethyleneimine as a main component of the vehicle, and further, if necessary, a stabilizer, a curing agent, a crosslinking agent, a lubricant, an ultraviolet absorber, etc. with respect to 1 to 30% by mass of the polyethyleneimine. The additive is optionally added, and a solvent, a diluent and the like are added and mixed well to prepare an aqueous composition. The main component of the vehicle is polyethyleneimine, and the silane coupling agent is 0.05 to 10% by mass, preferably 0.1 to 5% by mass, and the filler 0.1 to 1 to 30% by mass of the polyethyleneimine. -20% by mass, preferably 1-10% by mass, and if necessary, additives such as stabilizers, curing agents, crosslinking agents, lubricants, UV absorbers, etc. may be optionally added. Alternatively, an aqueous composition may be prepared by adding a solvent, a diluent and the like and mixing them well.

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-fusible layer and the like, and improves the elongation of the anchor coat layer. 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 the inorganic oxide during post-processing.

  In the above, the polyethyleneimine constituting the composition 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 be closely_contact | adhered 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）」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、無機酸化物の蒸着膜と熱接着性樹脂層等との密接着性等を向上させると共にプライマー剤層の伸長度を向上させ、例えば、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 “Epomin (registered trademark)” manufactured by Nippon Shokubai Co., Ltd. In the present invention, by using the polyethyleneimine as described above, the adhesiveness between the inorganic oxide vapor-deposited film and the heat-adhesive resin layer is improved and the elongation of the primer layer is improved, for example, Further, it is possible to improve post-processing suitability such as laminating or box making, and to prevent generation of cracks or the like in the deposited film of the inorganic oxide during post-processing.

  As the silane coupling agent constituting the composition, organic functional silane monomers having binary reactivity can be used, for example, γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane. , Vinyl-tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane , Γ-mercaptopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, bis (Β-hydroxye Le)-.gamma.-aminopropyltriethoxysilane, .gamma.-aminopropyl silicone - can be used one or more of the aqueous solution or the like of the emission.

  In the silane coupling agent, a functional group at one end of the molecule, usually, chloro, alkoxy, or acetoxy group is hydrolyzed to form a silanol group (SiOH), which forms an inorganic oxide vapor-deposited film. The surface of the inorganic oxide vapor deposition film is caused to react with active groups on the surface of the metal or inorganic oxide vapor deposition film, for example, a functional group such as a hydroxyl group, for example, by a reaction such as a dehydration condensation reaction. The silane coupling agent is modified with a covalent bond or the like, and further, a strong bond is formed on the surface of the deposited inorganic oxide film of the silanol group by adsorption or hydrogen bond. On the other hand, an organic functional group such as vinyl, methacryloxy, amino, epoxy, or mercapto at the other end of the silane coupling agent is formed on the thin film of the silane coupling agent. It reacts with substances constituting other layers, etc. to form a strong bond, and further, other base materials are firmly and tightly bonded through the above-mentioned thermal adhesive resin layer, etc., and its laminate strength Thus, in the present invention, a strong laminated structure with high laminate strength can be formed. In the present invention, the inorganic property and organic property of the silane coupling agent are utilized, and the substrate is in close contact with another substrate or the like through a layer such as a vapor-deposited film of an inorganic oxide and a heat-adhesive resin layer or the like. The wearability is improved, thereby significantly increasing the laminate strength and the like.

  As the filler, for example, calcium carbonate, barium sulfate, alumina white, silica, talc, glass frit, resin powder, and the like can be used. 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, in the above composition, if necessary, for example, polyurethane resin, polyester resin, polyamide resin, epoxy resin, phenol resin, (meth) acrylic resin, polyvinyl acetate resin, polyethylene or A composition can 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.

(9) Thermal fusion layer As the thermal fusion layer constituting the gas barrier laminate film layer, the same layer as the outermost layer can be used. For example, various heats that can be melted by heat and fused to each other A polyolefin resin having a sealing property, and the like 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-sealing layer can be formed by dry lamination.

  One of the features of the present invention is that a heat fusion layer is formed on an anchor coat layer made of an anchor coat composition containing polyethyleneimine, and even when low-density polyethylene is used as the heat fusion layer. The laminate 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 an 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 fusion 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 polyethylene imine. Therefore, sufficient adhesive strength and gas barrier properties can be secured in the gas barrier laminate film.

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

(10) Print layer In the present invention, a desired print pattern layer can be formed between the paper substrate, the gas barrier laminate film layer, and any other layers. Examples of the printed pattern layer include, for example, a normal gravure ink composition, an offset ink composition, and a relief printing ink composition on a paper base material, a base film constituting a gas barrier laminate film layer, and a gas barrier coating film. , Using screen ink compositions, other ink compositions, for example, gravure printing method, offset printing method, letterpress printing method, silk screen printing method, other printing methods, for example, characters, figures, patterns, It can be configured by forming a desired printed picture made up of symbols and the like.

