JP4629362B2 - Barrier film and laminated material using the same - Google Patents

Description

  The present invention relates to a barrier film and a laminate material using the same, and more specifically, has excellent gas barrier properties that prevent permeation of oxygen gas, water vapor, and the like, and further has transparency, moisture resistance, and impact resistance. The present invention relates to a gas barrier film excellent in hot water resistance and a laminated material 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 of 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, but when incinerated as garbage after use, 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, water vapor, and the like made of polyvinylidene chloride resin, ethylene-vinyl alcohol copolymer, and the like. ing.
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 uses are 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 substrate 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 to 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) through 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 by the above (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 on the outside (part) A transparent gas barrier laminate film comprising a cured film containing a polyvinyl alcohol crosslinked with a hydrolyzate, its (partial) condensate 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 a water molecule, and thus has a problem 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 is deteriorated or deteriorated.
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 high gas barrier properties, particularly improves water vapor barrier properties, 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 and the like and a laminate using the same.

As a result of various studies to solve the above-described problems, the present inventor first provided a plasma-treated surface with an inert gas on one surface of the base film, and then, on the surface of the plasma-treated surface. In addition, a vapor deposition film of an inorganic oxide by physical vapor deposition is provided, and further, a plasma treatment surface by oxygen gas is provided on the surface of the vapor deposition film of the inorganic oxide, and then a general formula is formed on the surface of the plasma treatment surface. 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 an integer of 0 or more. , M represents an integer of 1 or more, and n + m represents the valence of M.) and at least one alkoxide represented by the following formula: polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer And a gas bath obtained by polycondensation by a sol-gel method. Providing a first gas barrier coating film by a rear composition, and further providing a vapor deposition film of an inorganic oxide by physical vapor deposition or chemical vapor deposition on the surface of the first gas barrier coating film; Next, a plasma-treated surface with oxygen gas is provided on the surface of the inorganic oxide vapor-deposited film, and then a general formula R ¹ _n M (OR ² ) _m (wherein, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents M At least one alkoxide represented by the following formula: and a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and further polycondensed by a sol-gel method. A second gas barrier coating film is formed from the resulting gas barrier composition. A barrier film is manufactured, and further, a heat-seal resin layer is laminated on the surface of the second gas barrier coating film constituting the barrier film using the barrier film. When the material is manufactured, or first, a plasma-treated surface with an inert gas is provided on one surface of the base film, and then, the surface of the plasma-treated surface is coated with an inorganic oxide by physical vapor deposition. A vapor deposition film is provided, and further, a plasma treatment surface with oxygen gas is provided on the surface of the inorganic oxide vapor deposition film, and then a general formula R ¹ _n M (OR ² ) _m (provided that the plasma treatment surface is provided) 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, n + m represents the valence of M. And a gas barrier composition obtained by polycondensation by a sol-gel method, containing at least one alkoxide represented by formula (II)), a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. A first gas barrier coating film is provided, and a vapor deposition film of an inorganic oxide by physical vapor deposition or chemical vapor deposition is provided on the surface of the first gas barrier coating film. A plasma-treated surface with oxygen gas is provided on the surface of the inorganic oxide vapor-deposited film, and then a primer agent layer made of a composition containing a polyester resin or a polyurethane-based resin as a main component of the plasma-treated surface. A barrier film, and using the barrier film, a heat seal resin is used on the surface of the primer layer constituting the barrier film. When a laminated material is manufactured by laminating, it has excellent gas barrier properties that prevent permeation of oxygen gas, water vapor, etc., and further has transparency, and has excellent gas barrier properties such as moisture resistance, impact resistance, hot water resistance, etc. The present invention has been completed by finding that a film and a laminate using the film can be produced.

That is, in the present invention, a plasma treatment surface with an inert gas is provided on one surface of a base film, and then an inorganic oxide vapor deposition film by physical vapor deposition is provided on the surface of the plasma treatment surface. Further, a plasma-treated surface with oxygen gas is provided on the surface of the vapor-deposited film of the inorganic oxide, and then the general formula R ¹ _n M (OR ² ) _m (wherein, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents M At least one alkoxide represented by the following formula: and a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and further polycondensed by a sol-gel method. First gas barrier coating film by gas barrier composition obtained Furthermore, a vapor deposition film of an inorganic oxide by a physical vapor deposition method or a chemical vapor deposition method is provided on the surface of the first gas barrier coating film, and then the surface of the vapor deposition film of the inorganic oxide A plasma-treated surface with oxygen gas is provided, and then the surface of the plasma-treated surface is represented by the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² have 1 to 8 carbon atoms) M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents the valence of M. Second gas barrier property by a gas barrier composition containing one or more alkoxides, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and obtained by polycondensation by a sol-gel method. A barrier film characterized by providing a coating film; and The present invention relates to a laminate using the same.

In the present invention, a plasma treatment surface with an inert gas is provided on one surface of the base film, and then an inorganic oxide vapor deposition film by physical vapor deposition is provided on the surface of the plasma treatment surface. Further, a plasma-treated surface with oxygen gas is provided on the surface of the vapor-deposited film of the inorganic oxide, and then the general formula R ¹ _n M (OR ² ) _m (wherein, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents M At least one alkoxide represented by the following formula: and a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and further polycondensed by a sol-gel method. A first gas barrier coating film is formed from the resulting gas barrier composition. Furthermore, an inorganic oxide vapor-deposited film by physical vapor deposition or chemical vapor deposition is provided on the surface of the first gas barrier coating film, and then the inorganic oxide vapor-deposited film is formed on the surface of the inorganic oxide vapor-deposited film. A barrier property characterized by providing a plasma-treated surface with oxygen gas, and then providing a primer layer made of a composition comprising a polyester resin or a polyurethane resin as a main component of the vehicle on the surface of the plasma-treated surface The present invention relates to a film and a laminated material using the film.

