JP2006056007A - Gas barrier laminated film and laminated material using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas barrier laminated film keeping high gas barrier properties stably, especially enhanced in steam barrier properties and having good transparency, moistureproof properties, impact resistance, hot water resistance, adhesion and the like, and a laminated material using it. <P>SOLUTION: The gas barrier laminated film is constituted by successively laminating a gas barrier coating film, which comprises a gas barrier composition containing at least one kind of an alkoxide represented by the general formula: R<SP>1</SP><SB>n</SB>M(OR<SP>2</SP>)<SB>m</SB>(wherein R<SP>1</SP>and R<SP>2</SP>are each a 1-8C organic group, M is a metal atom, n is an integer of 0 or above, m is an integer of 1 or above and n+m is the valency of M), a polyvinyl alcohol resin and/or an ethylene-vinyl alcohol copolymer and obtained by polycondensation due to a sol-gel method and a vapor deposition film of an inorganic oxide on one side of a base material film. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a gas barrier laminate film and a laminate using the same, and more specifically, has excellent gas barrier properties that prevent permeation of oxygen gas, water vapor, etc., and further has transparency, moisture resistance, and impact resistance. The present invention relates to a gas barrier laminate film excellent in properties, hot water resistance, tight adhesion, and the like, and a laminate using the same.

Conventionally, as packaging materials for filling and packaging foods, beverages, chemicals, miscellaneous goods, etc., the permeation of oxygen gas, water vapor, etc. is blocked in order to prevent deterioration, discoloration, etc. of the contents to be filled and packaged. Barrier substrates having various forms have been developed and proposed.
For example, an aluminum foil or a vapor-deposited film thereof has been proposed as the most typical one, but this one exhibits an extremely stable gas barrier property. There is a problem that it is inferior to incineration, and disposal processing after use is not easy, and there is also a problem that transparency is lacking.

In order to cope with this, for example, it is attempted to use a barrier resin film that blocks or prevents permeation of oxygen gas, water vapor, and the like made of polyvinylidene chloride resin, ethylene-vinyl alcohol copolymer, etc. It has been.
However, since the polyvinylidene chloride resin contains chlorine atoms in its structure, when it is incinerated as waste after use, harmful chlorine gas is generated, which is unfavorable for environmental hygiene.
On the other hand, the ethylene-vinyl alcohol copolymer has the advantages that the oxygen permeability is low and the adsorptivity of the flavor component is low, but there is a problem that the gas barrier property is remarkably lowered when it comes into contact with water vapor. .
For this reason, in order to block the ethylene-vinyl alcohol copolymer as a barrier base material from water vapor, it is necessary to make it a complicated laminated structure, and the fact is that the manufacturing cost is increasing.

Therefore, in recent years, a barrier layer made of a thin film of an inorganic oxide such as silicon oxide or aluminum oxide has been provided as a barrier material that exhibits high gas barrier properties and fragrance stability stably and has transparency. Barrier substrates have been developed and proposed.
Thus, the above-mentioned barrier base material is made of, for example, silicon oxide, aluminum oxide or the like on one surface of a base film made of a resin film such as a polyester resin, a polyamide resin, or a polypropylene resin. It is manufactured by depositing an inorganic oxide by vacuum deposition and providing a thin film of the inorganic oxide.
This product has excellent gas barrier properties that prevent the permeation of oxygen gas, water vapor, etc., and has excellent transparency. Also, after use, it is suitable for disposal without generating harmful substances during incineration disposal. It is excellent in environmental suitability and the like, and its use is developed in various fields, and the demand is expanding.
However, the barrier layer made of a thin film of an inorganic oxide such as silicon oxide or aluminum oxide is simply obtained by heating and vaporizing the inorganic oxide to deposit and deposit the particles on the base film. Therefore, there is a gap called a grain boundary between the inorganic oxide particles, and although it has excellent gas barrier properties, it cannot be said to have sufficiently satisfactory gas barrier properties. The fact is that there is.
For this reason, for example, an improvement proposal such as increasing the film thickness (500 to 1000 mm) or decreasing the oxygen atom ratio in the inorganic oxide thin film to improve the gas barrier property is proposed. However, on the other hand, for example, when the film thickness is increased, the transparency is lowered, and by increasing the film thickness, the thin film of the inorganic oxide is inferior in stretchability, spreadability, etc., and cracks etc. There are various problems such as being easy to occur and poor adhesion between the base film and the particles constituting the inorganic oxide thin film.

Therefore, in order to solve the problems of the barrier base material having a barrier layer made of a thin film of an inorganic oxide such as silicon oxide and aluminum oxide as described above, and improve its gas barrier performance, for example, a plastic substrate A barrier substrate comprising a multilayer laminate in which an olefin-vinyl acetate copolymer saponified resin layer having a thickness of at least 1 μm is laminated on a metal or metal oxide thin film formed on the surface of the material. It has been proposed (see, for example, Patent Document 1).
Also, a barrier substrate made of a multilayer laminate in which a polyvinyl alcohol-based resin layer having a thickness of at least 3 μm is laminated on a metal or metal oxide thin film formed on the surface of a plastic substrate. It has been proposed (see, for example, Patent Document 2).
Further, a barrier made of a gas barrier film in which at least one surface of the base film layer (1) is coated with a barrier resin coating layer (3) via an inorganic substance (2) having transparency. Also proposed is a conductive substrate (see, for example, Patent Document 3).
JP-A-6-246868 (Claims etc.) JP-A-6-316025 (Claims etc.) Japanese Patent Laid-Open No. 7-80986 (claims, etc.)

Further, for example, a vapor deposition layer made of an inorganic compound is used as a first layer on a base material made of a polymer resin composition, and a water-soluble polymer and (a) one or more alkoxides and / or a hydrolyzate thereof or (B) Applying a coating agent mainly composed of an aqueous solution containing at least one of tin chlorides or a water / alcohol mixed solution, followed by heating and drying, and laminating a gas barrier film as a second layer. There has also been proposed a gas barrier laminate film characterized in that it is formed (see, for example, Patent Document 4).
Further, in the transparent gas barrier laminate film having a metal oxide layer on at least one surface of the transparent polymer film, the portion of the alkoxysilane represented by the following general formula (1) is in contact with the metal oxide (part) A transparent gas barrier laminate film comprising a cured film containing a polyvinyl alcohol crosslinked with a hydrolyzate, a (partial) condensate thereof, or a mixture thereof.
R ¹ _n —Si (OR ² ) _4-n (1)
(Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms; vinyl group; or an organic group having one or more groups selected from the group consisting of a methacryloxy group, an epoxy group, and a mercapto group, and R ² is a carbon number. 1 to 4 alkyl groups and n is an integer of 0 to 2) has also been proposed (see, for example, Patent Document 5).
Japanese Patent No. 2790054 (Claims etc.) Japanese Patent No. 3403880 (claims, etc.)

However, in the barrier base material proposed in the above Patent Documents 1 to 3, for example, the hydroxyl group in the olefin-vinyl acetate copolymer saponified resin layer or the polyvinyl alcohol-based resin layer A polar group such as an amide group easily binds to water molecules, and therefore, there is a problem in that its gas barrier property decreases as the environmental humidity increases.
That is, as the contents to be filled and packaged, for example, when filling and packaging a liquid containing moisture, or a food or drink containing moisture, the gas barrier property is reduced due to the moisture vapor etc. of the contents, and during storage There is a problem that the quality of the contents deteriorates and changes.
In addition, depending on the food and drink to be filled and packaged, the packaged product may be manufactured by sterilizing with hot water by boil treatment or retort treatment after filling and packaging. The substrate has a problem that the gas barrier property is remarkably deteriorated during the treatment, and further, the adhesive strength and the like are lowered, the mechanical strength is deteriorated, and is not suitable for the sterilization treatment method as described above. .
Moreover, in the barrier base material proposed in the above Patent Documents 4 to 5, a high gas barrier property can be obtained, and the oxygen barrier property has sufficient performance. For example, in the same manner as described above, when a packaged product is manufactured by filling and packaging food and drink, followed by boil treatment or retort treatment with hot water to produce a packaged product, The material is inferior in water vapor barrier property, the gas barrier property is remarkably deteriorated during processing, the adhesive strength is also lowered, delamination is caused, and the mechanical strength is also deteriorated. The fact is that it is not suitable for such a sterilization treatment method.
Therefore, in view of the circumstances as described above, the present invention stably maintains a high gas barrier property, particularly improves the water vapor barrier property, and has good transparency, moisture resistance, and impact resistance. An object of the present invention is to provide a barrier film having hot water resistance, tight adhesion, and the like and a laminate using the same.

As a result of various studies to solve the above-mentioned problems, the present inventor firstly performed chemical vapor deposition on one surface of the base film, if necessary, through a plasma treatment surface with an inert gas. Alternatively, an inorganic oxide vapor-deposited film is formed by physical vapor deposition, and the general formula R ¹ _n M (through a plasma-treated surface with oxygen gas, if necessary, on the surface of the inorganic oxide vapor-deposited film. OR ² ) _m (wherein, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, and m represents 1) And at least one alkoxide represented by the following formula: n + m represents the valence of M), and a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer. Furthermore, according to a gas barrier composition obtained by polycondensation by a sol-gel method Gas barrier coating film is provided, and further, if necessary, vapor deposition of inorganic oxide by chemical vapor deposition method or physical vapor deposition method through plasma treatment surface with inert gas on the surface of the gas barrier coating film. A gas barrier laminated film is produced by providing a film, and further, the gas barrier laminated film is used, and if necessary, a plasma treatment with oxygen gas is performed on the surface of the vapor-deposited film of the inorganic oxide constituting the gas barrier laminated film. A laminated material is produced by laminating a heat-sealable resin layer via a surface and / or a primer agent layer, and using the laminated material, a bag is produced from the resulting laminated material. In the packaging bag, for example, when a packaged product is manufactured by filling and packaging contents such as food and drink, etc., it is excellent in gas barrier properties to prevent permeation of oxygen gas, water vapor, etc. Transparency and prevention A gas barrier laminate film that is excellent in heat resistance, impact resistance, hot water resistance, tight adhesion, etc., and can prevent the occurrence of delamination and the like, and a laminate material, a packaging bag, etc. using the gas barrier laminate film The present invention has been found and completed.

That is, according to the present invention, an inorganic oxide vapor deposition film is provided on one surface of the base film, and then the general formula R ¹ _n M (OR ² ) _m ( However, in the formula, R ^1, R ² represents an organic group having 1 to 8 carbon atoms, M represents a metal atom, n is an integer of 0 or more, m represents an integer of 1 or more N + m represents the valence of M.) and contains a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer, and a sol-gel method. A gas barrier laminate film comprising a gas barrier composition obtained by polycondensation by a gas barrier composition, and further, an inorganic oxide vapor deposition film is provided on the surface of the gas barrier coating film, and a gas barrier laminate film comprising the same It relates to the laminated material used.

In the gas barrier laminate film and the laminate using the same according to the present invention, an oxygen gas, water vapor is obtained by laminating an inorganic oxide vapor deposition film, a gas barrier coating film, and an inorganic oxide vapor deposition film in multiple layers. Excellent gas barrier properties, especially water vapor barrier properties that prevent permeation, etc., and excellent post-processing suitability such as laminating, bag making, etc. The water-resistant strength in such as can be remarkably improved, and is extremely excellent in moisture-proof property.
Further, in the gas barrier laminate film according to the present invention and the laminate using the same, when laminating the inorganic oxide deposition film, the gas barrier coating film and the inorganic oxide deposition film on the base film, By laminating each surface with a plasma-treated surface with an inert gas or a plasma-treated surface with oxygen gas or a primer material layer, the tight adhesion between each layer can be made extremely strong, Their tight adhesion is remarkably improved, and phenomena such as delamination (delamination) between those layers are not recognized at all, and the lamination strength can be remarkably improved. It has the advantage that it is extremely excellent in water resistance.
In the present invention, the gas barrier coating film comprises a very strong three-dimensional network composite polymer in which a polyvinyl alcohol resin or an ethylene / vinyl alcohol copolymer and one or more alkoxides chemically react with each other. -Consists of a layer, and a vapor deposition film of inorganic oxide synergizes with it, maintaining an extremely high gas barrier property in a stable manner, as well as good transparency, impact resistance, hot water resistance, and tight adhesion It is possible to produce a gas barrier laminate film and a laminate provided with properties and the like.
In particular, in the present invention, when a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer are used in combination, the polyvinyl alcohol-based resin and at least one alkoxide, the ethylene / vinyl alcohol copolymer, and at least one or more types are used. An alkoxide, a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer, and one or more alkoxides are combined to form a very complex hybrid three-dimensional network composite polymer layer. Therefore, they and the vapor-deposited films of inorganic oxides synergistically maintain an extremely high gas barrier property, and in particular, the oxygen gas barrier property and the water vapor barrier property are remarkably improved, and good transparency is achieved. , Gas barrier laminate film and laminate material having impact resistance, hot water resistance, tight adhesion, etc. Those that can be obtained to produce.

The gas barrier laminate film and the laminate using the same according to the present invention will be described below in more detail with reference to the drawings.
1, 2 and 3 are schematic cross-sectional views showing a few examples of the layer structure of the gas barrier laminate film according to the present invention, and FIGS. 4, 5 and 6 show the gas barrier according to the present invention. FIG. 7 and FIG. 8 are schematic cross-sectional views showing a few examples of the layer structure of a laminated material using a porous laminated film, and FIGS. 7 and 8 are bag-making using the laminated material using the gas barrier laminated film according to the present invention. It is a schematic perspective view which shows an example of the structure about the packaging bag which was made.

First, as shown in FIG. 1, the gas barrier laminate film A according to the present invention is provided with an inorganic oxide vapor-deposited film 2 on one surface of a base film 1, and then the inorganic oxide vapor-deposited film. 2 on the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, and n represents , 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-based resin and / or A gas barrier coating film 3 comprising a gas barrier composition containing an ethylene / vinyl alcohol copolymer and obtained by polycondensation by a sol-gel method; Containing a structure in which an oxide vapor deposition film 4 is provided as a basic structure It is.

Thus, a specific example of the gas barrier laminate film according to the present invention is illustrated as shown in FIG. 2 on one surface of the base film 1, if necessary, through a plasma treatment surface 5 with an inert gas. Then, an inorganic oxide vapor-deposited film 2 is formed by chemical vapor deposition or physical vapor deposition, and then the surface of the inorganic oxide vapor-deposited film 2 is, if necessary, a plasma-treated surface 6 with oxygen gas. , 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, and n represents 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 polyvinyl alcohol-based resin and / or ethylene.・ Contains vinyl alcohol copolymer and is further condensed by sol-gel method A first gas barrier coating film 3 made of the gas barrier composition obtained in combination is provided, and further, if necessary, a chemical treatment is performed on the surface of the gas barrier coating film 3 via a plasma treatment surface 7 with an inert gas. Examples thereof include a barrier film A ₁ having a configuration in which a vapor-deposited film 4 of an inorganic oxide by a vapor phase growth method or a physical vapor phase growth method is provided.

Moreover, when another example is illustrated about the gas-barrier laminated | multilayer film which concerns on this invention, as shown in FIG. 3, if needed, it will pass through the plasma processing surface 5 by an inert gas as needed. Then, an inorganic oxide vapor-deposited film 2 is formed by chemical vapor deposition or physical vapor deposition, and then a plasma-treated surface 6 with oxygen gas is provided on the surface of the inorganic oxide vapor-deposited film 2 if necessary. And 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, and n represents 0 And m represents an integer of 1 or more, and n + m represents a valence of M.), at least one alkoxide represented by the following formula: polyvinyl alcohol resin and / or ethylene Contains vinyl alcohol copolymer and polycondensation by sol-gel method The first gas barrier coating film 3 made of the gas barrier composition obtained as described above is provided, and further, if necessary, the chemical vapor is formed on the surface of the gas barrier coating film 3 via the plasma treatment surface 7 using an inert gas. An inorganic oxide vapor-deposited film 4 formed by a phase growth method or a physical vapor deposition method is provided, and furthermore, the surface of the inorganic oxide vapor-deposited film 4 and, if necessary, a plasma-treated surface 8 and / or polyester with oxygen gas A gas barrier laminate film A ₂ according to the present invention having a constitution in which a primer agent layer 9 made of a composition containing a main resin or a polyurethane resin as a main component of a vehicle can be exemplified.