  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.

(11) Innermost layer The innermost layer in the laminated material used in the present invention may be the same as the outermost layer or the heat-sealing layer described above. In general, it is preferable to use a resin that can be melted by heat and fused to each other, specifically, a low-density polyethylene or a polyolefin resin such as a linear (linear) low-density polyethylene.

  On the other hand, a low-density polyethylene or a linear (linear) low-density polyethylene is used, and the heat-adhesive resin layer can be formed with the melt-extruded resin layer while heating and extruding it. In this case, however, low density polyethylene or linear (linear) low density polyethylene is heated to about 330 to 350 ° C. and melt extruded. For this reason, the heating temperature of about 330 to 350 ° C. acts on the vapor deposition film of inorganic oxide such as silicon oxide and aluminum oxide constituting the gas barrier laminate film, and vapor deposition of inorganic oxide such as silicon oxide and aluminum oxide. Cracks and the like are likely to occur in the film, and the barrier property that prevents the permeation of oxygen gas, water vapor and the like may be significantly deteriorated. Therefore, in the present invention, as the innermost layer, an ethylene-α / olefin copolymer polymerized using a metallocene catalyst having a low temperature sealing property may be suitably used. This has the advantage of preventing the occurrence of pinholes and avoiding poor sealing, liquid leakage, and the like. In particular, an ethylene-α / olefin copolymer polymerized using a metallocene catalyst has the advantage of improving impact resistance with less propagation of breakage due to its stickiness, and the innermost layer is always in contact with the contents. Therefore, it is also effective for preventing deterioration of environmental stress cracking resistance. In the present invention, another resin can be blended with the ethylene-α / olefin copolymer polymerized using a metallocene catalyst. For example, by blending an ethylene-butene copolymer, Although it is inferior in heat resistance and tends to deteriorate the seal stability in a high temperature environment, there is an advantage that the tearability is improved and it contributes to easy opening. In the present invention, in particular, when using the innermost layer composed of an ethylene-α / olefin copolymer layer polymerized using a metallocene catalyst, low temperature heat sealability is possible when a liquid paper container is boxed. It has the advantage of being.

  Examples of the ethylene-α / olefin copolymer polymerized using the above metallocene catalyst include, for example, a catalyst by a combination of a metallocene complex and an alumoxane, such as a catalyst by a combination of zirconocene dichloride and methylalumoxane, that is, a metallocene catalyst. The ethylene-α-olefin copolymer obtained by copolymerizing ethylene and α-olefin can be used. The above metallocene catalyst is also called a single-site catalyst because the current catalyst is called a multi-site catalyst with non-uniform active sites (below, the active sites are uniform). The metallocene catalyst has the same meaning as the single-site catalyst.) Specifically, as an ethylene-α / olefin copolymer polymerized using a metallocene catalyst, trade name “Kernel” manufactured by Mitsubishi Chemical Corporation, trade name “Evolue” manufactured by Mitsui Petrochemical Co., Ltd., Product name “EXACT” manufactured by EXXONCHEMICAL, USA, product name “AFFINITY”, product name “engage” manufactured by Dow Chemical, USA An ethylene-α-olefin copolymer polymerized using a metallocene catalyst can be used. Thus, in the present invention, the innermost layer composed of the ethylene-α / olefin copolymer layer polymerized using the metallocene catalyst as described above, for example, an anchor on the base film surface of the gas barrier laminate film layer. It can be formed using a normal lamination method such as a melt extrusion lamination method in which lamination is performed via a coat layer or the like, or a dry lamination method in which lamination is carried out via an adhesive layer for lamination. In the present invention, the film thickness of the innermost layer is about 10 μm to 300 μm, preferably about 20 μm to 100 μm.