In the barrier film according to the present invention and the laminate material using the same, the gas barrier property prevents permeation of oxygen gas, water vapor, and the like by laminating an inorganic oxide vapor deposition film and a gas barrier coating film in multiple layers. In particular, it has excellent water vapor barrier properties, and excellent post-processing suitability such as laminating processing, bag making processing, etc. Furthermore, for example, water resistance strength in heat sterilization processing such as retort processing, boil processing, etc. is markedly improved. And is extremely excellent in moisture resistance and the like.
Further, in the barrier film according to the present invention and the laminated material using the same, when laminating the vapor-deposited film of each inorganic oxide and the gas barrier coating film, plasma treatment with an inert gas is performed on each surface. By providing a surface or a plasma-treated surface with oxygen gas, etc., the adhesion between the layers is extremely strong, and the adhesion between the two is remarkably improved. ) And the like are not recognized at all, and the lamination strength can be remarkably improved, and accordingly, it has the advantage of being extremely excellent in water resistance strength.
In the present invention, the first and second gas barrier coating films are extremely strong because the polyvinyl alcohol resin or ethylene / vinyl alcohol copolymer and one or more alkoxides chemically react with each other. The three-dimensional network composite polymer layer is composed, and it and the deposited film of inorganic oxide are synergistic, and the extremely high gas barrier property is stably maintained, as well as good transparency and impact resistance. A barrier film having hot water resistance can be produced.
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 resin and an ethylene / vinyl alcohol copolymer, and one or more alkoxides are combined to form an extremely complex, hybrid, strong 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. Which can produce a barrier film having the property, impact resistance, hot water resistance, etc. That.

The barrier film according to the present invention and a laminate using the same will be described in more detail below with reference to the drawings.
1, FIG. 2, FIG. 3 and FIG. 4 are schematic sectional views showing a few examples of the layer structure of the barrier film according to the present invention, and FIG. 5, FIG. 6 and FIG. FIG. 8 is a schematic cross-sectional view showing a few examples of the layer structure of a laminated material using such a barrier film, and FIG. 8 and FIG. 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 barrier film A according to the present invention is provided with a plasma treatment surface 2 using an inert gas on one surface of a base film 1, and then the surface of the plasma treatment surface 2. In addition, an inorganic oxide vapor deposition film 3 formed by physical vapor deposition is provided, and a plasma treatment surface 4 using oxygen gas is further provided on the surface of the inorganic oxide vapor deposition film 3. On the surface, a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, 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 A vinyl alcohol copolymer and obtained by polycondensation by a sol-gel method. A first gas barrier coating film 5 made of a gas barrier composition, and an inorganic oxide vapor deposition film formed on the surface of the first gas barrier coating film 5 by physical vapor deposition or chemical vapor deposition 6, and then a plasma-treated surface 7 using oxygen gas is provided on the surface of the inorganic oxide vapor-deposited film 6, and then a general formula R ¹ _n M (OR ² ) is provided on the surface of the plasma-treated surface 7. _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) N + m represents the valence of M.) and contains at least one alkoxide represented by the following formula: a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer; A second gas barrier composition obtained by polycondensation by the sol-gel method is used. The basic structure is that the gas barrier coating film 8 is provided.

As another example of the barrier film according to the present invention, as shown in FIG. 2, a plasma-treated surface 2 with an inert gas is provided on one surface of the base film 1, and then the plasma An inorganic oxide vapor deposition film 3 formed by physical vapor deposition is provided on the treatment surface 2, and a plasma treatment surface 4 using oxygen gas is further provided on the surface of the inorganic oxide vapor deposition film 3. On the surface of the plasma treated surface 4, 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, and M represents a metal atom) , N represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M) and a polyvinyl alcohol-based resin. And / or an ethylene / vinyl alcohol copolymer, and a sol-gel method The first gas barrier coating film 5 made of a gas barrier composition obtained by polycondensation by the above method is provided, and further, the surface of the first gas barrier coating film 5 is formed by physical vapor deposition or chemical vapor deposition. An inorganic oxide vapor-deposited film 6 is provided, then a plasma-treated surface 7 with oxygen gas is provided on the surface of the inorganic oxide vapor-deposited film 6, and then a polyester-based resin or Examples of the barrier film A ₁ include a structure in which a primer agent layer 9 made of a composition containing a polyurethane resin as a main component of a vehicle is provided.

Furthermore, as another example of the barrier film according to the present invention, as shown in FIG. 3, a plasma-treated surface 2 with an inert gas is provided on one surface of the base film 1, and then the plasma An inorganic oxide vapor deposition film 3 formed by physical vapor deposition is provided on the treatment surface 2, and a plasma treatment surface 4 using oxygen gas is further provided on the inorganic oxide vapor deposition film 3. On the surface of the plasma treated surface 4, 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, and M represents a metal atom) , N represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M), and a polyvinyl alcohol-based resin. And / or an ethylene-vinyl alcohol copolymer, and a sol-gel method A first gas barrier coating film 5 made of a gas barrier composition obtained by polycondensation by the above is provided, and a plasma treatment surface 10 made of an inert gas is further provided on the surface of the first gas barrier coating film 5. In addition, a vapor deposition film 6 of an inorganic oxide by physical vapor deposition or chemical vapor deposition is provided on the surface of the plasma treatment surface 10, and then oxygen gas is deposited on the surface of the vapor deposition film 6 of the inorganic oxide. The plasma treatment surface 7 is then provided, and then the surface of the plasma treatment surface 7 is represented by the general formula R ¹ _n M (OR ² ) _m (where R ¹ and R ² are organic having 1 to 8 carbon atoms) Represents a group, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M. The above alkoxide, polyvinyl alcohol resin and / or ethylene vinyl alcohol An example is a barrier film A ₂ comprising a call copolymer and further comprising a second gas barrier coating film 8 made of a gas barrier composition obtained by polycondensation by a sol-gel method. it can.