Next, in the present invention, the laminated material using the gas barrier laminated film according to the present invention will be described by exemplifying the case of the laminated material using the gas barrier laminated film A according to the present invention shown in FIG. As shown in FIG. 4, a structure in which a heat-seal resin layer 11 is laminated on the surface of the inorganic oxide vapor deposition film 4 constituting the gas barrier laminate film A according to the present invention shown in FIG. A laminated material B using the gas barrier laminate film according to the present invention, or an inorganic oxide vapor deposition film constituting the gas barrier laminate film A according to the present invention shown in FIG. 1 as shown in FIG. 4 is a laminate B ₁ using a gas barrier laminate film according to the present invention comprising a structure in which a heat-seal resin layer 11 is laminated on the surface of 4 via an intermediate substrate 12, and further shown in FIG. So on A plastic substrate 13 is further laminated on the other surface of the substrate film 1 constituting the gas barrier laminate film A according to the present invention shown in FIG. 1, and the gas barrier laminate film A according to the present invention is constructed. Examples thereof include a laminate B ₂ using a gas barrier laminate film according to the present invention having a structure in which a heat-seal resin layer 11 is laminated on the surface of the inorganic oxide vapor deposition film 4.
In FIG. 4, FIG. 5, and FIG. 6, reference numerals 1, 2, 3, 4 and the like have the same meaning as reference numerals 1, 2, 3, 4, and the like shown in FIG.
Of course, in the present invention, although not shown, the gas barrier laminate film according to the present invention shown in FIG. 2 and FIG. 3 is used, and the gas barrier laminate according to the present invention is the same as above. It is possible to produce a laminated material using a film.

  Furthermore, in this invention, if the example is given about the packaging bag which made a bag using the gas-barrier laminated film which concerns on this invention, and a laminated material using the same, as this packaging bag concerning this invention, The packaging bag made using the laminated material B shown in FIG. 4 will be described as an example. As shown in FIG. 7, two laminated materials B and B are prepared, and the innermost layer thereof is prepared. Heat seal resin layers 11, 11 positioned on each other are overlapped with each other, and thereafter, heat seal is applied to three ends of the outer periphery and heat seal portions 15, 15 and 15, and an opening 16 is formed thereabove to form a three-sided seal type according to the present invention, which is made by using the gas barrier laminate film according to the present invention and the laminate material using the gas barrier laminate film. A packaging bag C can be manufactured.

Thus, in the present invention, as shown in FIG. 8, the three-sided seal according to the present invention produced by using the gas barrier laminate film according to the present invention produced above and the laminate material using the same is manufactured. The packaging bag C of the mold is used, and, for example, the contents 17 such as food and drink are filled from the opening portion 16, and then the upper opening portion 16 is heat sealed and the upper sealing portion is filled. 18 etc. can be formed and the packaging product D which consists of various forms can be manufactured.
In the present invention, although not shown in the drawings, the three-sided seal type packaging bag according to the present invention produced by using the gas barrier laminated film according to the present invention produced above and the laminated material using the same is provided. From the opening, for example, desired food and drink such as curry, stew, soup, meat sauce, hamburger, meatball, sweet potato, oden, etc. And then heat seal the upper opening to form an upper seal or the like to produce a packaged semi-finished product, after which, for example, Temperature, 110 ° C to 130 ° C, pressure, 1 to 3 kgf / cm 2 · Retort treatment such as pressure heat sterilization is applied for about 20 to 60 minutes at the G position to produce retort packaging products of various forms. Is something that can be done.
In addition, in this invention, it replaces with the above retort processes, for example, it can boil for about 30 minutes at about 90 degreeC, and can also heat-sterilize, etc., and can also manufacture a bactericidal treatment packaging product. .
Further, in the present invention, although not shown, using the gas barrier laminate film according to the present invention shown in FIG. 5 and FIG. 6 and a laminate using the same, the same as above, The gas barrier laminate film according to the present invention and a packaging bag, a packaging product, etc., produced using the laminate material using the gas barrier laminate film can be produced.
In the present invention, it is needless to say that the packaging bag, packaged product and the like according to the present invention are not limited to the shape of the illustrated packaging bag illustrated above, and its purpose, use, etc. Thus, packaging bags having various forms such as a four-side seal type, a self-supporting type, a gusset type, a square bottom type, a pillow type, and the like can be manufactured.

The above examples illustrate one or two examples of the gas barrier film according to the present invention, a laminated material using the gas barrier film, a packaging bag made using the laminated material, a packaged product, and the like. However, the present invention is not limited to these.
For example, in the present invention, although not shown in the drawing, the gas barrier laminate film having various forms, a laminate material using the same, and other materials and the like are arbitrarily used depending on the purpose of use, application, and the like, and It is possible to design and manufacture packaging bags, packaging products, etc., which are made using laminated materials.
In addition, for example, although not shown in the drawings, the inorganic oxide vapor-deposited film includes not only a single-layer film composed of one inorganic oxide vapor-deposited film but also two or more layers of inorganic oxide vapor-deposited films. It can also consist of a multilayer film or the like.
Further, for example, although not shown, in the present invention, the gas barrier coating film can be provided not only in one layer but also in two or more layers.
In the present invention, as a method of laminating a laminate using the gas barrier laminate film according to the present invention as described above, although not shown, for example, an anchor coat using an anchor coat agent is used. Via a melt extrusion laminating method in which the adhesive layer is laminated via a melt-extruded resin layer obtained by melt-extruding a polyolefin resin or the like, for example, via a laminating adhesive layer by a laminating adhesive, etc. Can be laminated by a dry lamination method, etc.

Next, in the present invention, the gas barrier laminated film according to the present invention, the laminated material, the packaging bag, the material constituting the packaged product, the production method, etc. will be described. The base film to be described will be described. As such a base film, this is a basic material constituting the gas barrier laminate film according to the present invention, and further, a vapor deposited film of inorganic oxide or a gas barrier coating film, First, it can withstand the conditions of their formation, processing, etc., and can hold them well without impairing their characteristics, In the case of a bag, it is excellent in various physical properties such as workability, heat resistance, slipperiness, pinhole resistance, etc., and also a resin film that can satisfy other conditions - it is possible to use the door.
In the present invention, specific examples of the resin film or sheet include polyolefin resins such as polyethylene resins and polypropylene resins, cyclic polyolefin resins, polystyrene resins, and acrylonitrile-styrene copolymer. Polyester such as coalescence (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate, polyethylene naphthalate Films or sheets of various resins such as polyamide resins, polyamide resins such as various nylon resins, polyurethane resins, acetal resins, cellulose resins, and the like can be used.
In the present invention, it is particularly preferable to use a polyester resin, a polyolefin resin, or a polyamide resin film or sheet among the resin films or sheets.

In the present invention, as the above-mentioned various resin films or sheets, 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 are used. -A method of forming the above-mentioned various resins independently using a film-forming method such as an ionization method or the like, or a method of forming a multilayer co-extrusion film using two or more types of various resins In addition, by using two or more kinds of resins, various film or sheet of resin is manufactured by a method of mixing and forming before forming a film, and if necessary, for example, Various resin films or sheets formed by stretching in a uniaxial or biaxial direction using a tenter system, a tuber system, or the like can be used.
In the present invention, the film thickness of various resin films or sheets is preferably about 6 to 200 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 be used.

By the way, in the gas barrier laminate film according to the present invention, on one surface of the base film as described above, or on the surface of the gas barrier coating film described later, one of the base film and the base film is provided. Chemical vapor deposition method or chemical vapor deposition method provided on the surface of the gas barrier coating film and the gas barrier coating film In order to improve the tight adhesion of the inorganic oxide vapor-deposited film by physical vapor deposition method, etc., in the end, to firmly adhere both of them and prevent the occurrence of delamination, etc. It is preferable to provide a plasma-treated surface with an inert gas on one surface of the base film or the surface of a gas barrier coating film described later.
Thus, in the present invention, the plasma processing surface by the inert gas will be described. As the plasma processing surface, the plasma is subjected to surface modification using plasma gas generated by ionizing the gas by arc discharge. A plasma treatment surface can be formed by using a surface treatment method or the like.
That is, in the present invention, a plasma treatment surface is formed by an inert gas by performing a plasma treatment by a plasma surface treatment method using an inert gas such as nitrogen gas, argon gas, helium gas, etc. as a plasma gas. Can do.
In the present invention, as the plasma gas, a mixed gas obtained by further adding oxygen gas to the above inert gas can also be used.
In the present invention, when forming a plasma-treated surface with an inert gas, an inorganic oxide vapor-deposited film by chemical vapor deposition or physical vapor deposition or a gas barrier property is formed on one surface of the substrate film. Immediately before forming a vapor deposition film of an inorganic oxide by chemical vapor deposition or physical vapor deposition on the surface of the coating film, by performing in-line plasma treatment, the surface of the base film or gas barrier coating film is formed. This is desirable because it allows removal of moisture, dust, etc. and surface treatment such as smoothing, activation, etc. of the surface.
Further, in the present invention, it is preferable to perform the plasma discharge treatment in consideration of conditions such as plasma output, plasma gas type, plasma gas supply amount, treatment time, and the like.
In the present invention, as a method for generating plasma, for example, a direct current glow discharge, a high frequency discharge, a microwave discharge, or the like can be used.
Of course, in the present invention, the plasma processing surface can be formed also by the atmospheric pressure plasma processing method.

  Next, in the present invention, an inorganic oxide vapor deposition film provided on one surface of the base film constituting the gas barrier laminate film or the gas barrier coating film according to the present invention will be described. As the vapor deposition film, for example, a chemical vapor deposition method, a physical vapor deposition method, or a combination of both, a single-layer film consisting of one layer of an inorganic oxide vapor deposition film or two or more layers can be used. It can be manufactured by forming a multilayer film or a composite film.

In the present invention, the inorganic oxide vapor-deposited film formed by the chemical vapor deposition method will be described in more detail. Examples of the inorganic oxide vapor-deposited film formed by the chemical vapor deposition method include, A vapor deposition film of an inorganic oxide can be formed using a chemical vapor deposition method (chemical vapor deposition method, CVD method) such as a chemical vapor deposition method or a photochemical vapor deposition method.
In the present invention, specifically, the organic film is formed on one surface of the base film or the surface of the gas barrier coating film provided on the inorganic oxide vapor deposition film provided on the one surface of the base film. Low temperature plasma generator using a monomer gas for vapor deposition such as silicon compound as a raw material, using an inert gas such as argon gas or helium gas as a carrier gas, and further using oxygen gas or the like as an oxygen supply gas A vapor-deposited film of an inorganic oxide such as silicon oxide can be formed using a low-temperature plasma chemical vapor deposition method using the above.
In the above, for example, high-frequency plasma, pulse wave plasma, microwave plasma, or the like can be used as the low-temperature plasma generator. Thus, in the present invention, highly active and stable plasma is obtained. Therefore, it is desirable to use a high-frequency plasma generator.

Specifically, an example of the formation method of the deposited film of the inorganic oxide by the low temperature plasma chemical vapor deposition method will be described as an example. FIG. 9 shows the inorganic oxide deposited by the plasma chemical vapor deposition method. It is a schematic block diagram of the low temperature plasma chemical vapor deposition apparatus which shows the outline | summary about the formation method of a vapor deposition film.
In the present invention, as shown in FIG. 9, a base film 1 or a vapor deposition film of an inorganic oxide is provided from an unwinding roll 23 disposed in a vacuum chamber 22 of a plasma chemical vapor deposition apparatus 21. The base film 1 provided with the gas barrier coating film is fed out, and the base film 1 or the base film 1 provided with the inorganic oxide vapor deposition film and the gas barrier coating film is further provided as an auxiliary roll. 24 is conveyed onto the circumferential surface of the cooling / electrode drum 25 at a predetermined speed.
Thus, in the present invention, oxygen gas, inert gas, a monomer gas for vapor deposition such as an organosilicon compound, and the like are supplied from the gas supply devices 26 and 27 and the raw material volatilization supply device 28, and the like. The vapor deposition mixed gas composition was introduced into the vacuum chamber 22 through the raw material supply nozzle 29 without adjusting the vapor deposition mixed gas composition, and was conveyed onto the cooling / electrode drum 25 peripheral surface. The plasma is generated by the glow discharge plasma 30 on one surface of the base film 1 or on the surface of the gas barrier coating film of the base film 1 provided with an inorganic oxide vapor deposition film and a gas barrier coating film. This is irradiated to form a deposited film of an inorganic oxide such as silicon oxide.
In the present invention, at that time, the cooling / electrode drum 25 is applied with a predetermined power from the power source 31 disposed outside the vacuum chamber 22, and the cooling / electrode drum 25 is disposed in the vicinity of the cooling / electrode drum 25. The generation of plasma is promoted by arranging the magnet 32.
Next, an inorganic material such as silicon oxide is formed on the surface of the gas barrier coating film provided on one surface of the base film 1 or the inorganic oxide vapor deposition film provided on the one surface of the base film 1 as described above. After forming the oxide vapor deposition film, the base film 1 is formed by holding the auxiliary roll 33 while holding the inorganic oxide vapor deposition film or the inorganic oxide vapor deposition film and the gas barrier coating film. The inorganic oxide vapor deposition film can be formed by the plasma chemical vapor deposition method according to the present invention.
In the figure, 35 represents a vacuum pump.
The above exemplification is an example, and it goes without saying that the present invention is not limited thereby.
Although not shown, in the present invention, the inorganic oxide vapor deposition film may be not only one layer of the inorganic oxide vapor deposition film but also a multilayer film in which two or more layers are laminated, and is used. The materials may be used alone or as a mixture of two or more, and an inorganic oxide vapor deposition film mixed with different materials may be formed.

In the above, the inside of 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 desirable to do.
In the raw material volatilization supply device, the organic silicon compound as the raw material is volatilized and mixed with oxygen gas, inert gas, etc. supplied from the gas supply device, and this mixed gas is supplied to the vacuum chamber through the raw material supply nozzle. It is introduced in the inside.
In this case, the content of the organosilicon compound in the mixed gas is about 1 to 40%, the content of oxygen gas is about 10 to 70%, and the content of inert gas is about 10 to 60%. For example, the mixing ratio of the organosilicon compound, oxygen gas, and inert gas can be about 1: 6: 5 to 1:17:14.
On the other hand, since a predetermined voltage is applied to the cooling / electrode drum from the power source, 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. The glow discharge plasma is derived from one or more gas components in the mixed gas. In this state, the substrate film is conveyed at a constant speed, and the glow discharge plasma is used to cool the electrode drum peripheral surface. On the surface of the upper base film or on the surface of the gas barrier coating film provided on the inorganic oxide vapor deposition film provided on one side of the base film, an inorganic oxide vapor deposition film such as silicon oxide is provided. It can be formed.
At this time, the degree of vacuum in the vacuum chamber should be adjusted to 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably to 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr. In addition, it is desirable that the conveying speed of the base film is adjusted to about 10 to 300 m / min, preferably about 50 to 150 m / min.

In the above plasma chemical vapor deposition apparatus, the formation of a vapor-deposited film of an inorganic oxide such as silicon oxide is performed on one surface of the base film or one surface of the base film. the surface of the gas barrier coating film provided on the vapor deposited film, since it is formed into a thin film in the form of SiO _X while the plasma raw material gas is oxidized with oxygen gas, inorganic oxide such as silicon oxide, which is the form The deposited film of an object is a continuous layer that is dense, has few gaps, and is highly flexible. Therefore, the barrier property of a deposited film of an inorganic oxide such as silicon oxide is determined by a conventional vacuum deposition method or the like. It is much higher than a deposited film of an inorganic oxide such as silicon oxide formed, and a sufficient gas barrier property can be obtained with a thin film thickness.
In the present invention, the surface of the base film or the surface of the gas barrier coating film provided on the inorganic oxide vapor deposition film provided on one surface of the base film is cleaned by SiO _X plasma. Since polar groups, free radicals, etc. are generated on the surface of the base film or the gas barrier coating film provided on the inorganic oxide vapor deposition film provided on one surface of the base film. A gas barrier coating film provided on an inorganic oxide vapor deposition film formed on the surface of the base film or an inorganic oxide vapor deposition film provided on one surface of the base film. It has the advantage that the tight adhesion is high.
Furthermore, as described above, the degree of vacuum when forming a continuous film of an inorganic oxide such as silicon oxide is about 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10. ^{-2 Since} it is prepared at the Torr position, the degree of vacuum when forming a deposited film of an inorganic oxide such as silicon oxide by the conventional vacuum evaporation method is compared with the 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Torr position. Since the degree of vacuum is low, the base material film or the base film provided with an inorganic oxide vapor-deposited film and a gas barrier coating film can be shortened in the vacuum state setting time at the time of replacing the raw material. It is easy to stabilize the degree, and the film forming process is stabilized.