  The ethylene-α / olefin copolymer polymerized using the above metallocene catalyst will be described in more detail. Specifically, for example, a catalyst comprising a combination of a metallocene-based transition metal compound and an organoaluminum compound, that is, a metallocene catalyst ( An ethylene-α / olefin copolymer obtained by copolymerizing ethylene and an α-olefin can be used. In addition, said metallocene catalyst may be supported and used for an inorganic substance. In the above, examples of the metallocene transition metal compound include a transition metal selected from group IVB, specifically, titanium (Ti), zirconium (Zr), hafnium (Hf), cyclopentadienyl group, substituted cyclohexane. 1 to 2 of a pentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluoronyl group, and a substituted fluorenyl group, or two of these groups Those covalently bonded are bonded, and in addition, hydrogen atom, oxygen atom, halogen atom, alkyl group, alkoxy group, aryl group, acetylacetonate group, carbonyl group, nitrogen molecule, oxygen molecule, Lewis base, silicon Those having ligands such as substituents containing atoms and unsaturated hydrocarbons can be used. . In the above, as the organoaluminum compound, alkylaluminum, chain or cyclic aluminoxane, or the like can be used. Here, as the alkylaluminum, for example, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride. Etc. can be used. The chain or cyclic aluminoxane can be produced, for example, by bringing alkyl aluminum into contact with water. For example, it can be produced by adding alkylaluminum at the time of polymerization and adding water later, or by reacting crystallization water of a complex salt or adsorbed water of an organic / inorganic compound with alkylaluminum. Next, in the above, as the inorganic material for supporting the metallocene catalyst, for example, silica gel, zeolite, silicon earth or the like can be used.

Next, in the above, as the polymerization method, for example, various polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and gas phase polymerization can be performed. In addition, the polymerization may be any method such as a batch method or a continuous method. In the above, the polymerization conditions are polymerization temperature, −100 to 250 ° C., polymerization time, 5 minutes to 10 hours, reaction pressure, normal pressure to 300 kg / cm ² . Further, in the present invention, examples of the α-olefin which is a comonomer copolymerized with ethylene include propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 1 -Octene, decene, etc. can be used. The above α · olefin fin may be used alone or in combination of two or more. Moreover, the mixing ratio of the above-mentioned α · olefin fin is, for example, 1 to 50% by mass, and preferably 10 to 30% by mass. Therefore, in the present invention, the physical properties of the ethylene-α / olefin copolymer polymerized using the metallocene catalyst are, for example, molecular weight, 5 × 10 ^{3 to} 5 × 10 ⁶ , density, 0.890 to 0 930 g / cm ³ , melt flow rate [MFR], 0.1 to 50 g / 10 quantile. In the present invention, the ethylene-α / olefin copolymer polymerized using the above metallocene catalyst includes, for example, an antioxidant, an ultraviolet absorber, an antistatic agent, an antiblocking agent, a lubricant (fatty acid amide, etc.). ), Flame retardants, inorganic or organic fillers, dyes, pigments and the like can be optionally added and used.

  Furthermore, in the present invention, as the innermost layer composed of an ethylene-α / olefin copolymer layer polymerized by a metallocene catalyst, an ethylene-α / olefin copolymer polymerized by the metallocene catalyst as described above, It consists of a co-extruded resin layer with a polyolefin resin such as low-density polyethylene and linear low-density polyethylene, and an ethylene-α / olefin-based resin layer polymerized by a metallocene catalyst that constitutes the co-extruded resin layer. A co-extruded resin layer can be used. In the above, the co-extruded resin layer can be produced by a T-die co-extrusion method or a co-extrusion inflation method, and the layer structure is composed of two or more layers. It is composed of a co-extruded resin layer, and it is desirable that the thickness of each resin layer is arbitrarily adjusted within a range of about 2 to 20 μm.

(12) Adhesive resin layer In the present invention, when laminating the gas barrier laminate film layer and the paper base material in the laminate, the paper base material and the heat fusion layer are interposed via the adhesive resin layer. Can be laminated.

  As such an adhesive resin, it is preferable to use a polyolefin-based resin having heat-fusibility, and it can be used after being melt-extruded. As such a polyolefin-based resin, a polyolefin-based resin that constitutes the heat-sealing layer constituting the outermost layer or the gas barrier laminate film layer described above, or the like can be used. Specifically, for example, 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 -Vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, 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 resin, Can be used Li (meth) acrylic resin, polyvinyl chloride resin, a resin other like.

  In the present invention, one or more of the above-mentioned polyolefin-based resins having heat-fusibility are used as an adhesive resin, and this is used, for example, by using an extruder or the like as a paper substrate. In addition, a gas-extruded resin film is formed between a heat-bonding layer of a gas barrier laminate film layer or a base film, and, if necessary, via a anchor coat layer, etc. The substrate and the gas barrier laminate film layer are extrusion laminated. In the above, the film thickness of the polyolefin resin melt-extruded resin layer is preferably about 10 to 50 μm, more preferably about 15 to 35 μm.

(13) Laminate Adhesive In the present invention, when laminating laminates, a laminate adhesive can be used and laminated using a dry laminate lamination method. For example, when laminating the innermost layer on the gas barrier laminate film layer, it can be laminated via an adhesive for lamination.

  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.

  The laminating adhesive is not limited to laminating the gas barrier laminate film layer and the innermost layer, and may be used for laminating other layers.