Next, as another example of the barrier film according to the present invention, as shown in FIG. 4, a plasma-treated surface 2 with an inert gas is provided on one surface of the base film 1. On the surface of the plasma treatment surface 2 is provided an inorganic oxide vapor deposition film 3 by physical vapor deposition, and further on the surface of the inorganic oxide vapor deposition film 3 is provided a plasma treatment surface 4 with oxygen gas, On the surface of the plasma-treated surface 4, 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, and M represents a metal atom) N represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M.) and a polyvinyl alcohol system A resin and / or ethylene / vinyl alcohol copolymer, and a sol-gel method A first gas barrier coating film 5 made of a gas barrier composition obtained by polycondensation by the above is provided, and a plasma treatment surface 10 made of an inert gas is further provided on the surface of the first gas barrier coating film 5. In addition, a vapor deposition film 6 of an inorganic oxide by physical vapor deposition or chemical vapor deposition is provided on the surface of the plasma treatment surface 10, and then oxygen gas is deposited on the surface of the vapor deposition film 6 of the inorganic oxide. A barrier film A having a structure in which a plasma treatment surface 7 is provided, and then a primer agent layer 9 made of a composition containing a polyester resin or a polyurethane resin as a main component of a vehicle is provided on the surface of the plasma treatment surface 7. ₃ can be exemplified.

Next, in the present invention, the laminated material using the barrier film according to the present invention will be described with an example of the laminated material using the barrier film A according to the present invention shown in FIG. As shown in FIG. 5, a heat seal resin layer 11 is laminated on the surface of the second gas barrier coating film 8 constituting the barrier film A according to the present invention shown in FIG. On the surface of the gas barrier coating film 8 constituting the barrier film A according to the present invention shown in FIG. 1 as shown in FIG. 6, or the laminate B using the barrier film according to the present invention comprising The laminate B ₁ using the barrier film according to the present invention having a structure in which the heat-seal resin layer 11 is laminated through the intermediate substrate 12, and as shown in FIG. Barrier property according to the present invention shown in FIG. A plastic substrate 13 is further laminated on the other surface of the base film 1 constituting the film A, and the heat barrier is applied to the surface of the gas barrier coating film 8 constituting the barrier film A according to the present invention. - it can be exemplified laminate B _2, etc. using the barrier film according to the present invention having the structure obtained by laminating the Le resin layer 11.
In FIGS. 5, 6, and 7, reference numerals 1, 2, 3, 4, 5, 7, 8, etc. denote the reference numerals 1, 2, 3, 4, 5, 6, It has the same meaning as 7, 8, etc.
Of course, in the present invention, although not shown, the barrier film according to the present invention shown in FIGS. 2, 3 and 4 is used, and the barrier according to the present invention is performed in the same manner as described above. It is possible to produce a laminated material using a conductive film.

  Furthermore, in this invention, if the example is given about the packaging bag which made a bag using the barrier film which concerns on this invention, and the laminated material using it, as this packaging bag concerning this invention, for example, An example of a packaging bag made using the laminate B shown in FIG. 5 will be described as an example. As shown in FIG. 8, two laminates B and B are prepared, Heat seal resin layers 11, 11 positioned in the inner layer face each other and overlap each other, and thereafter, heat seal is performed on the three sides of the outer periphery and the heat seal portion 21. , 21 and 21 and the opening 22 are formed, and the three-sided seal type packaging bag according to the present invention is formed using the barrier film according to the present invention and the laminated material using the barrier film. C can be produced.

Thus, in the present invention, as shown in FIG. 9, the three-way seal type according to the present invention produced by using the barrier film according to the present invention produced above and the laminated material using the same is manufactured. For example, curry, stew, soup, meat sauce, hamburger, meatball, sushi, oden, etc. Filling the contents 23 such as desired food and drink, etc., and then heat sealing the upper opening 22 to form the upper seal part 24 and the like to produce a packaging semi-finished product D, Thereafter, the packaging semi-finished product D is subjected to, for example, retort treatment such as pressure heat sterilization treatment for about 20 to 60 minutes at a temperature, about 110 ° C. to 130 ° C., pressure, 1 to 3 kgf / cm 2 · G position. A retort packaging product E having various forms can be produced.
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 perform a heat sterilization process etc., and can also manufacture a sterilization treatment packaged product. .
In the present invention, although not shown, the barrier film according to the present invention shown in FIGS. 6 and 7 and the laminated material using the same are used, and the same as above, It is possible to manufacture a packaging bag, a packaged product, and the like that are made using the barrier film according to the invention and a laminate material using the barrier film.
In the present invention, it is needless to say that the packaging bag, packaged product, etc. according to the present invention are not limited to the shape of the illustrated packaging bag illustrated above, and its purpose, use, etc. Thus, a packaging bag having various forms such as a four-sided 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 barrier film according to the present invention, a laminated material using the barrier film, and 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, other materials and the like are arbitrarily used depending on the purpose of use, application, and the like, and a barrier film having various forms, a laminate using the barrier film, and It is possible to design and manufacture packaging bags, packaging products and the like that are made using laminated materials.
Further, 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 first and second gas barrier coating films can be provided not only in one layer but also in two or more layers.
In the present invention, as a method of laminating the laminated material using the barrier film according to the present invention as described above, although not shown, for example, an anchor coat agent using an anchor coat agent is used. Through a melt extrusion laminating method in which layers are laminated via a melt extruded resin layer obtained by melt extruding a polyolefin resin or the like, or via a laminating adhesive layer by a laminating adhesive, for example. Lamination can be performed by a dry lamination method, or the like.

Next, in the present invention, the material constituting the barrier film, the laminated material, the packaging bag, the packaged product, etc. according to the present invention, the production method, etc. will be described. First, the base constituting the barrier film according to the present invention. The material film will be described. As such a base film, this serves as a basic material constituting the barrier film according to the present invention, and further holds an inorganic oxide vapor-deposited film or a gas barrier coating film. Because it is a base material, etc., it can withstand the conditions of their formation, processing, etc., and can hold them satisfactorily without impairing their properties, and further, when making bags for packaging, It is possible to use a resin film or sheet that is excellent in various work properties such as workability, heat resistance, slipperiness, pinhole resistance, etc., and that can satisfy other conditions. That.
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, 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.