In the present invention, a deposited film of silicon oxide formed using a vapor-deposited monomer gas such as an organosilicon compound chemically reacts with a vapor-deposited monomer gas such as an organosilicon compound and oxygen gas. Is closely adhered to one surface of the base film or the surface of the gas barrier coating film provided on the inorganic oxide vapor-deposited film provided on one surface of the base film. is intended to form a thin film rich usually formula SiO _X (provided that, X is a number from 0 to 2) is a continuous form of a thin film mainly composed of silicon oxide represented by.
Thus, the silicon oxide vapor-deposited film is represented by the general formula SiO _x (where X represents a number from 1.3 to 1.9) from the viewpoint of transparency and barrier properties. A thin film mainly composed of a deposited silicon oxide film is preferable.
In the above, the value of X varies depending on the molar ratio of the vapor-deposited monomer gas and oxygen gas, the energy of the plasma, etc. Generally, the gas permeability decreases as the value of X decreases, but the film itself Becomes yellowish and the transparency is poor.

In addition, the silicon oxide vapor-deposited film is mainly composed of silicon oxide, and further, at least one kind of compound composed of one kind of carbon, hydrogen, silicon, or oxygen, or two or more kinds thereof is chemically used. It consists of the vapor deposition film | membrane contained by a coupling | bonding etc., It is characterized by the above-mentioned.
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, etc. A derivative may be contained by a chemical bond or the like.
Specific examples include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl, 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 deposited film of silicon oxide can be changed by changing the conditions of the vapor deposition process.
Thus, the content of the above compound in the deposited film of silicon oxide is about 0.1 to 50%, preferably about 5 to 20%.
In the above, if the content is less than 0.1%, the impact resistance, spreadability, flexibility, etc. of the deposited silicon oxide film become insufficient, and scratches, cracks, etc. are likely to occur due to bending. It is difficult to stably maintain a high barrier property, and if it exceeds 50%, the barrier property is lowered, which is not preferable.
Further, in the present invention, in the silicon oxide vapor-deposited film, the content of the above-mentioned compound is preferably decreased in the depth direction from the surface of the silicon oxide vapor-deposited film. The gas barrier provided on the surface of the base film or an inorganic oxide vapor-deposited film provided on one side of the base film can be improved on the surface of Gas barrier provided on the base film or an inorganic oxide vapor deposition film provided on one surface of the base film because the content of the above compound is small at the interface with the surface of the conductive coating film This has the advantage that the tight adhesion between the conductive coating film and the deposited silicon oxide film becomes strong.

Thus, in the present invention, the above-described silicon oxide vapor deposition film is subjected to, for example, a surface analysis such as an X-ray photoelectron spectrometer (Xray Photoelectron Spectroscopy (XPS)), a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS), or the like. The physical properties as described above can be confirmed by performing an elemental analysis of the deposited film of silicon oxide using a method of analyzing by ion etching in the depth direction using an apparatus.
In the present invention, the thickness of the silicon oxide vapor deposition film is preferably about 50 to 4000 mm, more specifically about 100 to 1000 mm. In the above, if it is thicker than 1000 mm, and more preferably 4000 mm, it is not preferable because cracks and the like are likely to occur in the film, and if it is less than 100 mm, and further less than 50 mm, there is an effect of barrier properties. Is not preferable because it becomes difficult.
In the above, 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. In the above, as means for changing the film thickness of the silicon oxide vapor deposition film, the volume velocity of the vapor deposition film is increased, that is, the method of increasing the amount of monomer gas and oxygen gas and the vapor deposition rate. This can be done by a method of slowing down.

Next, in the above, as a vapor deposition monomer gas such as an organic silicon compound for forming a vapor deposition film of an inorganic oxide such as silicon oxide, for example, 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane Siloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyl Trimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, etc. can be used.
In the present invention, among the organic silicon compounds as described above, use of 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is easy to handle and formed continuous film. In view of the above characteristics and the like, it is a particularly preferable raw material.
Moreover, in the above, as an inert gas, argon gas, helium gas, etc. can be used, for example.

Next, in the present invention, the inorganic oxide vapor-deposited film by the physical vapor deposition method will be described in more detail. Examples of the inorganic oxide vapor-deposited film by the physical vapor deposition method include, for example, vacuum vapor deposition and sputtering. A vapor deposition film of an inorganic oxide can be formed using a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a method, an ion plating method, or an ion cluster beam method.
In the present invention, specifically, a metal or a metal oxide is used as a raw material, and this is heated and vaporized, and this is provided on one side of the base film or one side of the base film. Vacuum deposition method for vapor deposition on the surface of the gas barrier coating film provided on the inorganic oxide vapor deposition film, or using a metal or metal oxide as a raw material and introducing oxygen to oxidize the base film An oxidation reaction vapor deposition method that vapor-deposits on the surface of a gas barrier coating film provided on one surface of the substrate film or an inorganic oxide vapor deposition film provided on one surface of the base film, and further assists the oxidation reaction with plasma. A deposited film can be formed using a plasma-assisted oxidation reaction deposition method or the like.
In the above, as a heating method for 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.

In the present invention, a specific example of a method for forming a thin film of an inorganic oxide by physical vapor deposition will be described. FIG. 10 is a schematic configuration diagram showing an example of a take-up vacuum deposition apparatus.
As shown in FIG. 10, the base film 1 or the inorganic oxide vapor deposition film and the gas barrier coating film fed out from the unwinding roll 43 in the vacuum chamber 42 of the take-up type vacuum vapor deposition apparatus 41. The base film 1 provided with is guided to the cooled coating drum 46 through guide rollers 44 and 45.
Thus, one surface of the base film 1 guided on the cooled coating drum 46 or the base film 1 provided with an inorganic oxide vapor deposition film and a gas barrier coating film is provided. The vapor deposition source 48 heated by the crucible 47, for example, metal aluminum or aluminum oxide is evaporated on the surface of the gas barrier coating film, and if necessary, oxygen gas or the like is ejected from the oxygen gas outlet 49. While supplying this, a vapor-deposited film of an inorganic oxide such as aluminum oxide is formed through the masks 50 and 50, and then, in the above, for example, a vapor-deposited film of an inorganic oxide such as aluminum oxide is formed. The formed base film 1 or the base film 1 on which an inorganic oxide vapor deposition film such as aluminum oxide, a gas barrier coating film and an inorganic oxide vapor deposition film are formed is guided. - sending via the Le 51, winding Russia - by winding Le 53, it is possible to form a deposited film of an inorganic oxide by according a physical vapor deposition method of the present invention.
In the present invention, the first-layer inorganic oxide vapor deposition film is first formed using the above-described take-up vacuum vapor deposition apparatus, and then the inorganic oxide vapor deposition film is formed in the same manner. Further, an inorganic oxide vapor deposition film is formed on the substrate, or by using the above-described take-up vacuum vapor deposition apparatus, these are connected in series, and the inorganic oxide vapor deposition is continuously performed. By forming the film, it is possible to form a vapor-deposited film of an inorganic oxide composed of two or more multilayer films.

In the above, as a vapor deposition film of an inorganic oxide, basically, any thin film on which a metal oxide is deposited can be used. For example, silicon (Si), aluminum (Al), magnesium (Mg), Metal oxides such as calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) The deposited film can be used.
Thus, preferable examples include vapor-deposited films of metal oxides such as silicon (Si) and aluminum (Al).
The metal oxide vapor deposition film can be referred to as a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide, etc., and the notation thereof is, 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.
As the range of the value of X, 0 to 2 for silicon (Si), 0 to 1.5 for aluminum (Al), 0 to 1 for magnesium (Mg), 0 to 1 for calcium (Ca). 1, 0 to 0.5 for potassium (K), 0 to 2 for tin (Sn), 0 to 0.5 for sodium (Na), 0 to 1, 5 for boron (B), titanium ( Ti) can be 0 to 2, lead (Pb) is 0 to 1, zirconium (Zr) is 0 to 2, and yttrium (Y) is 0 to 1.5.
In the above, when X = 0, it is a complete metal and is not transparent and cannot be used at all. The upper limit of the range of X is a completely oxidized value.
In the present invention, generally, examples other than silicon (Si) and aluminum (Al) are scarce, silicon (Si) is 1.0 to 2.0, and aluminum (Al) is 0.5. A value in the range of -1.5 can be used.
In the present invention, the film thickness of the inorganic oxide vapor-deposited film as described above varies depending on the metal used or the type of metal oxide, but is, for example, about 50 to 2000 mm, preferably 100 to 1000 mm. It is desirable to select and form arbitrarily within the range.
Moreover, in this invention, as a vapor deposition film of an inorganic oxide, as a metal or metal oxide to be used, it is used by 1 type, or 2 or more types of mixtures, and vapor deposition of the inorganic oxide mixed by the dissimilar material A membrane can also be constructed.

By the way, in the gas barrier laminate film according to the present invention, as described above, the inorganic oxide vapor-deposited film provided on one surface of the base film, or one surface of the base film is provided with the inorganic oxide. A vapor-deposited film and a gas barrier coating film are provided, and the surface of the inorganic oxide vapor-deposited film provided on the gas barrier-coated film is provided with a gas barrier coating film provided on the inorganic oxide vapor-deposited film. Improving tight adhesion or tight adhesion with primer layer, printed pattern layer, heat seal resin layer, intermediate substrate, etc., which will be described later, provided on the inorganic oxide vapor deposition film In the end, it is preferable to form a plasma-treated surface with oxygen gas in order to firmly adhere both of them and prevent the occurrence of delamination or the like.
Thus, in the present invention, the plasma-treated surface with oxygen gas can be formed in the same manner as the plasma-treated surface with the aforementioned inert gas.
That is, in the present invention, the oxygen-treated plasma treatment surface is a plasma surface treatment method in which surface modification is performed using a plasma gas generated by ionizing a gas by arc discharge. It is possible to form a plasma-treated surface.
Thus, in the present invention, the plasma gas is a plasma surface treatment method using oxygen gas or a mixed gas of oxygen gas and inert gas such as nitrogen gas, argon gas, helium gas, or the like. By performing the treatment, a plasma treatment surface with oxygen gas can be formed.
In the present invention, when forming a plasma-treated surface with oxygen gas, after forming an inorganic oxide vapor-deposited film, immediately after that, the inorganic oxide vapor-deposited film is subjected to plasma discharge treatment with oxygen gas in-line. By doing so, a plasma-treated surface with oxygen gas can be formed.
Further, in the present invention, it is preferable to perform the plasma discharge treatment in consideration of conditions such as plasma output, plasma gas type, plasma gas supply amount, treatment time, and the like.
In the present invention, as a method for generating plasma, for example, a direct current glow discharge, a high frequency discharge, a microwave discharge, or the like can be used.
Of course, in the present invention, the plasma processing surface can be formed also by the atmospheric pressure plasma processing method.

Next, in the present invention, the gas barrier coating film constituting the gas barrier laminated film according to the present invention will be described. As the gas barrier coating film, for example, a general formula R ¹ _n M (OR ² ) _m (however, In the formula, 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 at least one alkoxide represented by M), a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and a sol-gel catalyst, A step of preparing a gas barrier composition that is polycondensed by a sol-gel method in the presence of an acid, water, and an organic solvent, on the vapor-deposited film of an inorganic oxide provided on one surface of the substrate film, Heavy by sol-gel method The step of applying a gas barrier composition to be condensed to provide a coating film, the base film provided with the coating film on the inorganic oxide vapor-deposited film, at 20 ° C. to 180 ° C. and the above A gas barrier made of the above-described gas barrier composition on a vapor-deposited film of an inorganic oxide provided on one surface of the above base film by heat treatment at a temperature not higher than the melting point of the base film for 10 seconds to 10 minutes. It can manufacture by the manufacturing process including the process of forming a conductive coating film.

In the present invention, the gas barrier coating film constituting the gas barrier laminated film according to the present invention has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² are the number of carbon atoms) 1 to 8 organic groups, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents the valence of M). In the presence of a sol-gel catalyst, an acid, water, and an organic solvent, containing at least one alkoxide, a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer. , A step of preparing a gas barrier composition that is polycondensed by a sol-gel method, and a gas barrier composition that is polycondensed by the sol-gel method described above on an inorganic oxide vapor-deposited film provided on one surface of a base film. 2 or more coating films A base film provided with a coating film in which two or more layers are stacked on the above-described inorganic oxide vapor-deposited film at a temperature of 20 ° C. to 180 ° C. and below the melting point of the base film. Then, two or more gas barrier coating films made of the above gas barrier composition were stacked on the inorganic oxide vapor deposition film provided on one surface of the above base film. It can be manufactured by a manufacturing process including a process of forming a composite polymer layer.

In the above, the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m forming the gas barrier coating film constituting the gas barrier laminated film according to the present invention includes a partial hydrolyzate of alkoxide, hydrolyzate of alkoxide. At least one kind of decomposition condensate can be used, and as the partial hydrolyzate of the above alkoxide, it is not necessary that all alkoxy groups are hydrolyzed, and one or more of them are hydrolyzed. Further, the hydrolysis condensate may be a dimer or more of a partially hydrolyzed alkoxide, specifically a 2 to 6 mer. .

In the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , silicon, zirconium, titanium, aluminum, and the like can be used as the metal atom represented by M.
Thus, in the present invention, examples of a preferable metal include silicon.
In the present invention, the alkoxide can be used alone or in combination of two or more different metal atom alkoxides in the same solution.

In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ¹ include, for example, a methyl group, an ethyl group, an n-propyl group, i Examples thereof include alkyl groups such as -propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group and others.
In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ² include, for example, a methyl group, an ethyl group, an n-propyl group, i -Propyl group, n-butyl group, sec-butyl group, and the like.
In the present invention, these alkyl groups may be the same or different in the same molecule.

Thus, in the present invention, as the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , for example, it is preferable to use an alkoxysilane in which M is Si.
The alkoxysilane is represented by the general formula Si (ORa) ₄ (wherein Ra represents a lower alkyl group).
In the above, as Ra, methyl group, ethyl group, n-propyl group, n-butyl group, and others are used.
Specific examples of the above alkoxysilane include, for example, 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 ) ₄ , etc. can be used.

In the present invention, examples of the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m include, for example, the general formula Rb _n Si (ORc) _4-m (where n is 0 The above-mentioned integer is represented, m represents an integer of 1, 2, and 3, and Rb and Rc represent a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and the like. Alkoxysilanes can be used.
Specific examples of the above-mentioned alkylalkoxysilane include, for example, methyltrimethoxysilane CH ₃ Si (OCH ₃ ) ₃ , methyltriethoxysilane CH ₃ Si (OC ₂ H ₅ ) ₃ , dimethyldimethoxysilane (CH ₃ ) ₂ Si (OCH ₃ ) ₂ , dimethyldiethoxysilane (CH ₃ ) ₂ Si (OC ₂ H ₅ ) ₂ , etc. can be used.
Said alkoxysilane, alkylalkoxysilane, etc. can be used individually or in mixture of 2 or more types.
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.

Next, in the present invention, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , for example, a zirconium alkoxide in which M is Zr can be used.
Specific examples of the zirconium alkoxide include, for example, tetramethoxyzirconium Zr (OCH ₃ ) ₄ , tetraethoxyzirconium Zr (OC ₂ H ₅ ) ₄ , tetra ipropoxyzirconium Zr (is0-0C ₃ H ₇ ) ₄ , tetra nButoxyzirconium Zr (OC ₄ H ₉ ) ₄ , etc. can be used.

In the present invention, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , for example, a titanium alkoxide in which M is Ti can be used.
Specific examples of the titanium alkoxide include, for example, tetramethoxytitanium Ti (OCH ₃ ) ₄ , tetraethoxytitanium Ti (OC ₂ H ₅ ) ₄ , tetraisopropoxytitanium Ti (is0-0C ₃ H ₇ ) ₄ , tetra n-butoxy titanium Ti (OC ₄ H ₉ ) ₄ , etc. can be used.

Furthermore, in the present invention, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , for example, an aluminum alkoxide in which M is Al can be used.
Specific examples of the aluminum alkoxide include, for example, tetramethoxyaluminum Al (OCH ₃ ) ₄ , tetraethoxyaluminum Al (OC ₂ H ₅ ) ₄ , tetraisopropoxyaluminum Al (is0-0C ₃ H ₇ ) ₄ , tetra nButoxyaluminum Al (OC ₄ H ₉ ) ₄ , etc. can be used.