(14) Other laminated materials As a material for forming the laminated material constituting the liquid paper container according to the present invention, for example, low density polyethylene having a barrier property such as water vapor, water, medium density polyethylene, high density polyethylene, linear chain Film or sheet of resin such as low-density polyethylene, polypropylene, ethylene-propylene copolymer, etc., or polyvinylidene chloride resin, polyvinyl alcohol resin, ethylene-vinyl alcohol copolymer having a barrier property against oxygen, water vapor, etc. Films and sheets of resins such as MXD polyamide resin and polynaphthalene terephthalate resin, various colorants such as pigments to the resin, and various light-shielding properties obtained by kneading into a film by adding desired additives. A colored resin film or sheet can be used. These materials can be used alone or in combination. The thickness of the film or sheet is arbitrary, but is usually about 5 μm to 300 μm, more preferably about 10 μm to 100 μm.

  In the present invention, since the liquid paper container is usually subjected to severe physical and chemical conditions, the packaging material constituting the liquid paper container is required to have strict packaging suitability and deformation. Various conditions such as prevention strength, drop impact strength, pinhole resistance, heat resistance, sealability, quality maintenance, workability, hygiene, etc. are required. For this reason, in the present invention, as described above Any material satisfying various conditions can be selected and used. Specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, and ethylene-propylene copolymer are used. Polymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, methyl pentene Polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylonitrile resin, polystyrene resin , Acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol resin, ethylene-vinyl acetate copolymer A saponified compound, a fluorine resin, a diene resin, a polyacetal resin, a polyurethane resin, a nitrocellulose, and other known resin films or sheets can be arbitrarily selected and used. In the present invention, the film or sheet may be any of unstretched, uniaxially or biaxially stretched. The thickness is arbitrary, but can be selected from a range of several μm to 300 μm. Furthermore, in the present invention, the film or sheet may be a film having any property such as extrusion film formation, inflation film formation, and coating film. In addition, for example, a film such as cellophane, a synthetic paper, or the like can be used.

  In laminating these layers, for example, they may be bonded via the above-mentioned adhesive resin layer, or they may be laminated using the above-mentioned laminating adhesive by a dry laminating method.

(15) Liquid paper container The laminated material used in the present invention is a method of laminating a normal laminated material, for example, a wet lamination method, a dry lamination method, a solventless dry lamination method, an extrusion lamination method, a T-die extrusion molding method. The coextrusion lamination method, the inflation method, the coextrusion inflation method, and the like can be used.

  The liquid paper container of the present invention is formed by boxing a laminated material composed of an outermost layer, a paper base material, a gas barrier laminated film layer, and an innermost layer. As the laminated material, a gas barrier laminated film is used in advance. A layer is prepared, and is not limited to the case where the outermost layer, the paper base material, and the innermost layer are laminated thereon. There is no limitation.

  As the liquid paper container according to the present invention, for example, a liquid paper container such as a brick type, a flat type, or a gable top type can be manufactured. Further, the shape can be any of a rectangular container, a cylindrical paper can such as a round shape, and the like. Furthermore, in the present invention, the liquid paper container according to the present invention is filled and packed with various articles such as various foods and drinks, chemicals such as adhesives and pressure-sensitive adhesives, cosmetics, miscellaneous goods such as pharmaceuticals, and the like. Is something that can be done. Thus, in the present invention, the liquid paper container according to the present invention particularly includes, for example, juices such as liquor and fruit juice beverages, liquid seasonings such as mineral water, soy sauce, sauces and soups, or curry, stew and soup. It is useful as a liquid paper container for filling and packaging various liquid foods such as others.

  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, hexamethyldisiloxane as a raw material is introduced into the corona-treated surface, the amount of introduced gas; hexamethyldisiloxane: oxygen gas: helium = 1.0: 3.0: 3.0 (unit: slm), in a vacuum chamber The degree of vacuum was 2-6 × 10 ⁻⁶ mBar, the degree of vacuum in the deposition chamber was 2-5 × 10 ⁻³ mBar, the cooling / electrode drum supply power was 10 kW, the line speed was 100 m / 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) Laminate a biaxially stretched polyethylene terephthalate film having a gas barrier coating film produced in (2) above with an ethylene-α / olefin copolymer film 60 μm polymerized using a metallocene catalyst facing the film. An adhesive for coating was used, and this was coated by a gravure roll coating method so as to have a film thickness of 4.0 g / m ² (dry state) and laminated.

(4) Next, a polyethyleneimine-based anchor coating agent is applied to the gas barrier coating film of the film formed in the above (3) by a gravure roll coating method so that the film thickness becomes 0.1 g / m ² (dry state). The anchor coat layer was formed by coating and drying, and a low density polyethylene resin layer was formed by extrusion laminating a low density polyethylene resin to the anchor coat layer at an extrusion temperature of 320 ° C. and an extrusion film thickness of 15 μm.