Next, in the present invention, the plasma treatment surface with an inert gas constituting the barrier film according to the present invention will be described. As the plasma treatment surface with such an inert gas, one surface of the base film, or described later The first gas barrier coating film is provided on the surface of the first gas barrier coating film, and has a close adhesion between the base film and a vapor deposition film of an inorganic oxide by a physical vapor deposition method, or the first gas barrier coating film. And improve the close adhesion of the deposited film of inorganic oxide by physical vapor deposition method or chemical vapor deposition method, etc. Eventually, both of them are firmly adhered to each other, such as delamination It is provided to prevent the occurrence.
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, the plasma processing surface can be formed by performing plasma processing by a plasma surface processing method using an inert gas such as nitrogen gas, argon gas, helium gas or the like as the plasma gas.
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 addition, in the present invention, when a plasma-treated surface with an inert gas is formed, an inorganic oxide vapor-deposited film by a physical vapor deposition method or a first gas barrier coating film is formed on one surface of a base film. Immediately before forming a vapor deposition film of an inorganic oxide by physical vapor deposition or chemical vapor deposition on the surface, by performing in-line plasma treatment, the surface of the base film or the first gas barrier coating film This is desirable because it allows removal of moisture, dust, etc., and surface treatment such as smoothing, activation, etc. of the surface.
Furthermore, 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.

Next, in the present invention, an inorganic oxide vapor-deposited film formed by physical vapor deposition that constitutes the barrier film according to the present invention will be described. A surface of a plasma-treated surface with an inert gas provided on one surface of the material film or a surface of a first gas barrier coating film described later (a plasma-treated surface with an inert gas on the surface of the first gas barrier coating film) For example, a vacuum vapor deposition method, a sputtering method, an ion plating method, or an ion cluster beam method (Physical Vapor deposition method). A deposited film of an inorganic oxide can be formed by using a deposition method or a PVD method.
In the present invention, specifically, a metal or metal oxide is used as a raw material, and this is heated and vaporized, and this is vapor-deposited on the surface of the plasma-treated surface with an inert gas provided on one surface of the base film. Vacuum deposition method, or oxidation using a metal or metal oxide as a raw material, introducing oxygen to oxidize, and depositing on the surface of the plasma treated surface with an inert gas provided on one side of the substrate film The vapor deposition film can be formed by a reactive vapor deposition method, a plasma-assisted oxidation reaction vapor deposition method in which an oxidation reaction is further aided by plasma, 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 vapor deposition film of an inorganic oxide by physical vapor deposition is shown. FIG. 10 is a schematic configuration diagram showing an example of a winding type vacuum vapor deposition apparatus.
As shown in FIG. 10, in the vacuum chamber 32 of the take-up type vacuum vapor deposition apparatus 31, it has the plasma processing surface by the inert gas on one side manufactured from the unwinding roll 33 as described above. The base film 1 is fed out, and then the base film 1 is guided to the cooled coating drum 35 through a guide roll 34 or the like, if necessary.
Alternatively, in the present invention, the base film 1 is fed out from the unwinding roll 33 as described above, and then the base film 1 is cooled, if necessary, via a guide roll 34 or the like. When guiding to the coating drum 35, for example, a magnetron sputtering device or the like is disposed between them, and using this, one surface of the substrate film 1 is subjected to plasma treatment with an inert gas. The plasma processing surface can also be formed in-line.
Thus, a crucible 36 is attached to, for example, an electron gun 37 on the surface of the plasma-treated surface with an inert gas provided on one surface of the base film 1 guided on the cooled coating drum 35. Then, the electron beam 38 is irradiated to evaporate a vapor deposition source 39, for example, metal aluminum or aluminum oxide, which is heated by the electron beam 38, and if necessary, it is disposed outside the take-up vacuum vapor deposition apparatus 31. An oxygen gas or the like is ejected from the oxygen gas cylinder 40 through an oxygen gas outlet 41, and an inorganic oxide vapor deposition film such as aluminum oxide is formed through the mask 42 while supplying the oxygen gas. The base film 1 in which a vapor-deposited film of an inorganic oxide such as aluminum oxide is formed on the surface of the plasma-treated surface with an inert gas provided on one side of the base film 1 is necessary. Then, it is fed out through the guide roll 43 and the like, and then wound around the take-up roll 44 so that the surface of the plasma-treated surface with the inert gas provided on one side of the base film 1 is inorganicly oxidized. The base film 1 provided with the vapor deposition film of the product can be manufactured.
In the above, the vapor deposition source 39 is heated by an electron beam heating method (EB) or the like in which an electron beam 38 is irradiated by an electron gun 37 such as an electron beam.
In FIG. 1, reference numerals 45 and 45 denote magnetron sputtering apparatuses that perform plasma processing or the like.
Thus, in the present invention, for example, magnetron sputtering devices 45, 45, etc. are provided, and thereby, for example, one surface of the substrate film 1 is subjected to plasma treatment with an inert gas to generate plasma in-line. By forming a treated surface, the adhesion between the base film and an inorganic oxide vapor-deposited film such as aluminum oxide can be improved via the plasma-treated surface. The surface of the deposited inorganic oxide film such as aluminum oxide is subjected to plasma treatment with oxygen gas to form a plasma treatment surface in-line, and is adhered to the first or second gas barrier coating film described later. It is also possible to improve the performance.
In the present invention, first, a first layer of an inorganic oxide vapor deposition film is formed using the above-described winding type 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 thickness of the inorganic oxide vapor-deposited film as described above varies depending on the type of metal or metal oxide used, 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.