In the present invention, the above alkoxides may be used as a mixture of two or more thereof.
Thus, in the present invention, in particular, by using a mixture of alkoxysilane and zirconium alkoxide, the toughness, heat resistance, etc. of the resulting gas barrier laminate film can be improved, and the resistance of the film during stretching can be improved. A decrease in retort property is avoided.
The amount of the zirconium alkoxide used is in the range of 10 parts by weight or less with respect to 100 parts by weight of the alkoxysilane, preferably about 5 parts by weight. In the above, when the amount exceeds 10 parts by weight, the formed gas barrier coating film is easily gelled, and the brittleness of the film is increased, so that the gas barrier coating film is easily peeled off when the base film is coated. This is not preferable.

In the present invention, in particular, by using a mixture of alkoxysilane and titanium alkoxide, there is an advantage that the heat conductivity of the obtained gas barrier coating film is lowered and the heat resistance of the gas barrier laminated film is remarkably improved. .
In the above, the amount of titanium alkoxide used is in the range of 5 parts by weight or less with respect to 100 parts by weight of the alkoxysilane, and preferably about 3 parts by weight.
In the above, if it exceeds 5 parts by weight, the gas barrier coating film to be formed becomes more brittle, and it is not preferable because the gas barrier coating film tends to peel off when the base film is coated. is there.

Next, as a polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer forming a gas barrier coating film constituting the gas barrier laminate film according to the present invention, a polyvinyl alcohol resin, or An ethylene / vinyl alcohol copolymer can be used alone, or a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer can be used in combination. In the invention, by using a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer, the physical properties such as gas barrier properties, water resistance, weather resistance, etc. of the gas barrier coating film can be remarkably improved. It can be done.
In particular, in the present invention, by using a combination of a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer, in addition to the above physical properties such as gas barrier properties, water resistance, and weather resistance, hot water resistance and hot water A gas barrier coating film remarkably excellent in gas barrier properties after the treatment can be formed.

  In the present invention, when a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer are used in combination, the blending ratio of each is polyvinyl alcohol resin: ethylene / vinyl alcohol by weight ratio. The copolymer is preferably in the 10: 0.05 to 10: 6 position, and more preferably in a blending ratio of about 10: 1.

In the present invention, the content of the polyvinyl alcohol-based resin and / or the ethylene / vinyl alcohol copolymer is in the range of 5 to 500 parts by weight with respect to 100 parts by weight of the total amount of the alkoxide, It is preferable to prepare the gas barrier composition at a blending ratio of about 20 to 200 parts by weight.
In the above, exceeding 500 parts by weight is not preferable because the brittleness of the gas barrier coating film is increased, and the water resistance and weather resistance of the resulting gas barrier laminated film tend to decrease. If it is below, the gas barrier property is lowered, which is not preferable.

In the present invention, as the polyvinyl alcohol-based resin and / or ethylene / vinyl alcohol copolymer, first, as the polyvinyl alcohol-based resin, generally obtained by saponifying polyvinyl acetate is used. be able to.
As the above-mentioned polyvinyl alcohol resin, a partially saponified polyvinyl alcohol resin in which several tens% of acetic acid groups remain, or a completely saponified polyvinyl alcohol in which no acetic acid groups remain, or an OH group has been modified. A modified polyvinyl alcohol resin may be used and is not particularly limited.
Specific examples of the polyvinyl alcohol-based resin include RS-110 (saponification degree = 99%, polymerization degree = 1,000) manufactured by Kuraray Co., Ltd., and Kuraray Poval LM-20SO (saponification degree) manufactured by Kuraray Co., Ltd. Degree = 40%, degree of polymerization = 2,000), Gohsenol NM-14 (degree of saponification = 99%, degree of polymerization = 1,400) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. can be used.

In the present invention, 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 should be used. Can do.
Specific examples include partial saponification products in which several tens mol% of acetic acid groups remain to complete saponification products in which acetic acid groups remain only a few mol% or no acetic acid groups remain. However, it is desirable 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. The content of repeating units derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. Is preferably used.
Specific examples of the ethylene / vinyl alcohol copolymer include Kuraray Co., Ltd., Eval EP-F101 (ethylene content: 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content: 29 mol%). ) Etc. can be used.

Next, in the present invention, the gas barrier composition for forming the gas barrier coating film constituting the gas barrier laminated film according to the present invention will be described. As the gas barrier composition, the general formula R ¹ _n as described above is used. M (OR ² ) _m (wherein, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, and m represents An integer of 1 or more, and n + m represents the valence of M.) and at least one alkoxide represented by the above-mentioned polyvinyl alcohol resin and / or ethylene / vinyl alcohol. A gas barrier composition containing a polymer and further polycondensed by a sol-gel method in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent is prepared.

In preparing the gas barrier composition, for example, a silane coupling agent or the like can be added.
Thus, as the silane coupling agent, known organic reactive group-containing organoalkoxysilanes can be used.
In the present invention, an organoalkoxysilane having an epoxy group is particularly suitable. For example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane or the like can be used.
The above silane coupling agents may be used alone or in combination of two or more. In this invention, the usage-amount of the above silane coupling agents can be used within the range of 1-20 weight part with respect to 100 weight part of said alkoxysilane.
In the above, use of 20 parts by weight or more is not preferable because the gas barrier coating film to be formed has increased rigidity and brittleness, and the insulating property and workability of the gas barrier coating film tend to be lowered. It is.

Next, as a sol-gel method catalyst, mainly a polycondensation catalyst, used in the gas barrier composition, a tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used.
Specifically, for example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine, and the like can be used.
In the present invention, N, N-dimethylbenzylamine is particularly preferred.
The amount used is 0.01 to 1.0 part by weight, preferably about 0.03 parts by weight per 100 parts by weight of the total amount of alkoxide and silane coupling agent.
The acid used in the gas barrier composition is used as a catalyst for the sol-gel method, mainly as a catalyst for hydrolysis of an alkoxide, a silane coupling agent, or the like.
Examples of the acid include mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid, organic acids such as acetic acid and tartaric acid, and the like.
The amount of the acid used is about 0.001 to 0.05 mol, preferably about 0.01 mol, relative to the total molar amount of the alkoxide and the alkoxide content of the silane coupling agent (for example, silicate moiety). Is preferred.

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 the water exceeds 2 mol, the polymer obtained from the alkoxysilane and the metal alkoxide becomes spherical particles, and the spherical particles are three-dimensionally cross-linked to form a porous material having a low density. Therefore, such a porous polymer is not preferable because the gas barrier property of the gas barrier laminate film cannot be improved.
Moreover, when the amount of the water is less than 0.8 mol, it is not preferable because the hydrolysis reaction tends to hardly proceed.

Furthermore, as the organic solvent used in the gas barrier composition, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol, and the like can be used.
Furthermore, in the gas barrier composition, the polyvinyl alcohol-based resin and / or the ethylene / vinyl alcohol copolymer is in a state of being dissolved in a coating solution containing the alkoxide or the silane coupling agent. Therefore, the type of the organic solvent is appropriately selected.
In the case of using a combination of a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer, it is preferable to use n-butanol.
In the present invention, as the ethylene / vinyl alcohol copolymer solubilized in a solvent, for example, those commercially available as Soarnol (trade name) can be used.
The amount of the organic solvent used is usually 30 per 100 parts by weight of the total amount of the alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, acid and sol-gel catalyst. ~ 500 parts by weight.

Next, in the present invention, the gas barrier coating film according to the present invention is specifically manufactured as follows, for example.
First, an alkoxide such as alkoxysilane, a silane coupling agent, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, a sol-gel catalyst, an acid, water, an organic solvent, and, if necessary, A metal alkoxide or the like is mixed to prepare a gas barrier composition (coating liquid).
Next, a polycondensation reaction gradually proceeds in the gas barrier composition (coating liquid).
Next, the above gas barrier composition (coating liquid) is applied by an ordinary method on an inorganic oxide vapor-deposited film formed on one surface of the base film, and dried.
Thus, by the above drying, polycondensation of the alkoxide such as alkoxysilane, metal alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer proceeds, and the coating film Is formed.
Further, preferably, the above coating operation is repeated to laminate a plurality of coating films composed of two or more layers.
Finally, the base film coated with the above coating solution is at a temperature of about 20 ° C. to 180 ° C. and below the melting point of the base film, preferably at a temperature in the range of about 50 ° C. to 160 ° C. A gas barrier coating film of the above gas barrier composition (coating liquid) is formed on one layer of the inorganic oxide vapor-deposited film formed on one surface of the base film by heating for 10 seconds to 10 minutes. Two or more layers can be formed to produce the gas barrier coating film according to the present invention.
The gas barrier coating film according to the present invention obtained in this way is excellent in gas barrier properties.

  In the present invention, in place of the polyvinyl alcohol resin, an ethylene / vinyl alcohol copolymer, or both a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer are used in the same manner as described above. The gas barrier coating film according to the present invention produced by performing drying and heat treatment has an advantage that the gas barrier property after hot water treatment such as boil treatment and retort treatment is further improved.

  Furthermore, in the present invention, as described above, when ethylene vinyl alcohol copolymer or polyvinyl alcohol resin and ethylene vinyl alcohol copolymer are not used in combination, that is, only polyvinyl alcohol resin is used. In the case of producing a gas barrier coating film according to the present invention, in order to improve the gas barrier property after the hot water treatment, for example, a gas barrier composition using a polyvinyl alcohol resin is applied in advance. Then, a first coating layer is formed, and then a gas barrier composition containing an ethylene / vinyl alcohol copolymer is coated on the coating layer to form a second coating layer. By forming these composite layers, it is possible to improve the gas barrier properties of the gas barrier coating film according to the present invention.

  Furthermore, the coating layer formed by the gas barrier composition containing the above-mentioned ethylene / vinyl alcohol copolymer, or the gas barrier composition containing a combination of a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer. Forming a plurality of coating layers formed of an object as a plurality of layers is also an effective means for improving the gas barrier property of the gas barrier coating film according to the present invention.

Next, the operation of the method for producing a gas barrier coating film according to the present invention will be described by using an alkoxysilane as an alkoxide as an example. First, an alkoxysilane and a metal alkoxide are hydrolyzed by added water. Is done.
At that time, the acid serves as a catalyst for hydrolysis.
Next, protons are taken from the generated hydroxyl groups by the action of the sol-gel method catalyst, and 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, due to the action of the base catalyst, ring opening of the epoxy group also occurs and a hydroxyl group is generated.
A polycondensation reaction between the hydrolyzed silane coupling agent and the hydrolyzed alkoxide also proceeds.
Furthermore, since the reaction system contains a polyvinyl alcohol resin, an ethylene / vinyl alcohol copolymer, or a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer, the polyvinyl alcohol resin and the ethylene / vinyl alcohol Reaction with the hydroxyl group of the copolymer also occurs.
The resulting polycondensate contains, for example, an inorganic part composed of bonds such as Si—O—Si, Si—O—Zr, Si—O—Ti, and the like, and an organic part derived from the silane coupling agent. In the above reaction constituting the composite polymer, 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. .
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 an existing acid as a catalyst, and the OH group is first deprotonated by the action of a sol-gel method catalyst (base catalyst), and then polycondensation proceeds.
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)), and Si—O— 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) having Si bonds is formed.

The above reaction proceeds at room temperature, and the viscosity of the gas barrier composition (coating liquid) increases during preparation.
When this gas barrier composition (coating liquid) is applied onto a vapor-deposited film of an inorganic oxide provided on one side of the base film and heated to remove the solvent and the alcohol produced by the polycondensation reaction, The polycondensation reaction is completed, and a transparent coating layer is formed on the inorganic oxide vapor deposition film provided on one surface of the base film.
In the case of laminating a plurality of the above-mentioned coating layers, the composite polymers in the coating layers between the layers are also condensed, and the layers are firmly bonded to each other.
Further, since 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 deposited inorganic oxide film provided on one surface of the substrate film, The adhesion between the surface of the vapor-deposited film of the inorganic oxide provided on one surface and the coating layer, the adhesiveness, and the like are also good.

In the method of the present invention, the amount of water added is adjusted to 0.8 to 2 mol, preferably 1.5 mol, relative to 1 mol of the alkoxide, so that the linear polymer described above 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). Furthermore, a polar group (OH group) is partially present in the molecule, and the molecular aggregation energy is high. Excellent gas barrier properties due to high rigidity.

Gas barrier coating film according to the present invention has the excellent properties as described above are useful as packaging materials, in particular, gas barrier properties _{(O 2, N 2, H} 2 O, CO 2, and other such transparent Therefore, it is preferably used as a barrier substrate constituting a food packaging film.
In particular, when used in so-called gas-filled packaging filled with N ₂ or CO ₂ gas, the excellent gas barrier property is extremely effective for holding the filled gas.
Furthermore, the gas barrier coating film according to the present invention is excellent in hot water treatment, particularly high-pressure hot water treatment (retort treatment), and exhibits extremely excellent gas barrier properties.

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, and the like. And the gas barrier coating film can be improved, and a synergistic effect of the two layers can provide a better gas barrier effect.
As a method for applying the gas barrier composition of the present invention, for example, a roll coating such as a gravure roll coater, a spray coating, a spin coating, a date coating, a brush, a barcode, an applicator, etc. Alternatively, 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. Preferably, condensation is performed by heating and drying at a temperature of 70 to 200 ° C. for 0.005 to 60 minutes, preferably 0.01 to 10 minutes, and the gas barrier coating film of the present invention is formed. can do.
If necessary, when applying the gas barrier composition of the present invention, a primer agent or the like can be applied on the inorganic oxide vapor-deposited film in advance, and corona discharge treatment or A pretreatment such as plasma treatment or the like can be optionally performed.

Next, in the present invention, the primer agent layer constituting the gas barrier laminate film according to the present invention will be described. As the primer agent layer, an inorganic oxide vapor deposition film is formed on one surface of the base film. Next, a gas barrier coating film is provided on the vapor-deposited film of the inorganic oxide, and further, an inorganic oxide by chemical vapor deposition or physical vapor deposition is formed on the gas barrier coating film. After providing the vapor deposition film, a primer agent layer is provided on the surface of the inorganic oxide vapor deposition film with or without the plasma treatment surface with oxygen gas. In the case of laminating an inorganic oxide vapor-deposited film and, for example, a printed pattern layer, a heat-seal resin layer, an intermediate base material, other base materials, etc., by the agent layer, an inorganic oxide vapor-deposited film Each material to be laminated is improved by improving adhesion etc. By firmly adhered, is provided in order to prevent the delamination (delamination) occurs such.
Thus, as the primer layer, first, a polyurethane resin or a polyester resin or the like is used as a main component of the vehicle, and 1 to 30% by weight of the polyurethane resin or the polyester resin or the like is silane coupling. 0.05 to 10% by weight, preferably 0.1 to 5% by weight, filler 0.1 to 20% by weight, preferably 1 to 10% by weight, Furthermore, if necessary, additives such as stabilizers, curing agents, cross-linking agents, lubricants, ultraviolet absorbers, etc. are optionally added, and a solvent, diluent, etc. are added and mixed well to be polyurethane or polyester. A resin composition is prepared, and then the polyurethane-based or polyester-based resin composition is used. For example, a roll coat, a gravure coat, a knife coat, a dip coat, a shoe Plasma treatment with oxygen gas is performed on the surface of the inorganic oxide vapor deposition film provided on the gas barrier coating film constituting the gas barrier multilayer film according to the present invention by a ray coating or other coating method. Coating with or without a surface, and then drying the coating film to remove solvent, diluent, etc., and if necessary, aging treatment, etc. The primer layer according to the present invention can be formed.
In the present invention, the film thickness of the primer layer is preferably, for example, about 0.1 g / m ^{2 to} 1.0 g / m ² (dry state).
Thus, in the present invention, the primer layer as described above comprises an inorganic oxide vapor-deposited film that constitutes the gas barrier laminate film according to the present invention, a printed pattern layer, and a heat seal property. Improves close adhesion with substrates such as resin layers, intermediate substrates, etc. and improves the elongation of the primer layer, for example, laminating or post-processing suitability such as bag making This prevents the occurrence of cracks and the like in the vapor-deposited film of the inorganic oxide constituting the gas barrier laminate film according to the present invention during post-processing.