(5) One surface of a paper substrate (basis weight 400 g / m ² ) was subjected to a corona discharge treatment, and then a low density polyethylene resin (extrusion temperature: 320 ° C., extrusion film thickness: 20 μm) was extrusion coated to form a low density polyethylene resin layer.

(6) Polyethyleneimine-based anchor coating agent is coated and dried on the non-coated surface of the paper substrate by a gravure roll coating method to a film thickness of 0.1 g / m ² (dry state). An anchor coat layer is provided, and then the surface of the low density polyethylene resin layer formed in (4) above of the film having a gas barrier coating film is opposed to the anchor coat layer, and the low density polyethylene resin (extrusion) is formed between the layers. (Temperature: 320 ° C., extrusion film thickness: 15 μm) and extrusion laminated to laminate, PE 20 μm / paper base material 400 μm / PE 15 μm / PE 15 μm / anchor coat layer (polyethyleneimine compound) / gas barrier coating film / inorganic oxidation The laminated material which consists of a material vapor deposition layer (CVD) / PET / DL / m-PEF60micrometer was manufactured.

  (7) Using the above laminated material, according to the shape of a gobeltop liquid paper container, engraved creases in the vertical, horizontal or diagonal directions, and stamped to obtain a blank plate having an adhesive margin The end surface of the blank plate is subjected to skive and hemming treatment to prevent penetration of contents, liquid leakage, etc., and then subjected to end surface treatment. Part of the low-density polyethylene film was melted, and the other end of the blank plate was superposed on the melted surface and bonded together to form a cylinder-sealed seal part to produce a cylindrical sleeve. The inner surface of the bottom of the cylindrical sleeve manufactured above is blown with hot air, the low-density polyethylene film on the inner surface is melted, press-sealed to form a bottom seal portion, and juice juice is poured from the other opening. After filling, the inner surface of the top is scooped with hot air, the low-density polyethylene film on the inner surface is melted, press-sealed to form a gobel top seal portion, and the contents according to the present invention filled and packaged are sealed A liquid paper container was manufactured.

Example 2
(1) A biaxially stretched polyethylene terephthalate film having a gas barrier coating film was produced in the same manner as in (1) and (2) of Example 1.

(2) Next, a polyethyleneimine anchor coating agent is applied to the gas barrier coating film of the film formed in the above (1) by a gravure roll coating method so that the film thickness becomes 0.1 g / m ² (dry state). The anchor coat layer was formed by coating and drying.

(3) On the other hand, after applying corona discharge treatment to one surface of a paper substrate (basis weight 400 g / m ² ), a low density polyethylene resin is used on the corona discharge treatment surface, and this is extrusion coated. A 20 μm thick low density polyethylene resin layer was formed as the outermost layer.

(4) Next, using a tandem extrusion laminating machine, a film thickness of 0.1 g / m ² (in a dry state) is applied to the uncoated surface of the paper substrate by a gravure roll coating method using a polyethyleneimine anchor coating agent. The anchor coat layer is formed by coating and drying so that the surface of the anchor coat layer of the above (2) is opposed to the surface of the anchor coat layer, and the low-density polyethylene resin (extrusion temperature: 310 degreeC and extrusion film thickness 30micrometer) were used, the said paper base material and the film which has a gas-barrier coating film were bonded together, and the 1st extrusion lamination process was performed.

  Then, as a second extrusion lamination step, a two-component curable anchor coating agent was applied to the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm with a gravure coater and passed through a drying furnace. An ethylene-α / olefin copolymer film (film thickness 40 μm) polymerized using a metallocene catalyst is opposed to the anchor coat surface, and a low density polyethylene resin (extrusion temperature: 320 ° C., extrusion film thickness) is interposed between the layers. : 20 μm), both of which are extruded with polyethylene sand, and then subjected to an aging treatment in a constant temperature bath at 40 ° C. for 3 days to give PE 20 μm / paper substrate 400 μm / PE 30 μm / anchor coat layer (polyethyleneimine system) Compound) / Gas barrier coating film / Inorganic oxide vapor deposition layer (CVD) / PET / PE To produce a laminate consisting of 0μm / m-PEF40μm.

  (5) Using the above laminated material, in accordance with the shape of the gobeltop type liquid paper container, engraved creases in the vertical, horizontal, or diagonal directions, and punched into a blank plate having an adhesive margin After manufacturing, and then performing end face treatment by applying skive hemming to the end face of the blank board produced above to prevent permeation of contents, liquid leakage, etc., hot air treatment is applied to the glue margin And melt the low-density polyethylene film of the adhesive margin, and overlap the other end of the blank plate on the melted surface to bond them together to form a cylinder-sealed seal portion. Sleeves were manufactured.