Next, in the present invention, the plasma-treated surface with oxygen gas constituting the barrier film according to the present invention will be described. As the plasma-treated surface with oxygen gas, an inorganic oxide vapor deposition film formed by physical vapor deposition is used. Or an inorganic oxide vapor-deposited film formed by physical vapor deposition or chemical vapor deposition, and a first gas barrier coating. Close adhesion with the film, or improved adhesion between the vapor deposited inorganic oxide film by the physical vapor deposition method or the chemical vapor deposition method and the second gas barrier coating film or primer layer, etc. Specifically, they are provided in order to firmly bring them into close contact 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 formed by using 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 plasma surface treatment using oxygen gas or a mixed gas of oxygen gas and nitrogen gas, argon gas, helium gas, or other inert gas. By performing the treatment, a plasma treatment surface with oxygen gas can be formed.
In the present invention, when forming a plasma treatment surface with oxygen gas, an inorganic oxide vapor deposition film was formed by physical vapor deposition on the plasma treatment surface with an inert gas provided on one surface of the base film. After or after forming a vapor deposition film of an inorganic oxide by physical vapor deposition or chemical vapor deposition on the surface of the first gas barrier coating film, immediately after that, inorganic oxidation by physical vapor deposition is performed. The surface of a vapor deposition film of an object, or the surface of a vapor deposition film of an inorganic oxide by physical vapor deposition or chemical vapor deposition, or a plasma treatment surface by oxygen gas is formed by in-line plasma discharge treatment by oxygen gas. It is something that can be done.
Furthermore, 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.

Next, in the present invention, the first or second gas barrier coating film constituting the barrier film according to the present invention will be described. As the first or second gas barrier coating film, the general formula R ¹ _{n 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 1 or an integer, and n + m represents the valence of M.) and at least one alkoxide represented by: a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer. In addition, a step of preparing a gas barrier composition that is polycondensed by a sol-gel method in the presence of a sol-gel method catalyst, acid, water, and an organic solvent, a substrate film and a plasma-treated surface with an inert gas and physical properties By vapor deposition An inorganic oxide vapor-deposited film, or a substrate film and a plasma-treated surface with an inert gas, an inorganic oxide vapor-deposited film by a physical vapor deposition method, a plasma-treated surface with an oxygen gas, and a first gas barrier coating film A plasma-treated surface with an active gas and an inorganic oxide vapor-deposited film formed by physical vapor deposition or chemical vapor deposition are sequentially stacked on the inorganic oxide vapor-deposited film via an oxygen gas plasma-treated surface. A step of applying a gas barrier composition that is polycondensed by the sol-gel method to provide a coating film, and a base film provided with the coating film at a temperature of 20 ° C. to 180 ° C. and the above group Heat treatment for 10 seconds to 10 minutes at a temperature below the melting point of the material film, on the inorganic oxide vapor deposition film provided on one surface of the base film, through the plasma treatment surface with oxygen gas, Above gas It can be produced by comprising manufacturing process steps such as forming the first or second gas barrier coating film by the rear composition.

In the present invention, the first or second gas barrier coating film forming the barrier film according to the present invention may be represented by the general formula R ¹ _n M (OR ² ) _m (where R ¹ , R ² represents an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents the valence of M. At least one alkoxide represented by the formula (1)), a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and a sol-gel catalyst, acid, water, and organic A step of preparing a gas barrier composition that is polycondensed by a sol-gel method in the presence of a solvent, a plasma treatment surface with a base film and an inert gas, and a vapor deposition film of an inorganic oxide by a physical vapor deposition method, or a base material By film and inert gas Plasma-treated surface, inorganic oxide vapor-deposited film by physical vapor deposition, plasma-treated surface by oxygen gas, first gas barrier coating film, plasma-treated surface by inert gas, physical vapor deposition or chemical vapor deposition A gas barrier composition that is polycondensed by the above-mentioned sol-gel method is coated on the inorganic oxide vapor-deposited film obtained by sequentially stacking the inorganic oxide vapor-deposited film by the sol-gel method through the plasma-treated surface with oxygen gas. The step of layering two or more coating films, and the base film provided with the two or more layers of the coating film at a temperature of 20 to 180 ° C. and below the melting point of the base film Heat treatment is performed for 10 seconds to 10 minutes, and the first gas barrier composition is formed on the vapor-deposited film of the inorganic oxide provided on one surface of the base film through a plasma-treated surface with oxygen gas. 1 or 2 Gas barrier coating film of two or more layers layered composite polymer - can be produced by a production process comprising the step or the like to form a layer.

In the above, the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m for forming the first or second gas barrier coating film constituting the gas barrier film according to the present invention includes partial hydrolysis of the alkoxide. And at least one of the hydrolysis condensates of alkoxides, and the alkoxide partial hydrolyzate does not need to have all of the alkoxy groups hydrolyzed. The hydrolyzed condensate may be a dimer or more of a partially hydrolyzed alkoxide, specifically a 2 to 6 mer. Used ones.

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, Ra includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and the like.
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 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 n-Butoxyzirconium 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 above 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 by mixing two or more of them.
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 the polyvinyl alcohol-based resin and / or ethylene / vinyl alcohol copolymer forming the first or second gas barrier coating film constituting the barrier film according to the present invention, polyvinyl alcohol is used. Resin or ethylene / vinyl alcohol copolymer can be used alone or in combination with polyvinyl alcohol resin and ethylene / vinyl alcohol copolymer, Thus, in the present invention, by using a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer, physical properties such as gas barrier properties, water resistance, weather resistance, etc. of the gas barrier coating film can be obtained. It can be remarkably improved.
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, Preferably, it is preferable to prepare the gas barrier composition at a blending ratio of about 20 to 200 parts by weight.
In the above, if it exceeds 500 parts by weight, 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 be lowered, which is not preferable. If it is below, the gas barrier property is lowered, which is not preferable.