In the above, as a polyurethane-type resin which comprises a polyurethane-type resin composition, the polyurethane-type resin obtained by reaction of a polyfunctional isocyanate and a hydroxyl-group containing compound can be used, for example.
Specifically, for example, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, hexamethylene diisocyanate, xylylene diisocyanate One obtained by reacting a polyfunctional isocyanate such as an aliphatic polyisocyanate such as a salt with a hydroxyl group-containing compound such as a polyether polyol, a polyester polyol, a polyacrylate polyol, or the like. A liquid or two-component curable polyurethane resin can be used.
Thus, in the present invention, by using the polyurethane-based resin as described above, the adhesion property between the vapor-deposited film of the inorganic oxide and the heat sealable resin layer is improved and the primer layer. For example, the suitability of post-processing such as laminating or bag-making processing is improved, and the occurrence of cracks or the like in the deposited film of the inorganic oxide during post-processing is prevented.

In the above, the polyester resin constituting the polyester resin composition includes, for example, one or more aromatic saturated dicarboxylic acids having a benzene nucleus such as terephthalic acid as a basic skeleton, A thermoplastic polyester resin produced by polycondensation with one or more valent alcohols can be used. In the above, examples of the aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton include terephthalic acid, isophthalic acid, phthalic acid, diphenyl ether-4, 4-dicarboxylic acid, and the like.
In the above, saturated divalent alcohols include ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, Polytetramethylene glycol, hexamethylene glycol, dodecamethylene glycol, aliphatic glycols such as neopentyl glycol, alicyclic glycols such as cyclohexanedimethanol, 2.2- Bis (4'-β-hydroxyethoxyphenyl) propane, naphthalene diol, other aromatic geo- and the like can be used.

In the present invention, specific examples of the polyester resin include thermoplastic polyethylene terephthalate resin produced by polycondensation of terephthalic acid and ethylene glycol, terephthalic acid and tetramethylene glycol. Polybutylene terephthalate resin produced by polycondensation with styrene, thermoplastic polycyclohexanedimethylene terephthalate resin produced by polycondensation of terephthalic acid and 1,4-cyclohexanedimethanol, terephthalic acid Polyethylene terephthalate resin produced by copolycondensation of styrene, isophthalic acid and ethylene glycol, produced by copolycondensation of terephthalic acid, ethylene glycol and 1,4-cyclohexanedimethanol Thermoplastic polyethylene terephthalate resin, terephthalic acid and isophthalic acid And ethylene glycol - le and propylene glycol - thermoplastic polyethylene terephthalate produced by co-polycondensation of Le - DOO resins, polyester polyol - can be used Le resin, other like.
In the present invention, in addition to the saturated aromatic dicarboxylic acid having a benzene nucleus as a basic skeleton as described above, for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, One or more aliphatic saturated dicarboxylic acids such as sebacic acid and dodecanoic acid can be added and copolycondensed, and the amount used is an aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton, It is preferable to add 1 to 10% by weight.
Thus, in the present invention, by using the polyester resin as described above, the tight adhesion and the like are improved and the elongation of the primer layer is improved, for example, laminating, or This improves the suitability for post-processing such as bag-making and prevents the occurrence of cracks in the deposited film of the inorganic oxide during the post-processing.

  Next, in the above, as the silane coupling agent constituting the polyurethane-based or polyester-based resin composition, organic functional silane monomers having binary reactivity can be used, for example, γ-chloropropyl Trimethoxysilane, 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-aminopropylmethyl Dimethoxysilane, γ One or more of ureidopropyltriethoxysilane, bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, an aqueous solution of γ-aminopropylsilicone, and the like can be used.

In the silane coupling agent as described above, a functional group at one end of the molecule, usually chloro, alkoxy, or acetoxy group, is hydrolyzed to form a silanol group (SiOH), which is an inorganic oxide. The metal constituting the vapor deposition film of the object, or an active group on the film surface of the vapor deposition film of the inorganic oxide, for example, a reaction such as a dehydration condensation reaction by some action with a functional group such as a hydroxyl group, A silane coupling agent is modified on the film surface of the inorganic oxide vapor-deposited film by a covalent bond or the like, and further, a strong bond is obtained by adsorption or hydrogen bonding on the film surface of the inorganic oxide vapor-deposited film of the silanol group itself. Form.
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. -Reacts with substances constituting the adhesive layer, anchor coating layer, other layers, etc. to form a strong bond, and further, the above-mentioned printed pattern layer, laminating adhesive layer, The heat-sealable resin layer is firmly and tightly bonded through the anchor coating agent layer and the like to increase the laminating strength. Thus, in the present invention, the laminating strength is increased. It is possible to form a strong and highly laminated structure.
In the present invention, the inorganic and organic properties of the silane coupling agent are utilized, and the inorganic oxide vapor deposition film and the printed pattern layer, the adhesive layer, or the anchor coating agent layer are used as a heat sink. It improves the tight adhesion with the tosyl resin layer, thereby increasing the laminating strength and the like.

Next, in the present invention, examples of the filler constituting the polyurethane-based or polyester-based resin composition include 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 polyurethane-based or polyester-based resin composition liquid, improves its coating suitability, and is a silane coupling with a polyurethane-based or polyester-based resin as a binder resin. It binds via an agent to improve the cohesive strength of the coating film.

As explained above, the gas barrier laminate film according to the present invention is formed on one surface of the base film, if necessary, by a plasma treatment surface with an inert gas, chemical vapor deposition or physical vapor deposition. Deposition film of inorganic oxide, if necessary, plasma treatment surface by oxygen gas, gas barrier coating film, if necessary, plasma treatment surface by inert gas, inorganic oxide by chemical vapor deposition method or physical vapor deposition method In other words, the present invention relates to a gas barrier laminated film characterized in that a plasma-treated surface with oxygen gas and / or a primer agent layer are sequentially laminated.
Thus, the gas barrier laminate film according to the present invention has good close adhesion between the base film, the inorganic oxide vapor deposition film, the gas barrier coating film, the inorganic oxide vapor deposition film, and the like. While maintaining high gas barrier properties stably and having good transparency, heat resistance, impact resistance, etc., it is extremely useful as a gas barrier material constituting packaging bags, etc. For example, heat-sealable resin layers, intermediate base materials, plastic base materials, etc., are arbitrarily laminated to produce laminated materials as packaging materials having various layer configurations, and then used Then, bags can be made to produce packaging bags and packaging products of various forms.

Next, in the present invention, the heat-seal resin layer constituting the laminated material according to the present invention will be described. The heat-seal resin layer can be melted by heat and fused to each other. For example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate Polyolefin resin such as copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene or polypropylene, acrylic acid, methacrylic acid, maleic anhydride Acid-modified polyolefin resin modified with unsaturated carboxylic acid such as fumaric acid, etc. , One or a film of a resin or sheet consisting of more resins other like - can be used bets or a coating film.
The resin film or sheet can be used in a single layer or multiple layers, and the thickness of the resin film or sheet is about 5 μm to 300 μm, preferably 10 μm to 110 μm. The position is desirable.
Furthermore, in the present invention, the thickness of the above resin film or sheet is the inorganic oxide that uses the laminated material according to the present invention and constitutes the gas barrier laminated film when the packaging bag is produced. In order to prevent generation of scratches or cracks in the deposited film, it is preferable to relatively increase the film thickness, specifically, about 40 μm to 110 μm, preferably 50 μm. It is preferable that it is about ~ 100 micrometers.
Thus, in the present invention, among the resin films or sheets as described above, it is particularly preferable to use an unstretched polypropylene film or sheet having a thickness of about 50 μm to 100 μm.

Next, in the present invention, as an intermediate substrate constituting the laminated material according to the present invention, this is the basic or auxiliary material constituting the packaging bag according to the present invention, as with the aforementioned base film. From mechanical properties, physical properties, chemical properties, etc., excellent strength, excellent strength, heat resistance, moisture resistance, pinhole resistance, puncture resistance, transparency, etc. An excellent resin film or sheet can be used.
Specifically, for example, a film of tough resin such as polyester resin, polyamide resin, polyaramid resin, polypropylene resin, polycarbonate resin, polyacetal resin, fluorine resin, or the like. A sheet can be used.
Thus, as the resin film or sheet, any of an unstretched film or a stretched film stretched in a uniaxial direction or a biaxial direction can be used.
In the present invention, the thickness of the resin film or sheet may be a thickness that can be kept to the minimum necessary for strength, puncture resistance, rigidity, and the like. On the other hand, if it is too thin, the strength, puncture resistance, rigidity, etc. are lowered, which is not preferable.
In the present invention, for the reasons described above, about 10 μm to 100 μm, preferably about 12 μm to 50 μm is most desirable.
Thus, in the present invention, among the resin films or sheets as described above, it is particularly preferable to use a biaxially stretched polyamide resin film having a thickness of about 15 μm to 30 μm.

Next, in the present invention, the plastic substrate constituting the laminated material according to the present invention will be described. As such a plastic substrate, this is the basic material or auxiliary material constituting the packaging bag according to the present invention. Excellent mechanical, physical, chemical, etc. In addition, it has excellent puncture resistance, etc., as well as excellent heat resistance, moisture resistance, pinhole resistance, transparency, etc. Resin films or sheets can be used.
Specifically, for example, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as various nylon resins, polyaramid resins, polypropylene resins, polyethylene resins, polycarbonate resins, polyacetal resins, fluorine A film or sheet of a tough resin such as a resin or the like can be used.
In the above, as the resin film or sheet, any of an unstretched film or a stretched film stretched in a uniaxial direction or a biaxial direction can be used.
In the present invention, the thickness of the resin film or sheet may be a thickness that can be kept to the minimum necessary for strength, puncture resistance, and the like. If it is too thick, the cost increases. On the other hand, if it is too thin, the strength, puncture resistance, and the like are undesirably lowered.
In the present invention, about 9 μm to 100 μm, preferably about 12 μm to 50 μm is the most desirable for the reasons described above.
In the present invention, a desired printed pattern layer or the like can be provided on the front surface and / or back surface of the plastic substrate.

By the way, since packaging bags are usually subjected to severe physical and chemical conditions, the laminated materials constituting the packaging bags are required to have strict packaging suitability, deformation prevention strength, drop impact. Various conditions such as strength, pinhole resistance, heat resistance, sealability, quality maintenance, workability, hygiene, etc. are required. For this reason, in the present invention, in addition to the above materials, In addition, other materials that satisfy the above-mentioned conditions can be arbitrarily used. Specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, Ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, Ten 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 , Saponified ethylene-vinyl acetate copolymer, fluorine resin, diene resin, polyacetal resin, polyurethane resin, nitrocellulose, etc. Can be used.
In addition, for example, synthetic paper or the like can be used.
In the present invention, the above-described 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 particular, in the present invention, the other base material includes, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene having a barrier property that prevents permeation of water vapor, water, and the like. -Films or sheets of resin such as propylene copolymer, and various colored resin films having light-shielding properties formed by adding a colorant such as a pigment to the resin and kneading the resin with a desired additive. Or a sheet or the like 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, for example, characters, figures, symbols, patterns, etc. on one side or both sides of the above-mentioned base material constituting the gas barrier laminate film, laminate material, etc. according to the present invention. A desired printed pattern can be printed to form a printed pattern layer.
The printed pattern layer is mainly composed of one or more ordinary ink vehicles, and if necessary, a plasticizer, a stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a curing agent. One or more additives such as additives, crosslinking agents, lubricants, antistatic agents, fillers, etc. are optionally added, and colorants such as dyes and pigments are added, and solvents, diluents, etc. Kneaded sufficiently to prepare an ink composition, and then the ink composition is used. For example, gravure printing, offset printing, letterpress printing, screen printing, transfer printing, flexographic printing, etc. Can be used to form a printed pattern layer according to the present invention by printing a desired printed pattern consisting of characters, figures, symbols, patterns, etc. on one side of the substrate film. .

  In the above, as the ink vehicle, known ones such as sesame oil, drill oil, soybean oil, hydrocarbon oil, rosin, rosin ester, rosin modified resin, shellac, alkyd resin, phenolic resin, maleic acid Resin, natural resin, hydrocarbon resin, polyvinyl chloride resin, polyvinyl acetate resin, polystyrene resin, polyvinyl butyral resin, acrylic or methacrylic resin, polyamide resin, polyester resin, polyurethane resin, One or more of epoxy resins, urea resins, melamine resins, aminoalkyd resins, nitrocellulose, ethyl cellulose, chlorinated rubber, cyclized rubber, etc. can be used.

In the present invention, examples of the laminating adhesive constituting the laminating adhesive layer forming the laminate according to the present invention include, for example, polyvinyl acetate adhesive, ethyl acrylate, butyl, 2-ethylhexyl ester Homopolymers such as these, or polyacrylic acid ester adhesives, cyanoacrylate adhesives, ethylene and vinyl acetate, ethyl acrylate, acrylic acid, and the like, and their copolymers with methyl methacrylate, acrylonitrile, styrene, etc. , Ethylene copolymer adhesives composed of copolymers with monomers such as methacrylic acid, cellulose adhesives, polyester adhesives, polyamide adhesives, polyimide adhesives, amino acids composed of urea resins or melamine resins, etc. Resin adhesive, phenol resin adhesive, epoxy adhesive, Urethane adhesive, reactive (meth) acrylic adhesive, chloroprene rubber, nitrile rubber, rubber adhesive made of styrene-butadiene rubber, silicone adhesive, alkali metal silicate, low melting point glass, etc. Adhesives such as system adhesives and others can be used.
The composition system of the above-mentioned adhesive may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the property is any of film / sheet form, powder form, solid form, etc. Further, the bonding mechanism may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, a hot pressure type, and the like.
Thus, in the present invention, the above laminating adhesive is applied to one side of both of the laminated layers, for example, a coating method such as a roll coating method, a gravure roll coating method, a kiss coating method, or the like, or a printing method. Then, the solvent or the like is dried to form an adhesive layer for laminating, and the coating or printing amount is preferably about 0.1 to 10 g / m ² (dry state).

In the present invention, examples of the anchor coating agent constituting the anchor coating agent layer forming the laminated material according to the present invention include isocyanate (urethane), polyethyleneimine, and polybutadiene. Anchor coating agents such as those based on organic, organic titanium, etc. can be used.
Furthermore, in the present invention, as the melt-extruded resin in the melt-extrusion laminating method, for example, a low density polyethylene, a medium density polyethylene, a high density polyethylene, a linear (linear) low density polyethylene, or a metallocene catalyst is used. Polymerized ethylene-α-olefin copolymer, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene- Acid-modified polyolefin resins such as propylene copolymer, methylpentene polymer, polyethylene, polypropylene, etc. modified with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, etc., etc. Can be used.
In the present invention, when performing the above lamination, if necessary, for example, pretreatment such as corona treatment, ozone treatment, frame treatment, etc. can be optionally applied to the surface of the substrate to be laminated. .

By the way, in the present invention, as the anchor coat agent for forming the anchor coat layer as described above and the adhesive for laminate forming the laminate adhesive layer, for example, Aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, or aliphatics such as hexamethylene diisocyanate, xylylene diisocyanate A polyether polyurethane resin obtained by reacting a polyfunctional isocyanate such as a polyisocyanate with a hydroxyl group-containing compound such as a polyether polyol, a polyester polyol or a polyacrylate polyol, Mainly polyester-based polyurethane resin or polyacrylate polyurethane-based resin Lanka - co - DOO agents, or laminating - those it is desirable to use the preparative adhesive.
Thus, the anchor coat agent layer or the laminate adhesive layer formed by using the anchor coat agent or the laminating adhesive as described above, A soft, flexible and flexible thin film can be formed, its tensile elongation is improved, and it acts as a film having flexibility, flexibility, etc. on the inorganic oxide deposited film, For example, improving the post-processing suitability of the inorganic oxide vapor-deposited film at the time of post-processing such as laminating, printing or bag making, and cracking of the inorganic oxide vapor-deposited film at the post-processing This is to prevent generation and the like.
Incidentally, in the present invention, the anchor coat layer by the anchor coat agent and / or the laminate adhesive layer by the laminate adhesive as described above are based on JIS standard K7113. It has a tensile elongation of 100 to 300%.
Thus, in the present invention, the tensile elongation of the anchor coating layer by the anchor coating agent and / or the laminating adhesive layer by the laminating adhesive as described above, etc. This improves the tight adhesion between the barrier film and the heat seal resin layer, thereby preventing the occurrence of cracks in the vapor-deposited film of the inorganic oxide, the laminating strength, etc. It is something to enhance.
In the above, it is not preferable that the tensile elongation is less than 100%, because the flexibility as a laminated material is lost, and cracks and the like in the deposited film of the inorganic oxide are likely to occur, and the tensile elongation is not preferable. If it exceeds 300%, the adhesive strength as an anchor coating agent or a laminating adhesive is not sufficient, and the required laminating strength becomes difficult to be expressed. Is.