  Next, the inner surface of the bottom of the cylindrical sleeve manufactured above is scrubbed with hot air, the low-density polyethylene film on the inner surface is melted, press-sealed to form a bottom seal portion, and then the other side After filling the juice juice from the opening, hot air the inner surface of the top, melt the low-density polyethylene film on the inner surface, press seal to form the Goebel top seal part, filling the packaging A sealed liquid paper container according to the present invention was manufactured.

Example 3
(1) A biaxially stretched polyethylene terephthalate film with a thickness of 12 μm having a corona-treated surface on one side is attached to a take-up roll of a wind-up type vacuum vapor deposition apparatus, and then this is fed out to deposit aluminum. Using an oxygen gas as a source, an aluminum oxide vapor deposition film having a thickness of 200 mm was formed under the following vapor deposition conditions by an electron beam heating vacuum deposition method.

That is, the degree of vacuum in the vacuum chamber: 2 × 10 ⁻⁴ mBar, the degree of vacuum in the take-up chamber: 2 × 10 ⁻² mBar, cooling / electrode drum power supply: 25 kW, line speed: 240 m / min.

Next, immediately after forming a vapor deposition film of aluminum oxide having a thickness of 200 mm, a glow discharge plasma generator was used on the vapor deposition film surface of the aluminum oxide, 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, using the barrier coating solution in the same manner as in Example 1, this was coated on the plasma-treated surface of (1) by the gravure roll coating method, and then at 140 ° C. for 60 seconds. A heat treatment was performed to form a gas barrier coating film having a thickness of 0.3 μm (in the dry operation state).

(3) Laminate a biaxially stretched polyethylene terephthalate film having a gas barrier coating film produced in (2) above with an ethylene-α / olefin copolymer film 60 μm polymerized using a metallocene catalyst facing the film. An adhesive for coating was used, and this was coated by a gravure roll coating method so as to have a film thickness of 4.0 g / m ² (dry state) and laminated.

(4) Next, a polyethyleneimine-based anchor coating agent is applied to the gas barrier coating film of the film formed in the above (3) by a gravure roll coating method so that the film thickness becomes 0.1 g / m ² (dry state). The anchor coat layer was formed by coating and drying. The anchor coat layer was extrusion laminated at an extrusion temperature of 320 ° C. and an extrusion film thickness of 15 μm to form a low density polyethylene resin layer.

(5) One surface of a paper substrate (basis weight 400 g / m ² ) was subjected to a corona discharge treatment, and then a low density polyethylene resin (extrusion temperature: 320 ° C., extrusion film thickness: 20 μm) was extrusion coated to form a low density polyethylene resin layer.

(6) Polyethyleneimine-based anchor coating agent is coated and dried on the non-coated surface of the paper substrate by a gravure roll coating method to a film thickness of 0.1 g / m ² (dry state). An anchor coat layer is provided, and then the surface of the low density polyethylene resin layer formed in (4) above of the film having a gas barrier coating film is opposed to the anchor coat layer, and the low density polyethylene resin (extrusion) is formed between the layers. (Temperature: 320 ° C., extrusion film thickness: 15 μm) and extrusion laminated to laminate, PE 20 μm / paper base material 400 μm / PE 15 μm / PE 15 μm / anchor coat layer (polyethyleneimine compound) / gas barrier coating film / inorganic oxidation The laminated material which consists of a material vapor deposition layer (PVD) / PET / DL / m-PEF60micrometer was manufactured.

  (7) Using the above laminated material, according to the shape of a gobeltop liquid paper container, engraved creases in the vertical, horizontal or diagonal directions, and stamped to obtain a blank plate having an adhesive margin The end surface of the blank plate is subjected to skive and hemming treatment to prevent penetration of contents, liquid leakage, etc., and then subjected to end surface treatment. Part of the low-density polyethylene film was melted, and the other end of the blank plate was superposed on the melted surface and bonded together to form a cylinder-sealed seal part to produce a cylindrical sleeve. The inner surface of the bottom of the cylindrical sleeve manufactured above is blown with hot air, the low-density polyethylene film on the inner surface is melted, press-sealed to form a bottom seal portion, and juice juice is poured from the other opening. After filling, the inner surface of the top is scooped with hot air, the low-density polyethylene film on the inner surface is melted, press-sealed to form a gobel top seal portion, and the contents according to the present invention filled and packaged are sealed A liquid paper container was manufactured.