In the present invention, as the polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, first, as the polyvinyl alcohol resin, generally obtained by saponifying polyvinyl acetate is used. be able to.
As the above-mentioned polyvinyl alcohol-based resin, a partially saponified polyvinyl alcohol-based resin in which several tens percent of acetic acid groups remain, or a completely saponified polyvinyl alcohol in which no acetic acid groups remain, or OH groups have 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 the same company. 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 first or second gas barrier coating film constituting the barrier film according to the present invention will be described. As such a gas barrier composition, as described above, 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 an integer of 0 or more) M represents an integer of 1 or more, and n + m represents the valence of M.), at least one alkoxide represented by the above, a polyvinyl alcohol-based resin and / or ethylene as described above. A gas barrier composition containing a 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 is prepared.

In preparing the gas barrier composition, for example, a silane coupling agent or the like can be added.
Thus, known organic reactive group-containing organoalkoxysilanes can be used as the silane coupling agent.
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 and 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 alkoxysilanes.
In the above, if 20 parts by weight or more is used, the rigidity and brittleness of the gas barrier coating film to be formed are increased, and the insulating property and workability of the gas barrier coating film tend to decrease, which is not preferable. 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 preferable.
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 mole, preferably about 0.01 mole relative to the total mole 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.
On the other hand, if the amount of water is less than 0.8 mol, the hydrolysis reaction tends to hardly proceed, which is not preferable.

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 barrier film according to the present invention is specifically produced, for example, as follows.
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 the 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. Gas barrier property by the above gas barrier property composition (coating liquid) on the adhesion aid layer formed on one surface of the base film and the deposited film of the inorganic oxide by heat treatment for 10 seconds to 10 minutes. The barrier film according to the present invention can be produced by forming one or more coating films.
The barrier film according to the present invention thus obtained 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 barrier film according to the present invention produced by 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. And when manufacturing the barrier film which concerns on this invention, in order to improve the gas barrier property after a hot-water process, for example, the gas barrier composition which used the polyvinyl alcohol-type resin beforehand is applied. Forming a first coating layer, and then coating a gas barrier composition containing an ethylene / vinyl alcohol copolymer on the coating layer to form a second coating layer, By forming these composite layers, the gas barrier property of the barrier film according to the present invention can be improved.

  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 properties of the barrier film according to the present invention.

Next, the operation of the barrier film production method according to the present invention will be described with reference to the case of using alkoxysilane as an alkoxide. First, alkoxysilane and metal alkoxide are hydrolyzed by added water. The
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 provided on one surface of the base film and applied onto the inorganic oxide vapor-deposited film, it is 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 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 adhesion assistant layer and the inorganic oxide vapor deposition film provided on one surface and the coating layer, adhesion, and the like are also good.

In the method of the present invention, the amount of water added is 0.8 to 2 mol, preferably 1. Since it is adjusted to 5 moles, the above linear polymer 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.

Since the barrier film according to the present invention has the above-described excellent characteristics, it is useful as a packaging material. In particular, it has a gas barrier property (permeation of gas barrier properties (O ₂ , N ₂ , H ₂ O, CO ₂ , etc.). 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 barrier 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 vapor-deposited film of the inorganic oxide and the first or second gas barrier coating film form, for example, a chemical bond, a hydrogen bond, or a coordinate bond by a hydrolysis / co-condensation reaction, The adhesion between the inorganic oxide vapor-deposited film and the gas barrier coating film is improved, and a better gas barrier effect can be exhibited by the synergistic effect of the two layers.
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, the 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 first or second of the present invention. A gas barrier coating film can be formed.
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, an inorganic oxide vapor-deposited film by chemical vapor deposition that constitutes the barrier film according to the present invention will be described. The first gas barrier coating film surface (if the first gas barrier coating film surface is provided with a plasma processing surface with an inert gas, the surface of the plasma processing surface), for example, plasma It can be formed using chemical vapor deposition (chemical vapor deposition, CVD) such as chemical vapor deposition, thermal chemical vapor deposition, or photochemical vapor deposition.
In the present invention, specifically, the surface of the first gas barrier coating film provided on one surface of the base film (in the case of providing the plasma treatment surface with an inert gas on the surface of the first gas barrier coating film) The surface of the plasma treatment surface) uses a monomer gas for vapor deposition such as an organosilicon compound as a raw material, an inert gas such as argon gas or helium gas as a carrier gas, and an oxygen supply gas. As described above, a vapor deposition film of an inorganic oxide such as silicon oxide can be formed using a low temperature plasma chemical vapor deposition method using an oxygen gas or the like and using a low temperature plasma generator or the like.
In the above, 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. For this purpose, it is desirable to use a high-frequency plasma generator.