Next, in the present invention described above, the method for producing the laminated material according to the present invention will be described in more detail. As such a method, for example, a lamination method used when producing a normal packaging material, for example, wet lamination. , Dry lamination method, solvent-free lamination method, extrusion lamination method, coextrusion lamination method, inflation method, and other methods.
Thus, in the present invention, when performing the above-described lamination, if necessary, for example, pretreatment such as corona treatment, ozone treatment, or frame treatment is optionally applied to the surface of the substrate to be laminated. be able to.
In the above, when extrusion lamination is performed, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin. , A polyolefin resin such as ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene or polypropylene with acrylic acid, Acid-modified polyolefin resins modified with unsaturated carboxylic acids such as methacrylic acid, maleic anhydride, fumaric acid, etc. can be used as the resin for melt extrusion lamination.
At that time, as an adhesion assistant, for example, an anchor coating agent such as isocyanate, polyethyleneimine, or the like can be arbitrarily used.
In the present invention, when dry lamination is performed, for example, a solvent type, an aqueous type, an emulsion type having a vehicle as a main component such as vinyl, acrylic, polyurethane, polyamide, polyester, epoxy, etc. Other adhesives for laminating, etc. can be used.

Next, in the present invention, the packaging bag according to the present invention manufactured using the above laminated material will be described. The packaging bag uses the above laminated material, and its heat seal. The surfaces of the conductive resin layers are overlapped with each other, and then the peripheral end portion is heat sealed to form a seal portion, and a packaging bag having an opening at the upper end portion is formed. be able to.
Thus, as the bag making method, the above-mentioned laminated material is folded or overlapped so that the inner layer faces each other, and the peripheral edge thereof is, for example, a side seal type, two-layer type. Square seal type, three-way seal type, four-side seal type, envelope-attached seal type, jointed seal type (pill seal type), pleated seal type, flat bottom seal Heat-sealing in the form of a heat seal such as a shell type, square bottom seal type, gusset type, etc., and manufacturing packaging bags having various forms having an opening at the upper end. Can do.
In addition, as the packaging bag, for example, a self-supporting packaging bag (standing pouch) can be used.
In the above, as the heat seal method, for example, a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal and the like are known. It can be done by the method.

Next, in the present invention, various contents according to the present invention are filled by filling the contents from the opening of the packaging bag produced above, and then sealing the opening at the upper end with a heat seal or the like. A packaged product having the form of can be produced.
In the present invention, the contents are filled from the opening of the packaging bag produced above, and then the opening is sealed with a heat seal or the like at the upper end of the bag for retort according to the present invention. A semifinished packaging product using a pouch is manufactured, and then the semifinished packaging product is subjected to a heat treatment such as a retort treatment or a boil treatment, thereby producing a retort packaged food using the retort pouch according to the present invention. It is something that can be done.
In the above, as a method for retorting or boiling, for example, a normal retort kettle is used, and the temperature is about 110 to 130 ° C., preferably about 120 ° C., pressure, 1 to 3 kgf / cm ² · G, Preferably, a method of heating and pressurizing at about 2.1 kgf / cm ² · G, about 20 to 60 minutes, preferably about 30 minutes, or temperature, 90 to 100 ° C., preferably 90 ° C. It can be carried out by a method of performing a boil treatment in about front and rear, time, about 5 to 20 minutes, preferably about 10 minutes.
Thus, in the present invention, the contents can be subjected to heat sterilization, heat sterilization cooking, or the like by retort processing or boil processing as described above.

Next, in the present invention, the contents to be filled and packaged in the packaging bag according to the present invention include, for example, cooked food, marine product, frozen food, boiled food, simmered food, liquid soup, seasoning, drinking water, Other foods and drinks, such as curry, stew, soup, meat sauce, hamburger, meatball, sweet potato, oden, rice cake etc. Various foods and beverages such as foods, jelly-like foods, seasonings, water, etc. can be mentioned.
Thus, in the present invention, the packaging bag according to the present invention has heat resistance, pressure resistance, water resistance, heat seal resistance, pin hole resistance, puncture resistance, tight adhesion, etc. Excellent physical properties, especially barrier properties that prevent permeation of oxygen gas, water vapor, etc., transparency, withstands heat treatment associated with retort processing, etc., and further reduces weight and weight of containers and packaging waste In addition, the manufacturing cost can be reduced by shortening the manufacturing process, and the contents can be packed and packaged and the quality is excellent.

Specifically, in the present invention, for example, when a polyester-based resin film is used as the base film, a packaging bag having excellent physical properties such as heat resistance and bending resistance can be produced. In addition, for example, when a polyamide-based resin (nylon) film is used as the intermediate substrate, a packaging bag excellent in pinhole resistance and the like can be manufactured.
In the present invention, the vapor-deposited film of the inorganic oxide and the gas barrier coating film each have transparency and barrier properties that prevent permeation of oxygen gas, water vapor, etc. As a result, it exerts an effect such as barrier property that prevents permeation of oxygen gas, water vapor, etc., and finally, due to their synergistic effect, it exerts an effect such as barrier property, Unlike metal foil such as aluminum foil, it exhibits excellent transparency and excellent visibility of contents etc. This makes it possible to perform a metal detection test by means of, for example.
Further, in the present invention, the vapor deposition film of the inorganic oxide has a film thickness of several tens to several thousand mm, and the film thickness of the gas barrier coating film is also 0.1 g / m ^2. ~ 2.0 g / m ² (dry state), for example, compared with metal foils such as aluminum foils with a film thickness of around 5-20 μm. In addition, the weight of the container / packaging waste can be reduced and the weight thereof can be reduced.
Furthermore, in the present invention, an organic silicon compound is used as a vapor deposition monomer gas, and a silicon oxide vapor deposition film formed by plasma chemical vapor deposition is used as an inorganic oxide constituting the barrier layer. When used as a vapor deposition film of an object, the vapor deposition film of silicon oxide is rich in flexibility and has flexibility and the like. It has the advantage of not.
Next, the present invention will be described more specifically with reference to examples.

(1). First, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used as a base film, and this is mounted on an unwinding roll of a plasma chemical vapor deposition apparatus, and then conveyed at a line speed of 150 mm / min. Then, using a magnetron sputtering apparatus, introducing argon gas 600 sccm, performing plasma treatment at an output of 20 kW, forming a plasma-treated surface with an inert gas on the surface of the biaxially stretched polyethylene terephthalate film, Then, a 200 nm thick silicon oxide vapor deposition film was formed on the plasma treated surface under the following conditions.
(Deposition conditions)
Reaction gas mixing ratio: Hexamethyldisiloxane: Oxygen gas: Helium = 1.2: 5.0: 2.5 (Unit: Slm)
Ultimate pressure: 5.0 × 10 ^-5 mbar
Film forming pressure: 7.0 × 10 ⁻² mbar
Line speed: 150 m / min
Power: 35kW
Next, immediately after forming the silicon oxide vapor deposition film having a thickness of 200 mm as described above, a glow discharge plasma generator is used on the silicon oxide vapor deposition film surface, and the power is 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 ⁻² mbar and a processing speed of 150 m / min. Then, a plasma-treated surface was formed in which the surface tension of the deposited silicon oxide film surface was improved by 54 dyne / cm or more.
(2). On the other hand, according to the composition shown in Table 1 below, the composition a. Composition prepared in advance in EVOH solution in which EVOH (ethylene copolymerization ratio 29%) was dissolved in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzed solution composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water, and stirred, and further prepared in advance c. A mixed solution composed of an aqueous polyvinyl alcohol solution, a silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating solution.
(Table 1)
a EVOH (ethylene copolymerization rate 29%) 0.610 (wt%)
Isopropyl alcohol 3.294
H ₂ O 2.196
b Ethyl silicate 40 11.460
Isopropyl alcohol 17.662
Aluminum acetylacetone 0.020
H ₂ O 13.752
c Polyvinyl alcohol 1.520
Silane coupling agent 0.050
Isopropyl alcohol 13.844
H ₂ O 35.462
Acetic acid 0.130
Total 100.000 (wt%)
Next, the gas barrier composition produced above is used for the plasma treatment surface of the silicon oxide vapor deposition film formed in the above (1), and this is coated by the gravure roll coating method, and then at 100 ° C. Heat treatment was performed for 30 seconds to form a gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state).
(3). The 12 μm-thick biaxially stretched polyethylene terephthalate film on which the gas barrier coating film is formed as described above is mounted on the unwinding roll of the plasma chemical vapor deposition apparatus, and then transported at a line speed of 150 mm / min. Using an apparatus, an argon gas of 600 sccm is introduced, and plasma treatment is performed at an output of 20 kW to form a plasma treatment surface with an inert gas on the surface of the gas barrier coating film, and then on the plasma treatment surface. A vapor-deposited film of silicon oxide having a thickness of 200 mm was formed under the following conditions. (Deposition conditions)
Reaction gas mixing ratio: Hexamethyldisiloxane: Oxygen gas: Helium = 1.2: 5.0: 2.5 (Unit: Slm)
Ultimate pressure: 5.0 × 10 ^-5 mbar
Film forming pressure: 7.0 × 10 ⁻² mbar
Line speed: 150 m / min
Power: 35kW
Next, immediately after forming the silicon oxide vapor deposition film having a thickness of 200 mm as described above, a glow discharge plasma generator is used on the silicon oxide vapor deposition film surface, and the power is 9 kW, oxygen gas (O ₂ ): argon gas. (Ar) = 7Z0: 2.5 (unit: Slm) is used, and oxygen / argon mixed gas plasma treatment is performed at a mixed gas pressure of 6 × 10 ⁻² mbar and a processing speed of 150 m / min. A plasma-treated surface was formed in which the surface tension of the silicon deposition film surface was improved by 54 dyne / cm or more.
Further, an epoxy silane coupling agent (8.0 wt%) and an antiblocking agent (1.0 wt%) are added to the polyester resin initial condensate on the plasma-treated surface formed above. A primer resin composition obtained by sufficiently kneading is coated by a gravure roll coating method so that the film thickness is 0.2 g / m ² (dry state). A layer was formed to produce a gas barrier laminate film according to the present invention.
(4). Next, after forming a desired printing pattern on the surface of the primer layer of the gas barrier laminate film produced in the above (3), a two-component curable polyurethane laminating film is formed on the entire surface including the printing pattern. The adhesive for coating is coated to a thickness of 4.0 g / m ² (in a dry state) using a gravure roll coating method to form an adhesive layer for laminating, and then used for the lamination A biaxially stretched nylon 6 film having a thickness of 15 μm was laminated on the surface of the adhesive layer with the corona-treated surfaces facing each other, and then both were laminated by dry lamination.
Next, after applying the corona discharge treatment to the surface of the biaxially stretched nylon 6 film laminated as described above, a laminating adhesive layer is formed on the corona treatment surface in the same manner as described above, and thereafter The laminate material according to the present invention was manufactured by dry laminating and laminating an unstretched polypropylene film having a thickness of 60 μm on the laminating adhesive layer surface.
(5). Next, two sheets of the laminated material produced above are prepared, the non-stretched polypropylene film faces are overlapped with each other, and then the outer peripheral edge is sealed in a three-way heat seal. A three-sided seal-type flexible packaging bag having an opening portion and an opening on the upper side was manufactured. In the three-sided seal type soft packaging bag produced above, water is filled and packaged from the opening, and then the opening is heat sealed to form the upper seal. A semi-finished packaging product is manufactured, and then the semi-finished packaging product is placed in a retort kettle and subjected to retort treatment under conditions of temperature, 120 ° C., pressure, 2.1 kgf / cm ² · G, time, 30 minutes. The retort packaged food according to the present invention was produced.
The retort packaged food produced above has excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pinhole resistance, piercing properties, transparency, etc. Excellent barrier properties against oxygen gas, water vapor, etc., with no bag breakage or leakage of contents, etc., and functions as a food container, such as content filling and packaging suitability, distribution suitability, storage suitability, etc. .

(1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as the base film. Hereinafter, in the same manner as in Example 1 above, the plasma-treated surface with an inert gas was used in the same manner as in Example 1 above. Then, a 200 nm thick silicon oxide vapor deposition film was formed on the plasma treatment surface, and a plasma treatment surface with oxygen gas was further formed on the silicon oxide vapor deposition film.
(2). On the other hand, according to the composition shown in Table 2 below, composition a. EVOH (ethylene copolymerization ratio 29%) A previously prepared composition b. In an EVOH solution dissolved in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzate composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water, followed by stirring, and a previously prepared composition c. A mixed liquid composed of an aqueous polyvinyl alcohol solution, acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating liquid.
(Table 2)
a EVOH (ethylene copolymerization ratio 29%) 0.122 (wt%)
Isopropyl alcohol 0.659
H ₂ O 0.439
b Ethylsilicate 40 9.146
Isopropyl alcohol 8.780
Aluminum acetylacetone 0.018
H ₂ O 16.291
c Polyvinyl alcohol 1.220
Isopropyl alcohol 19.893
H ₂ O 43.329
Acetic acid 0.103
Total 100.000 (wt%)
Next, the gas barrier composition produced above is used for the plasma treatment surface of the silicon oxide vapor deposition film formed in the above (1), and this is coated by the gravure roll coating method, and then at 100 ° C. Heat treatment was performed for 30 seconds to form a gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state).
(3). Using a 12 μm thick biaxially stretched polyethylene terephthalate film having a gas barrier coating film formed as described above, the gas barrier coating was performed in the same manner as in Example 1 described above. A plasma-treated surface with an inert gas is formed on the surface of the film, and then a 200-nm thick silicon oxide vapor-deposited film is formed on the plasma-treated surface. Further, on the silicon oxide vapor-deposited film surface, A plasma-treated surface with oxygen gas was formed, and further a primer agent layer was formed to produce a gas barrier laminate film according to the present invention.
(4). Next, using the gas barrier laminate film produced in the above (3), the laminate material, the three-way sheet according to the present invention is used in the same manner as in the above-described Example 1 in the same manner as in the above-described Example 1. Le-shaped soft packaging bags, semi-finished packaging products, and retort-packed foods were manufactured.
The retort packaged food produced above has excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pinhole resistance, piercing properties, transparency, etc. Excellent barrier properties against oxygen gas, water vapor, etc., with no bag breakage or leakage of contents, etc., and functions as a food container, such as content filling and packaging suitability, distribution suitability, storage suitability, etc. .

(1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as the base film. Hereinafter, in the same manner as in Example 1 above, the plasma-treated surface with an inert gas was used in the same manner as in Example 1 above. Then, a 200 nm thick silicon oxide vapor deposition film was formed on the plasma treatment surface, and a plasma treatment surface with oxygen gas was further formed on the silicon oxide vapor deposition film.
(2). On the other hand, according to the composition shown in Table 3 below, the prepared composition a. A pre-prepared composition b. A hydrolyzate composed of ethyl silicate 40, isopropyl alcohol, aluminum acetylacetone and ion-exchanged water was added and stirred sufficiently to obtain a colorless and transparent barrier coating solution.
(Table 3)
a Polyvinyl alcohol 1.235 (wt%)
Isopropyl alcohol 20.139
H ₂ O 43.866
Acetic acid 0.104
b Ethylsilicate 40 9.257
Isopropyl alcohol 8.888
Aluminum acetylacetone 0.018
H ₂ O 16.493
Total 100.000 (wt%)
Next, the gas barrier composition produced above is used for the plasma treatment surface of the silicon oxide vapor deposition film formed in the above (1), and this is coated by the gravure roll coating method, and then at 100 ° C. Heat treatment was performed for 30 seconds to form a gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state).
(3). Using a 12 μm thick biaxially stretched polyethylene terephthalate film having a gas barrier coating film formed as described above, the gas barrier coating was performed in the same manner as in Example 1 described above. A plasma-treated surface with an inert gas is formed on the surface of the film, and then a 200-nm thick silicon oxide vapor-deposited film is formed on the plasma-treated surface. A plasma-treated surface with oxygen gas was formed, and further a primer layer was formed to produce a gas barrier laminate film according to the present invention.
(4). Next, using the gas barrier laminate film produced in the above (3), the laminate material, the three-way sheet according to the present invention is used in the same manner as in the above-described Example 1 in the same manner as in the above-described Example 1. Le-shaped soft packaging bags, semi-finished packaging products, and retort-packed foods were manufactured.
The retort packaged food manufactured above has excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. Excellent barrier properties against oxygen gas, water vapor, etc., with no bag breakage or leakage of contents, etc., and functions as a food container, such as content filling and packaging suitability, distribution suitability, storage suitability, etc. .