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

(2) An ethylene-α / olefin copolymer film 60 μm polymerized using a metallocene catalyst is made to face the biaxially stretched polyethylene terephthalate film surface of the film produced above, and a laminating adhesive is gravure-rolled. Coating was performed by coating so that the film thickness was 4.0 g / m ² (dry state).

(3) Next, a two-component curable anchor coating agent is used for the gas barrier coating film, and this is coated by a gravure roll coating method to a film thickness of 0.2 g / m ² (dry state). An anchor coat layer was formed, and a low density polyethylene resin layer was formed by extrusion laminating a low density polyethylene resin to the anchor coat layer at an extrusion temperature of 320 ° C. and an extrusion film thickness of 15 μm.

(4) One surface of a paper substrate (basis weight 400 g / m ² ) was subjected to a corona discharge treatment, and then the low-density polyethylene resin (extrusion temperature: 320 ° C., extrusion film thickness: 20 μm) was extrusion coated to form a low density polyethylene resin layer.

(5) A polyethyleneimine-based anchor coating agent is coated and dried on the uncoated surface of the paper substrate by a gravure roll coating method so as to have a film thickness of 0.1 g / m ² (dry state). An anchor coat layer is provided, and then the surface of the low density polyethylene resin layer formed in (3) above of the film having a gas barrier coating film is opposed to the anchor coat layer, and the low density polyethylene resin (extrusion) is formed between the layers. Temperature: 320 ° C., extrusion film thickness: 15 μm) is melt-extruded and laminated by extrusion lamination, PE 20 μm / paper substrate 400 μm / PE 15 μm / PE 15 μm / anchor coat layer (two-component curable anchor coat agent) / gas barrier coating film / A laminated material composed of inorganic oxide vapor deposition layer (CVD) / PET / DL / m-PEF 60 μm was produced.

  (6) Using the above laminated material, in accordance with the shape of the gobeltop type liquid paper container, engraved creases in the vertical, horizontal, or diagonal directions, and punched into a blank plate having an adhesive margin The end surface of the blank plate is subjected to skive and hemming treatment to prevent penetration of contents, liquid leakage, etc., and then subjected to end surface treatment. Part of the low-density polyethylene film was melted, and the other end of the blank plate was superposed on the melted surface and bonded together to form a cylinder-sealed seal part to produce a cylindrical sleeve. The inner surface of the bottom of the cylindrical sleeve manufactured above is blown with hot air, the low-density polyethylene film on the inner surface is melted, press-sealed to form a bottom seal portion, and juice juice is poured from the other opening. After filling, the inner surface of the top is scooped with hot air, the low-density polyethylene film on the inner surface is melted, press-sealed to form a gobel top seal portion, and the contents according to the present invention filled and packaged are sealed A liquid paper container was manufactured.

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

(2) Next, a polyethyleneimine anchor coating agent is applied to the gas barrier coating film of the film formed in the above (1) by a gravure roll coating method so that the film thickness becomes 0.1 g / m ² (dry state). The anchor coat layer was formed by coating and drying.

(3) On the other hand, after applying corona discharge treatment to one surface of a paper substrate (basis weight 400 g / m ² ), a low density polyethylene resin is used on the corona discharge treatment surface, and this is extrusion coated. A 20 μm thick low density polyethylene resin layer was formed as the outermost layer.

(4) Next, using a tandem extrusion laminating machine, a film thickness of 0.1 g / m ² (in a dry state) is applied to the uncoated surface of the paper substrate by a gravure roll coating method using a polyethyleneimine anchor coating agent. The anchor coat layer is formed by coating and drying so that the surface of the anchor coat layer faces the surface of the anchor coat layer of (2) above, and an ethylene-methacrylic acid copolymer ( Extrusion temperature: 280 ° C., extrusion film thickness 30 μm), the above-mentioned paper base material and a film having a gas barrier coating film were bonded to each other, and a first extrusion lamination process was performed.

  Next, as a second extrusion lamination step, a two-component curable anchor coating agent was applied to the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm with a gravure coater and passed through a drying furnace. An ethylene-α / olefin copolymer film (film thickness 40 μm) polymerized using a metallocene catalyst is opposed to the anchor coat surface, and a low density polyethylene resin (extrusion temperature: 320 ° C., extrusion film thickness) is interposed between the layers. : 20 μm), both of which are extruded while being polyethylene-sanded, and then subjected to an aging treatment in a constant temperature bath at 40 ° C. for 3 days, PE 20 μm / paper substrate 400 μm / EMAA 30 μm / anchor coat layer (polyethyleneimine) Compound) / Gas barrier coating film / Inorganic oxide deposition layer (CVD) / PET To produce a laminate consisting of PE20μm / m-PEF40μm.