Specifically, an example of the formation method of the vapor-deposited film of the inorganic oxide by the low temperature plasma chemical vapor deposition method will be described as an example. FIG. 11 shows the structure of the inorganic oxide 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.
Thus, in the present invention, as shown in FIG. 11, the plasma chemical vapor deposition apparatus 51 includes a supply chamber 52 for supplying the base film 1, a pretreatment chamber 53, a film forming chamber 54, and a posttreatment chamber. 55, and a winding chamber 56 for winding up the barrier film according to the present invention in which a deposited film of an inorganic oxide such as silicon oxide is formed on the base film 1 It is what.
Thus, in the present invention, first, the base film 1 provided with the first gas barrier coating film or the like wound around the unwinding roll 57 is passed through the guide roll 58 or the like. Then, it is guided to the pretreatment chamber 53. In the pretreatment chamber 53, if necessary, for example, a magnet 59 or the like is used to generate plasma and to supply plasma gas from the gas supply chamber 60 through the gas supply pipe 61. A plasma discharge treatment or the like is performed while supplying, and a pretreatment such as forming a plasma treatment surface on the surface of the first gas barrier coating film is performed.
Next, in the present invention, the base film 1 is guided to the film forming chamber 54 via the auxiliary rolls 62, 63, etc., and is conveyed onto the peripheral surface of the cooling / electrode drum 64 at a predetermined speed.
Thus, in the present invention, vapor deposition monomer gas such as an organosilicon compound, oxygen gas, inert gas, etc. are supplied from the raw material volatilization supply device 65 and the gas supply device 66, and the like. The mixed gas composition for vapor deposition is introduced into the film forming chamber 54 kept in vacuum through the raw material supply nozzle 67 without adjusting the mixed gas composition for vapor deposition. A plasma is generated by the glow discharge plasma 68 on the first gas barrier coating film or the like of the base film 1 conveyed on the surface, and irradiated with this to deposit an inorganic oxide such as silicon oxide. Is formed into a film.
In the present invention, at that time, the cooling / electrode drum 64 is applied with a predetermined power from a power source (not shown) arranged outside the film forming chamber 54, and the cooling / electrode drum 64 is also used. The generation of plasma is promoted by arranging a magnet 69 or the like in the vicinity of.
Next, the base film 1 on which the deposited film of inorganic oxide such as silicon oxide is formed is guided to the post-processing chamber 55 through the guide rolls 70 and 71 and the like.
Accordingly, in the present invention, in the post-processing chamber 55, as described above, if necessary, for example, a magnet 72 or the like is used to generate plasma, and the plasma gas is supplied from the gas supply chamber 73 through the supply pipe 74. A plasma discharge treatment or the like is performed while supplying a plasma, and a post-treatment such as forming a plasma treatment surface on the surface of the inorganic oxide vapor deposition film is performed.
Next, in the present invention, the base film 1 in which the inorganic oxide vapor-deposited film such as silicon oxide is formed as described above and the surface of the inorganic oxide vapor-deposited film is post-treated as necessary. Then, the plasma chemistry is guided to the winding chamber 56 through the guide roll 75 and the like, and the substrate film 1 is wound around the winding roll 76 in the winding chamber 56, and the plasma chemistry according to the present invention is performed. A vapor-deposited film of an inorganic oxide can be formed by vapor phase growth.
Although not shown, the plasma chemical vapor deposition apparatus 51 is equipped with a vacuum pump or the like to maintain the degree of vacuum in the film forming chamber.
The above exemplification is an example, and it goes without saying that the present invention is not limited thereby.

In the above, the inside of the vacuum chamber of the plasma chemical vapor deposition apparatus is depressurized by a vacuum pump, and the degree of vacuum is 1 × 10 ⁻¹ to 1 × 10 ⁻⁸ Torr, preferably the degree of vacuum is 1 × 10 ⁻³ to 1 ×. It is desirable to prepare it at 10 ⁻⁷ Torr position.
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 upper substrate film, an adhesion assistant layer made of a deposited film of an inorganic oxide such as silicon oxide 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 addition, in the plasma chemical vapor deposition apparatus described above, an inorganic oxide vapor deposition film such as silicon oxide is formed on the base film in the form of SiO _x while oxidizing the plasma source gas with oxygen gas. Since it is formed into a thin film, the formed deposited film of inorganic oxide such as silicon oxide is a dense, flexible, continuous layer with few gaps. The vapor-deposited film of inorganic oxide is excellent in adhesion with the first gas barrier coating film on the base film.
In the present invention, the surface of the base film is cleaned by SiO _x plasma, and polar groups and free radicals are generated on the surface of the base film. This has the advantage that the tight adhesion between the deposited film of the product and the first gas barrier coating film of the base film 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, it is possible to shorten the time for setting the vacuum state at the time of exchanging the base film, to easily stabilize the degree of vacuum, and to stabilize the film forming process.

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 the surface of the first gas barrier coating film of the base film to form a dense thin film rich in flexibility, etc., and generally has the general formula SiO _x (where X is 0 to 0). 2 is a continuous thin film mainly composed of silicon oxide.
And Thus, the deposited film of the silicon oxide, transparency, from the viewpoint of the adhesiveness, the general formula SiO _X (provided that, X represents represents. A number of 1.3 to 1.9) are represented by 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 vapor deposition monomer gas to oxygen gas, the energy of plasma, etc. In general, the gas permeability decreases as the value of X decreases, The film itself is yellowish and the transparency is poor.

In addition, the above-described deposited silicon oxide film is mainly composed of silicon oxide, and further, at least one kind of compound composed of one or more elements of carbon, hydrogen, silicon, or oxygen, or two or more elements thereof is chemically formed. It consists of a vapor deposition film contained by bonding or the like.
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 hydrocarbon 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, adhesion, etc. of the deposited silicon oxide film become insufficient, and scratches, cracks, etc. may occur due to bending. It tends to occur and it is difficult to stably maintain high adhesion, and if it exceeds 50%, the gas barrier property expected secondary to the deposited film of silicon oxide is undesirably lowered. .
Further, in the present invention, in the silicon oxide vapor-deposited film, the content of the above compound is preferably increased in the depth direction from the surface of the silicon oxide vapor-deposited film. On the surface, the impact resistance and the like can be enhanced by the above compound and the like, and the affinity with other substrates is increased and the adhesion thereof is enhanced. On the other hand, the first gas barrier coating film of the substrate film Since the content of the above-described compound is large at the interface between the first and second gas-barrier coating films of the base film and the silicon oxide vapor-deposited film, there is an advantage that the tight adhesion is strong It is.