(1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as the base film. Hereinafter, in the same manner as in Example 1 above, the plasma-treated surface with an inert gas was used in the same manner as in Example 1 above. Then, a 200 nm thick silicon oxide vapor deposition film was formed on the plasma treatment surface, and a plasma treatment surface with oxygen gas was further formed on the silicon oxide vapor deposition film.
(2). On the other hand, according to the composition shown in Table 4 below, the prepared composition b. In a mixture of polyvinyl alcohol, N, N-dimethylbenzylamine ethanol solution (32 wt%) and ion-exchanged water. A hydrolyzed solution consisting of ethyl silicate (tetraethoxysilane), ethanol, 2N hydrochloric acid, ion-exchanged water and a silane coupling agent (epoxysilica SH6040) was added and stirred to obtain a colorless and transparent barrier coating solution. .
(Table 4)
a Ethyl silicate 34.074 (wt%)
Ethanol 34.074
2N hydrochloric acid 2.535
H2O 2.058
Silane coupling agent 3.407
b Polyvinyl alcohol 2.372
H2O 21.344
N, N-dimethylbenzylamine ethanol solution (32 wt%)
0.136
Total 100.000 (wt%)
Next, the gas barrier composition produced above is used for the plasma treatment surface of the silicon oxide vapor deposition film formed in the above (1), and this is coated by the gravure roll coating method, and then at 100 ° C. Heat treatment was performed for 30 seconds to form a gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state).
(3). Using a 12 μm thick biaxially stretched polyethylene terephthalate film on which a gas barrier coating film was formed as described above, the gas barrier coating was performed in the same manner as in Example 1 described above. A plasma-treated surface with an inert gas is formed on the surface of the film, and then a 200-nm thick silicon oxide vapor-deposited film is formed on the plasma-treated surface. Further, on the silicon oxide vapor-deposited film surface, A plasma-treated surface with oxygen gas was formed, and further a primer layer was formed to produce a gas barrier laminate film according to the present invention.
(4). Next, using the gas barrier laminate film produced in the above (3), the laminate material, the three-way sheet according to the present invention is used in the same manner as in the above-described Example 1 in the same manner as in the above-described Example 1. Le-shaped soft packaging bags, semi-finished packaging products, and retort-packed foods were manufactured.
The retort packaged food manufactured above has excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. Excellent barrier properties against oxygen gas, water vapor, etc., with no bag breakage or leakage of contents, etc., and functions as a food container, such as content filling and packaging suitability, distribution suitability, storage suitability, etc. .

(1). First, a biaxially stretched nylon 6 film having a thickness of 15 μm was used as a base film, and this was mounted on an unwinding roll of a plasma chemical vapor deposition apparatus, and then conveyed at a line speed of 100 mm / min. A sputtering apparatus is used to introduce an argon gas of 600 sccm, and a plasma treatment is performed at an output of 20 kW to form a plasma treatment surface with an inert gas. Then, the thickness of the plasma treatment surface is reduced under the following conditions. A 200-nm silicon oxide vapor deposition film was formed.
(Deposition conditions)
Reaction gas mixing ratio: Hexamethyldisiloxane: Oxygen gas: Helium = 1: 11: 10 (Unit: Slm)
Ultimate pressure: 5.2 × 10 ⁻⁶ mbar
Film ^- forming pressure: 5.1 × 10 ⁻² mbar
Line speed: 100 m / min
Power: 30kW
Next, immediately after forming the silicon oxide vapor deposition film having a thickness of 200 mm as described above, 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 ⁻² mbar and a processing speed of 100 m / min. Then, a plasma-treated surface was formed in which the surface tension of the deposited silicon oxide film surface was improved by 54 dyne / cm or more.
(2). On the other hand, according to the composition shown in Table 1 below, the composition a. Composition prepared in advance in EVOH solution in which EVOH (ethylene copolymerization ratio 29%) was dissolved in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzed solution composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water, and stirred, and further prepared in advance c. A mixed solution composed of an aqueous polyvinyl alcohol solution, a silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating solution.
(Table 1)
a EVOH (ethylene copolymerization rate 29%) 0.610 (wt%)
Isopropyl alcohol 3.294
H ₂ O 2.196
b Ethyl silicate 40 11.460
Isopropyl alcohol 17.662
Aluminum acetylacetone 0.020
H ₂ O 13.752
c Polyvinyl alcohol 1.520
Silane coupling agent 0.050
Isopropyl alcohol 13.844
H ₂ O 35.462
Acetic acid 0.130
Total 100.000 (wt%)
Next, on the plasma-treated surface of silicon oxide formed in (1) above, the gas barrier composition produced above is used, and this is coated by a gravure roll coating method, and then at 100 ° C. for 30 seconds. A gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state) was formed by heat treatment.
(3). The biaxially stretched nylon 6 film having a thickness of 15 μm on which the gas barrier coating film is formed is mounted on the unwinding roll of the plasma chemical vapor deposition apparatus, and then conveyed at a line speed of 100 mm / min. In use, an argon gas of 600 sccm is introduced and plasma treatment is performed at an output of 20 kW to form a plasma treatment surface with an inert gas on the surface of the gas barrier coating film. A silicon oxide vapor deposition film having a thickness of 200 mm was formed under the conditions shown in FIG.
(Deposition conditions)
Reaction gas mixing ratio: Hexamethyldisiloxane: Oxygen gas: Helium = 1: 11: 10 (Unit: Slm)
Ultimate pressure: 5.2 × 10 ⁻⁶ mbar
Film ^- forming pressure: 5.1 × 10 ⁻² mbar
Line speed: 100 m / min
Power: 30kW
Next, immediately after forming the silicon oxide vapor deposition film having a thickness of 200 mm as described above, 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 ⁻² mbar and a processing speed of 100 m / min. Then, a plasma-treated surface was formed in which the surface tension of the deposited silicon oxide film surface was improved by 54 dyne / cm or more.
Furthermore, an epoxy-based silane coupling agent (8.0% by weight) and an anti-blocking agent (1.0% by weight) are added to the polyurethane resin initial condensate on the plasma-treated surface formed above. A primer resin composition obtained by sufficiently kneading is coated by a gravure roll coating method so as to have a film thickness of 0.5 g / m ² (dry state). A layer was formed to produce a gas barrier laminate film according to the present invention.
(4). Next, a normal gravure ink composition is used on the corona-treated surface of a biaxially stretched polypropylene film having a thickness of 20 μm, and a predetermined printing pattern composed of letters, figures, patterns, etc. is printed by a gravure printing method. A printed pattern layer was formed.
Next, a two-component curable polyurethane adhesive (main agent: polyester polyol, curing agent: aliphatic isocyanate) is used on the entire surface including the printed pattern layer formed above, and this is subjected to a gravure roll coating method. The laminate is coated to a thickness of 5.0 g / m ² (dry state) to form an adhesive layer for laminating, and then the gas barrier laminate film produced in (3) above is applied to the surface of the laminating adhesive layer. The surfaces of the primer agent layers were made to face each other, and then both layers were dry laminated.
Further, on the surface of the corona-treated surface of the biaxially stretched nylon 6 film of the gas barrier laminate film laminated with the dry laminate described above, a two-component curable urethane adhesive (main agent: polyester polyol, curing agent: aliphatic socyanate) Is coated using a gravure roll coat method to a thickness of 5.0 g / m ² (in a dry state) to form a laminating adhesive layer, and then on the laminating adhesive layer surface Then, an unstretched polypropylene film having a thickness of 60 μm was laminated by dry lamination to produce a laminate according to the present invention.
(5). Next, two sheets of the laminated material produced above are prepared, the non-stretched polypropylene film faces are overlapped with each other, and then the outer peripheral edge is sealed in a three-way heat seal. A three-sided seal-type flexible packaging bag having an opening portion and an opening on the upper side was manufactured. In the three-sided seal type soft packaging bag produced above, water is filled and packaged from the opening, and then the opening is heat sealed to form the upper seal. A semi-finished packaging product is manufactured, and then the semi-finished packaging product is placed in a retort kettle and subjected to retort treatment under conditions of temperature, 120 ° C., pressure, 2.1 kgf / cm ² · G, time, 30 minutes. The retort packaged food according to the present invention was produced.
The retort packaged food manufactured above has excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. Excellent in barrier properties against oxygen gas, water vapor, etc.

(1). First, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as a base film, and this was mounted on a winding roll of a take-up vacuum deposition apparatus, and then a biaxially stretched polyethylene terephthalate film. Without applying plasma treatment with an inert gas on the corona-treated surface of the above, using aluminum as a vapor deposition source and supplying oxygen gas, a vacuum vapor deposition method using an electron beam (EB) heating method, under the following vapor deposition conditions A vapor-deposited film of aluminum oxide having a thickness of 200 mm was formed.
(Deposition conditions)
Degree of vacuum in the deposition chamber; 2 × 10 ^-4 mbar
Degree of vacuum in winding chamber; 2 × 10 ^-2 mbar
Electron beam power: 25 kW
Film transport speed: 240 m / min
Next, immediately after the aluminum oxide vapor deposition film having a thickness of 200 mm is formed as described above, a glow discharge plasma generator is used on the aluminum oxide vapor deposition film surface, and the power is 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 ⁻² mbar and a processing speed of 200 m / min. Then, a plasma-treated surface was formed in which the surface tension of the vapor deposition film surface of aluminum oxide was improved by 54 dyne / cm or more.
(2). On the other hand, according to the composition shown in Table 1 below, the composition a. Composition prepared in advance in EVOH solution in which EVOH (ethylene copolymerization ratio 29%) was dissolved in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzed solution composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water, and stirred, and further prepared in advance c. A mixed solution composed of an aqueous polyvinyl alcohol solution, a silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating solution.
(Table 1)
a EVOH (ethylene copolymerization rate 29%) 0.610 (wt%)
Isopropyl alcohol 3.294
H ₂ O 2.196
b Ethyl silicate 40 11.460
Isopropyl alcohol 17.662
Aluminum acetylacetone 0.020
H ₂ O 13.752
c Polyvinyl alcohol 1.520
Silane coupling agent 0.050
Isopropyl alcohol 13.844
H ₂ O 35.462
Acetic acid 0.130
Total 100.000 (wt%)
Next, the gas barrier composition produced above is used for the plasma treatment surface of the aluminum oxide vapor deposition film formed in (1) above, and this is coated by the gravure roll coating method, and then at 100 ° C. Heat treatment was performed for 30 seconds to form a gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state).
(3). The 12 μm-thick biaxially stretched polyethylene terephthalate film on which the gas barrier coating film is formed as described above is used, and this is mounted on the unwinding roll of a take-up vacuum deposition apparatus, and then the above gas barrier coating film The film is subjected to the following deposition conditions by vacuum deposition using an electron beam (EB) heating method while supplying oxygen gas using aluminum as a deposition source without performing plasma treatment with an inert gas. A vapor-deposited film of aluminum oxide having a thickness of 200 mm was formed.
(Deposition conditions)
Degree of vacuum in the deposition chamber; 2 × 10 ^-4 mbar
Degree of vacuum in winding chamber; 2 × 10 ^-2 mbar
Electron beam power: 25 kW
Film transport speed: 240 m / min
Next, immediately after the aluminum oxide vapor deposition film having a thickness of 200 mm is formed as described above, a glow discharge plasma generator is used on the aluminum oxide vapor deposition film surface, and the power is 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 ⁻² mbar and a processing speed of 200 m / min. Then, a plasma-treated surface was formed in which the surface tension of the vapor deposition film surface of aluminum oxide was improved by 54 dyne / cm or more.
Furthermore, an epoxy-based silane coupling agent (8.0% by weight) and an anti-blocking agent (1.0% by weight) are added to the polyurethane resin initial condensate on the plasma-treated surface formed above. A primer resin composition obtained by sufficiently kneading is coated by a gravure roll coating method so as to have a film thickness of 0.5 g / m ² (dry state). A layer was formed to produce a gas barrier laminate film according to the present invention.
(4). Next, after forming a desired printing pattern on the surface of the primer layer of the gas barrier laminate film produced in the above (3), a two-component curable polyurethane laminating film is formed on the entire surface including the printing pattern. The adhesive for coating is coated to a thickness of 4.0 g / m ² (in a dry state) using a gravure roll coating method to form an adhesive layer for laminating, and then used for the lamination A biaxially stretched nylon 6 film having a thickness of 15 μm was laminated on the surface of the adhesive layer with the corona-treated surfaces facing each other, and then both were laminated by dry lamination.
Next, after applying the corona discharge treatment to the surface of the biaxially stretched nylon 6 film laminated as described above, a laminating adhesive layer is formed on the corona treatment surface in the same manner as described above, and thereafter The laminate material according to the present invention was manufactured by dry laminating and laminating an unstretched polypropylene film having a thickness of 60 μm on the laminating adhesive layer surface.
(5). Next, two sheets of the laminated material produced above are prepared, the non-stretched polypropylene film faces are overlapped with each other, and then the outer peripheral edge is sealed in a three-way heat seal. A three-sided seal-type flexible packaging bag having an opening portion and an opening on the upper side was manufactured. In the three-sided seal type soft packaging bag produced above, water is filled and packaged from the opening, and then the opening is heat sealed to form the upper seal. A semi-finished packaging product is manufactured, and then the semi-finished packaging product is placed in a retort kettle and subjected to retort treatment under conditions of temperature, 120 ° C., pressure, 2.1 kgf / cm ² · G, time, 30 minutes. The retort packaged food according to the present invention was produced.
The retort packaged food manufactured above has excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. Excellent barrier properties against oxygen gas, water vapor, etc., with no bag breakage or leakage of contents, etc., and functions as a food container, such as content filling and packaging suitability, distribution suitability, storage suitability, etc. .

(1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as the base film, and the following was performed in the same manner as in Example 6 above, and in the same manner as in Example 6 above, the biaxially stretched polyethylene terephthalate film. On the corona-treated surface, an aluminum oxide vapor-deposited film having a thickness of 200 mm was formed, and further, a plasma-treated surface with oxygen gas was formed on the aluminum oxide vapor-deposited film.
(2). On the other hand, according to the composition shown in Table 3 below, the prepared composition a. A pre-prepared composition b. A hydrolyzate composed of ethyl silicate 40, isopropyl alcohol, aluminum acetylacetone and ion-exchanged water was added and stirred sufficiently to obtain a colorless and transparent barrier coating solution.
(Table 3)
a Polyvinyl alcohol 1.235 (wt%)
Isopropyl alcohol 20.139
H ₂ O 43.866
Acetic acid 0.104
b Ethylsilicate 40 9.257
Isopropyl alcohol 8.888
Aluminum acetylacetone 0.018
H ₂ O 16.493
Total 100.000 (wt%)
Next, the gas barrier composition produced above is used for the plasma treatment surface of the aluminum oxide vapor deposition film formed in (1) above, and this is coated by the gravure roll coating method, and then at 100 ° C. Heat treatment was performed for 30 seconds to form a gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state).
(3). Using a 12 μm thick biaxially stretched polyethylene terephthalate film on which a gas barrier coating film was formed as described above, the gas barrier coating was performed in the same manner as in Example 6 described above. A 200 nm-thick aluminum oxide vapor deposition film is formed on the film surface without forming an inert gas plasma treatment surface. Further, an oxygen gas plasma treatment surface is formed on the aluminum oxide vapor deposition film surface. And further a primer layer was formed to produce a gas barrier laminate film according to the present invention.
(4). Next, using the gas barrier laminate film produced in the above (3), the laminate material, the three-way sheet according to the present invention is used in the same manner as in the above-described Example 6 as in the above-described Example 6. Le-shaped soft packaging bags, semi-finished packaging products, and retort-packed foods were manufactured.
The retort packaged food manufactured above has excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. Excellent barrier properties against oxygen gas, water vapor, etc., with no bag breakage or leakage of contents, etc., and functions as a food container, such as content filling and packaging suitability, distribution suitability, storage suitability, etc. .