  (5) Using the above laminated material, in accordance with the shape of the gobeltop type liquid paper container, engraved creases in the vertical, horizontal, or diagonal directions, and punched into a blank plate having an adhesive margin After manufacturing, and then performing end face treatment by applying skive hemming to the end face of the blank board produced above to prevent permeation of contents, liquid leakage, etc., hot air treatment is applied to the glue margin And melt the low-density polyethylene film of the adhesive margin, and overlap the other end of the blank plate on the melted surface to bond them together to form a cylinder-sealed seal portion. Sleeves were manufactured.

  Next, the inner surface of the bottom of the cylindrical sleeve manufactured above is scrubbed with hot air, the low-density polyethylene film on the inner surface is melted, press-sealed to form a bottom seal portion, and then the other side After filling the juice juice from the opening, hot air the inner surface of the top, melt the low-density polyethylene film on the inner surface, press seal to form the Goebel top seal part, filling the packaging A sealed liquid paper container according to the present invention was manufactured.

Evaluation Method The oxygen permeability and laminate strength of the laminates produced in Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated. The results are shown in Table 2.

(1) 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.

(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 liquid paper container according to the present invention is excellent in laminate strength and gas barrier properties and is useful.

1 (a) and 1 (b) are cross-sectional views illustrating a laminated material constituting the liquid paper container of the present invention. 2 (a) and 2 (b) are cross-sectional views illustrating the laminated material constituting the liquid paper container of the present 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 fusion layer,
A ... outermost layer,
B: paper substrate,
C: Gas barrier laminate film layer,
D: innermost layer,
E: Adhesive resin layer.

Claims (15)

A liquid paper container formed by boxing a laminated material in which an outermost layer, a paper base material, a gas barrier laminate film layer, and an innermost layer are laminated in this order,
The gas barrier laminate film layer is provided with an inorganic oxide vapor-deposited film on the base film surface, a gas barrier coating film made of a gas barrier composition on the surface of the inorganic oxide vapor-deposited film, and the gas barrier property A liquid paper container in which an anchor coat layer made of an anchor coat composition containing polyethyleneimine is provided on a coating film, and a heat-sealing layer is laminated on the anchor coat layer.   The liquid paper container according to claim 1, wherein the heat-sealing layer of the gas barrier laminate film layer and the paper base material are laminated facing each other.   The liquid paper container according to claim 2, wherein the gas barrier laminated film layer is laminated to face the paper substrate through an adhesive resin layer.   The liquid paper container according to any one of claims 1 to 3, wherein the outermost layer, the innermost layer and / or the adhesive resin layer are made of a polyolefin resin layer having heat-fusibility.   The heat-fusible layer constituting the gas-barrier laminated film layer and / or the heat-adhesive resin layer constituting the laminated material is laminated by heat-extrusion resin by melt extrusion lamination. The liquid paper container in any one of 1-4.   The heat-fusible layer constituting the gas barrier laminate film layer and / or the heat-adhesive resin layer constituting the laminate are laminated by heat-extrusion polyolefin-based resin by melt extrusion lamination, The liquid paper container in any one of Claims 1-5. The liquid paper container according to claim 1, wherein the paper base material is a paper base material having a basis weight of 80 to 600 g / m ² .   The liquid paper container according to any one of claims 1 to 7, wherein the base film constituting the gas barrier laminate film layer comprises a biaxially stretched resin film.   9. The liquid paper container 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.   9. The liquid paper container according to claim 1, wherein the inorganic oxide vapor-deposited film is an organic silicon compound vapor-deposited film formed by a chemical vapor deposition method.   The liquid paper container according to any one of claims 1 to 8, wherein the inorganic oxide vapor-deposited film comprises an aluminum oxide vapor-deposited film formed by physical vapor deposition.   The said innermost layer consists of a resin layer by the copolymer with ethylene- unsaturated carboxylic acid or its esterified material, The liquid paper container in any one of Claims 1-11 characterized by the above-mentioned.   12. The liquid paper container according to claim 1, wherein the innermost layer is composed of a resin layer melt-extruded at 310 ° C. or less by a copolymer with an ethylene-unsaturated carboxylic acid or an esterified product thereof.   The innermost layer is composed of a copolymer with an ethylene-unsaturated carboxylic acid or an esterified product thereof, and further contains a copolymer containing 5 to 30 mol% of the unsaturated carboxylic acid or the esterified product constituting the copolymer. The liquid paper container according to claim 1, comprising a resin layer made of a polymer. The gas barrier coating film has a 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, m represents an integer of 1 or more, and n + m represents a valence of M.), a polyvinyl alcohol resin and / or The liquid paper container in any one of Claims 1-14 which is a gas-barrier coating film by the gas-barrier composition which contains an ethylene vinyl alcohol copolymer and is further polycondensed by the sol-gel method.

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