(1). First, a biaxially stretched nylon 6 film having a thickness of 15 μm was used as a base film, and this was mounted on a winding roll of a take-up vacuum deposition apparatus, and then the corona of the above biaxially stretched nylon 6 film. Without subjecting the treatment surface to plasma treatment with an inert gas, using aluminum as a vapor deposition source and supplying oxygen gas, a vacuum vapor deposition method using an electron beam (EB) heating method is performed under the following vapor deposition conditions. A vapor-deposited film of aluminum oxide having a thickness of 200 mm was formed.
(Deposition conditions)
Degree of vacuum in the deposition chamber; 2 × 10 ^-4 mbar
Degree of vacuum in winding chamber; 2 × 10 ^-2 mbar
Electron beam power: 25 kW
Film transport speed: 240 m / min
Next, immediately after the aluminum oxide vapor deposition film having a thickness of 200 mm is formed as described above, a glow discharge plasma generator is used on the aluminum oxide vapor deposition film surface, and the power is 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 ⁻² mbar and a processing speed of 200 m / min. A plasma-treated surface was formed in which the surface tension of the vapor deposition film surface of aluminum oxide was improved by 54 dyne / cm or more.
(2). On the other hand, according to the composition shown in Table 1 below, the composition a. Composition prepared in advance in EVOH solution in which EVOH (ethylene copolymerization ratio 29%) was dissolved in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzed solution composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water, and stirred, and further prepared in advance c. A mixed solution composed of an aqueous polyvinyl alcohol solution, a silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating solution.
(Table 1)
a EVOH (ethylene copolymerization rate 29%) 0.610 (wt%)
Isopropyl alcohol 3.294
H ₂ O 2.196
b Ethyl silicate 40 11.460
Isopropyl alcohol 17.662
Aluminum acetylacetone 0.020
H ₂ O 13.752
c Polyvinyl alcohol 1.520
Silane coupling agent 0.050
Isopropyl alcohol 13.844
H ₂ O 35.462
Acetic acid 0.130
Total 100.000 (wt%)
Next, the gas barrier composition produced above is used for the plasma treatment surface of the aluminum oxide vapor deposition film formed in (1) above, and this is coated by the gravure roll coating method, and then at 100 ° C. Heat treatment was performed for 30 seconds to form a gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state).
(3). The biaxially stretched nylon 6 film having a thickness of 15 μm on which the gas barrier coating film was formed as described above was used, and this was mounted on a winding roll of a take-up vacuum deposition apparatus. Without subjecting the surface to plasma treatment with an inert gas, using an aluminum as a deposition source and supplying oxygen gas, a vacuum deposition method using an electron beam (EB) heating method is used to form a film thickness under the following deposition conditions. A 200-mm aluminum oxide vapor deposition film was formed.
(Deposition conditions)
Degree of vacuum in the deposition chamber; 2 × 10 ^-4 mbar
Degree of vacuum in winding chamber; 2 × 10 ^-2 mbar
Electron beam power: 25 kW
Film transport speed: 240 m / min
Next, immediately after the aluminum oxide vapor deposition film having a thickness of 200 mm is formed as described above, a glow discharge plasma generator is used on the aluminum oxide vapor deposition film surface, and the power is 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 ⁻² mbar and a processing speed of 200 m / min. A plasma-treated surface was formed in which the surface tension of the vapor deposition film surface of aluminum oxide was improved by 54 dyne / cm or more.
Furthermore, an epoxy-based silane coupling agent (8.0% by weight) and an anti-blocking agent (1.0% by weight) are added to the polyurethane resin initial condensate on the plasma-treated surface formed above. A primer resin composition obtained by sufficiently kneading is coated by a gravure roll coating method so as to have a film thickness of 0.5 g / m ² (dry state). A layer was formed to produce a gas barrier laminate film according to the present invention.
(4). Next, a normal gravure ink composition is used on the corona-treated surface of a biaxially stretched polypropylene film having a thickness of 20 μm, and a predetermined printing pattern composed of letters, figures, patterns, etc. is printed by a gravure printing method. A printed pattern layer was formed.
Next, a two-component curable polyurethane adhesive (main agent: polyester polyol, curing agent: aliphatic isocyanate) is used on the entire surface including the printed pattern layer formed above, and this is subjected to a gravure roll coating method. The laminate is coated to a thickness of 5.0 g / m ² (dry state) to form an adhesive layer for laminating, and then the gas barrier laminate film produced in (3) above is applied to the surface of the laminating adhesive layer. The surfaces of the primer agent layers were made to face each other, and then both layers were dry laminated.
Further, on the surface of the corona-treated surface of the biaxially stretched nylon 6 film of the gas barrier laminate film laminated with the dry laminate described above, a two-component curable urethane adhesive (main agent: polyester polyol, curing agent: aliphatic socyanate) Is coated using a gravure roll coat method to a thickness of 5.0 g / m ² (in a dry state) to form a laminating adhesive layer, and then on the laminating adhesive layer surface Then, an unstretched polypropylene film having a thickness of 60 μm was laminated by dry lamination to produce a laminate according to the present invention.
(5). Next, two sheets of the laminated material produced above are prepared, the non-stretched polypropylene film faces are overlapped with each other, and then the outer peripheral edge is sealed in a three-way heat seal. A three-sided seal-type flexible packaging bag having an opening portion and an opening on the upper side was manufactured. In the three-sided seal type soft packaging bag produced above, water is filled and packaged from the opening, and then the opening is heat sealed to form the upper seal. A semi-finished packaging product is manufactured, and then the semi-finished packaging product is placed in a retort kettle and subjected to retort treatment under conditions of temperature, 120 ° C., pressure, 2.1 kgf / cm ² · G, time, 30 minutes. The retort packaged food according to the present invention was produced.
The retort packaged food manufactured above has excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. Excellent barrier properties against oxygen gas, water vapor, etc., with no bag breakage or leakage of contents, etc., and functions as a food container, such as content filling and packaging suitability, distribution suitability, storage suitability, etc. .

[Experimental example]
About the gas-barrier laminated film manufactured in said Examples 1-8, oxygen permeability and water vapor permeability were measured.
Moreover, about the packaging bag manufactured by bag-making the laminated material manufactured using the barrier film manufactured in said Examples 1-8, oxygen permeability before and behind retort processing, water vapor permeability, and retort processing The laminating strength before and after was measured.
(1). Measurement of Oxygen Permeability This was measured with a measuring instrument (model name, OXTRAN) manufactured by MOCON, USA under the conditions of a temperature of 23 ° C. and a humidity of 90% RH.
(2). Measurement of Water Vapor Permeability This was measured with a measuring instrument (model name, PERMATRAN) manufactured by MOCON, USA, under conditions of a temperature of 40 ° C. and a humidity of 90% RH.
(3). Measurement of Laminate Strength Laminate strength was measured using a Tensilon measuring instrument with a test piece of 15 mm and a peeling speed of 50 min.
The measurement results are shown in Table 5 and Table 6 below.

(Table 5)
┌────┬───────┬────────┐ │ │ Oxygen permeability │ Water vapor permeability │ ├────┼───────┼─── ─────┤ │Example 1│ 0.3 │ 0.2 │ ├────┼───────┼────────┤ │Example 2│ 0.2 │ 0.2 │ ├────┼───────┼────────┤ │Example 3│ 0.3 │ 0.2 │ ├────┼─── ────┼────────┤ │Example 4│ 0.3 │ 0.1 │ ├────┼───────┼────────┤ │Example 5│ 0.2 │ 0.2 │ ├────┼───────┼────────┤ │Example 6│ 0.2 │ 0.2 │ ├ ────┼───────┼────────┤ │Example 7│ 0.2 │ 0.1 │ ├────┼───────┼── ───── ──┤ │Example 8│ 0.3 │ 0.2 │ └────┴───────┴────────┘ In Table 5 above, the unit of oxygen permeability Is [cc / m ² / day / atm · 23 ° C. · 90% RH], and the unit of water vapor permeability is [g / m ² / day · 40 ° C. · 90% RH].

(Table 6)
┌────┬───────────┬───────────┐ │ │ Oxygen permeability │ Water vapor permeability │ │ ├ ─────┬── ───┼─────┬ ─────┤ │ │Before retort │After retort │Before retort │After retort │ ├────┼─────┼─────┼── ───┼─────┤ │Example 1│ 0.3 │ 0.5 │ 0.2 │ 0.6 │ ├────┼─────┼─────┼── ────┼─────┤ │Example 2│ 0.2 │ 0.4 │ 0.2 │ 0.6 │ ├────┼─────┼─────┼ ─────┼─────┤ │Example 3│ 0.3 │ 0.4 │ 0.2 │ 0.7 │ ├────┼─────┼─────実 施 ─────┼─────┤ │Example 4│ 0.3 │ 0.5 │ 0.1 │ 0.5 │ ├────┼───── ─────┼─────┼─────┤ │Example 5│ 0.2 │ 0.6 │ 0.2 │ 0.8 │ ├ ────┼───── ┼─────┼─────┼─────┤ │Example 6│ 0.2 │ 0.4 │ 0.2 │ 0.6 │ ├ ────┼──── ─┼─────┼─────┼─────┤ │Example 7│ 0.2 │ 0.4 │ 0.1 │ 0.5 │ ├ ─────┼─── ──┼─────┼─────┼─────┤ │Example 8│ 0.3 │ 0.6 │ 0.2 │ 0.8 │ └────┴── ───┴─────┴─────┴─────┘
┌────┬───────────────────────┐ │ │ Laminate Strength │ │ ├ ─────────── ┬ ───────────┤ │ │ Before retorting │ After retorting │ ├────┼───────────┼─────────── │ │Example 1 │ Out of base material │ Out of base material │ ├────┼───────────┼───────────┤ │Example │ Base Out of material │ Out of base material │ ├────┼───────────┼───────────┤ │Example 3│ Out of base material │ Out of base material │ ├────┼───────────┼───────────┤ │Example 4│ Out of base material │ Out of base material │ ├────┼─ ──────────┼───────────┤ │Example 5│ Out of base material │ Out of base material │ ├────┼─── ────────┼───────────┤ │Example 6│ Out of base material │ Out of base material │ ├────┼────────── ─┼───────────┤ │Example 7│ Out of base material │ Out of base material │ ├────┼───────────┼────── ──────┤ │Example 8│ Out of base material │ Out of base material │ └────┴───────────┴───────────┘ In Table 6 above, the unit of oxygen permeability is [cc / m ² / day / atm · 23 ° C./90% RH], and the unit of water vapor permeability is [g / m ² / day · 40 ° C. 90% RH] and the unit of laminating strength is [gf / 15 mm].

  As is apparent from the measurement results shown in Table 5 and Table 6 above, it was confirmed that the samples according to Examples 1 to 8 were sufficiently practical in terms of oxygen permeability and water vapor permeability. In addition, the laminate strength was excellent, the transparency was further improved, and the contents were highly visible.

  The gas barrier laminate film according to the present invention, a laminate using the same, and a packaging bag made using the same, have barrier properties that prevent permeation of oxygen gas, water vapor, etc., in particular, water vapor barrier properties. Excellent, furthermore, excellent adhesion of laminated materials, for example, withstands heat treatment associated with processing such as retort processing, and further reduces the weight and weight of containers and packaging waste, and shortens the manufacturing process. It is useful for filling and packaging various foods and beverages such as cooked food, marine product, frozen food, boiled food, boiled rice cake, liquid soup, seasoning, drinking water, etc. The contents are excellent in filling and packaging suitability and quality maintenance.

It is a schematic sectional drawing which shows an example of the layer structure about the gas barrier laminated film which concerns on this invention. It is a schematic sectional drawing which shows an example of the layer structure about the gas barrier laminated film which concerns on this invention. It is a schematic sectional drawing which shows an example of the layer structure about the gas barrier laminated film which concerns on this invention. It is a schematic sectional drawing which shows an example of the layer structure about the laminated material which uses the gas-barrier laminated film which concerns on this invention shown in FIG. It is a schematic sectional drawing which shows an example of the layer structure about the laminated material which uses the gas-barrier laminated film which concerns on this invention shown in FIG. It is a schematic sectional drawing which shows an example of the layer structure about the laminated material which uses the gas-barrier laminated film which concerns on this invention shown in FIG. It is a schematic perspective view which shows an example of the structure about the packaging bag which uses the laminated material shown in FIG. It is a schematic perspective view which shows an example of the structure about the packaging bag which uses the laminated material shown in FIG. It is a schematic block diagram which shows the outline | summary of the example about a plasma chemical vapor deposition apparatus. It is a schematic block diagram which shows the outline | summary of the example about a winding-type vacuum evaporation system.

Explanation of symbols

A A ₁ , A ₂ gas barrier laminated film B, B ₁ , B ₂ laminated material C packaging bag D packaging product 1 substrate film 2 inorganic oxide vapor deposition film 3 gas barrier coating film 4 inorganic oxide vapor deposition film 5 Plasma treatment surface 6 Plasma treatment surface 7 Plasma treatment surface 8 Plasma treatment surface 9 Primer layer 11 Heat seal resin layer 12 Intermediate substrate 13 Plastic substrate 15 Heat seal portion 16 Opening portion 17 Contents 18 Upper seal

Claims (18)

An inorganic oxide vapor-deposited film is provided on one surface of the base film, and then, on the inorganic oxide vapor-deposited film, a general formula R ¹ _n M (OR ² ) _m (where, 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 M At least one alkoxide represented by valence), a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and further polycondensed by a sol-gel method. A gas barrier laminate film comprising: a gas barrier coating film formed of a gas barrier composition; and an inorganic oxide vapor deposition film provided on the surface of the gas barrier coating film. The gas barrier laminate film according to claim 1, wherein the base film is composed of a biaxially stretched polyester resin film, a biaxially stretched polyamide resin film, or a biaxially stretched polyolefin resin film. The gas barrier property according to any one of claims 1 and 2, wherein the vapor-deposited film of inorganic oxide is a vapor-deposited film of inorganic oxide by chemical vapor deposition or physical vapor deposition. Laminated film. The gas barrier laminate according to any one of claims 1 to 3, wherein the vapor-deposited film of the inorganic oxide by chemical vapor deposition comprises a vapor-deposited film of silicon oxide by chemical vapor deposition. the film. The gas barrier laminate according to any one of claims 1 to 3, wherein the vapor-deposited film of the inorganic oxide by the physical vapor deposition method comprises a vapor-deposited film of aluminum oxide by the physical vapor deposition method. the film. The M in the general formula R ¹ _n M (OR ² ) _m constituting the gas barrier coating film is made of silicon, zirconium, titanium, or aluminum. The gas barrier laminate film described in the item. The gas barrier laminate film according to any one of claims 1 to 6, wherein the alkoxide constituting the gas barrier coating film is composed of alkoxysilane. The gas barrier laminate film according to any one of claims 1 to 7, wherein the alkoxide constituting the gas barrier coating film comprises a hydrolyzate of alkoxide or a hydrolysis condensate of alkoxide. . The gas barrier laminate film according to any one of claims 1 to 8, wherein the gas barrier composition constituting the gas barrier coating film contains a silane coupling agent. The gas barrier composition constituting 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 being 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 gas barrier composition containing an alcohol-based resin and / or an ethylene / vinyl alcohol copolymer, and further polycondensed by a sol-gel method in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent. The gas barrier laminate film according to any one of claims 1 to 9, characterized by comprising: The gas barrier laminate film according to any one of claims 1 to 10, wherein the gas barrier coating film comprises a composite polymer layer in which one layer or two or more layers are laminated. The base film in which the gas barrier coating film is coated with the gas barrier composition and provided with the coating film is 30 ° C. to 10 seconds at a temperature of 20 ° C. to 150 ° C. and below the melting point of the base film. The gas barrier laminate film according to any one of claims 1 to 11, wherein the gas barrier laminate film comprises a cured film that has been heat-treated for minutes. 2. The sol-gel method catalyst in the gas barrier composition constituting the gas barrier coating film comprises a tertiary amine that is substantially insoluble in water and soluble in an organic solvent. The gas-barrier laminated film described in any one of -12. The gas barrier laminate according to any one of claims 1 to 13, wherein the tertiary amine in the gas barrier composition constituting the gas barrier coating film comprises N, N-dimethylbenzylamine. the film. The water in the gas barrier composition constituting the gas barrier coating film is used in a ratio of 0.1 to 100 moles with respect to 1 mole of alkoxide. Gas barrier laminate film described in 1. An inorganic oxide vapor-deposited film is provided on one surface of the base film, and then, on the inorganic oxide vapor-deposited film, a general formula R ¹ _n M (OR ² ) _m (where, 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 M At least one alkoxide represented by valence), a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and further polycondensed by a sol-gel method. A gas barrier laminate film comprising a gas barrier coating film made of a gas barrier composition and an inorganic oxide vapor deposition film on the surface of the gas barrier coating film is used to form the gas barrier laminate film. On the surface of the deposited inorganic oxide film. A laminated material characterized by laminating a tosyl resin layer. The laminated material according to claim 16, wherein a plastic substrate is laminated on the other surface of the substrate film. The laminated material according to any one of claims 16 to 17, wherein an intermediate base material is laminated between the gas barrier laminated film and the heat-sealable resin layer.

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