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 conducting 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 above-described silicon oxide vapor deposition film is preferably about 30 to 2000 mm, more specifically about 50 to 500 mm. Then, in the above, it is not preferable that the thickness is 2000 mm, or more than 500 mm, because cracks and the like are likely to be generated in the film. It 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 that forms 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, the 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 primer agent layer constituting the barrier film according to the present invention will be described. As the primer agent layer, the surface of the first gas barrier coating film (first gas barrier coating film) In the case of providing a plasma-treated surface with an inert gas on the surface, an inorganic oxide vapor-deposited film by physical vapor deposition or chemical vapor deposition is provided on the surface of the plasma-treated surface, and then the inorganic oxidation is performed. It is provided on the surface of the vapor-deposited film of the object through a plasma-treated surface with oxygen gas. First, a polyurethane resin or polyester resin is the main component of the vehicle, and the polyurethane resin or polyester resin 1 About 30 to 10% by weight of silane coupling agent, preferably about 0.05 to 10% by weight, preferably about 0.1 to 5% by weight, about 0.1 to 20% by weight of filler, Preferably, it is added at a ratio of about 1 to 10% by weight, and if necessary, additives such as stabilizers, curing agents, crosslinking agents, lubricants, ultraviolet absorbers, etc. are optionally added, A diluent or the like is added and mixed well to prepare a polyurethane-based or polyester-based resin composition. Thus, the polyurethane-based or polyester-based resin composition is used, for example, a roll coat. , Gravure coating, knife coating, dipping coating, spray coating, other coating methods, etc., the surface of the inorganic oxide vapor deposition film constituting the barrier film according to the present invention is oxygenated. Coating is performed through the plasma-treated surface with gas, and then the coating film is dried to remove the solvent, diluent, etc., and if necessary, an aging treatment is performed. Inventive primer It is possible to form the adhesive layer.
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).
Therefore, in the present invention, the primer layer as described above is used to closely contact the inorganic oxide vapor deposition film constituting the barrier film according to the present invention and the heat seal resin layer. The barrier film according to the present invention at the time of post-processing, such as laminating or bag making, for example, improving post-processability such as laminating or bag-making, and improving the adhesiveness and the like. This prevents the occurrence of cracks and the like in the vapor-deposited film of the inorganic oxide constituting the material.

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 and the like 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 high-strength 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 described above, the barrier film according to the present invention has a plasma treatment surface with an inert gas, an inorganic oxide vapor deposition film by physical vapor deposition, and a plasma with oxygen gas on one surface of the base film. A treatment surface, a first gas barrier coating film, if necessary, a plasma treatment surface by an inert gas, an inorganic oxide vapor deposition film by physical vapor deposition or chemical vapor deposition, a plasma treatment surface by oxygen gas, and In addition, a barrier film characterized by sequentially laminating a second gas barrier coating film, or a surface treated with an inert gas on one surface of a base film, an inorganic oxide by a physical vapor deposition method Vapor-deposited film, plasma-treated surface with oxygen gas, first gas barrier coating film, plasma-treated surface with inert gas, if necessary, physical vapor deposition method or chemical vapor phase It is characterized in that a vapor deposition film of an inorganic oxide by a long method, a plasma-treated surface by oxygen gas, and a primer layer made of a composition containing a polyester resin or a polyurethane resin as a main component of a vehicle are sequentially laminated. It relates to a barrier film.

Next, in the present invention, the heat sealable resin layer constituting the laminated material according to the present invention will be described. The heat sealable 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 Copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyolefin resin such as 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. 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-described resin film or sheet uses the laminated material according to the present invention, and the inorganic oxide constituting the barrier film at the time of making a packaging bag. In order to prevent the deposited film from being scratched or cracked, it is preferable to relatively increase the film thickness, specifically, about 40 μm to 110 μm, preferably 50 μm to A thickness of about 100 μm is preferable.
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 properties, 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 a tough resin such as a polyester resin, a polyamide resin, a polyaramid resin, a polypropylene resin, a polycarbonate resin, a polyacetal resin, a 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 above reasons, it is most desirable that the thickness is about 10 μm to 100 μm, preferably about 12 μm to 50 μm.
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 becomes a 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, etc., and if it is too thick, the cost increases. On the other hand, if it is too thin, the strength, puncture resistance, etc. are undesirably lowered.
In the present invention, for the reasons described above, about 9 μm to 100 μm, preferably about 12 μm to 50 μm is most desirable.
In the present invention, a desired printed pattern layer or the like can be provided on the front surface and / or the 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. 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, on one side or both sides of the above-mentioned base material constituting the barrier film, laminated material or the like according to the present invention, for example, it consists of characters, figures, symbols, patterns, etc. 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 base 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, and a hot pressure type.
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, for example, 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, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, or 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, the retort according to the present invention is filled by filling the contents from the opening of the packaging bag produced above, and then sealing the opening at its upper end with a heat seal or the like. Manufacturing a semi-wrapped product using a pouch for a container, and then subjecting the semi-packaged product to a heat treatment such as a retort treatment or a boil treatment to produce a retort packaged food using the pouch for retort according to the present invention. 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 is excellent in various physical properties such as heat resistance, pressure resistance, water resistance, heat seal resistance, pin hole resistance, puncture resistance, and others. In particular, it has excellent barrier properties, transparency, etc. that prevent permeation of oxygen gas, water vapor, etc., and withstands heat treatment associated with processing such as retort treatment, and further reduces the 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, such as aluminum foil, etc. 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 such as by the above.
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 foil such as aluminum foil having a film thickness of about 5 to 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 was used as a base film, and this was mounted on a winding roll of a winding type vacuum deposition apparatus shown in FIG. Conveyed in min, using a magnetron sputtering apparatus, introduced argon gas 500 sccm, performed plasma treatment at an output of 20 kW, and formed a plasma treatment surface with an inert gas on one surface of the base film, A 20 nm-thick aluminum oxide vapor deposition film is formed under the following vapor deposition conditions by a vacuum vapor deposition method using an electron beam (EB) heating method while supplying oxygen gas to the plasma processing surface using aluminum as a vapor deposition source. 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: 600 m / min
Thereafter, using another magnetron sputtering apparatus, oxygen gas 1000 sccm was introduced, plasma treatment was performed at an output of 5 kW, and the plasma treatment surface with oxygen gas was applied to the surface of the aluminum oxide vapor deposition film. Was formed and wound up.
(2). On the other hand, according to the composition shown in Table 1 below, the composition a. Composition prepared in advance in an 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, using the gas barrier composition produced above on the plasma treated surface with oxygen gas formed in (1) above, this is coated by the gravure roll coating method, and then at 100 ° C. for 30 seconds. Heat treatment was performed to form a first gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state).
(3). Next, using the base film on which the first gas barrier coating film is formed as described above, this is again mounted on the unwinding roll of the take-up vacuum deposition apparatus shown in FIG. 10, and then the line speed is 600 mm. / Min, using a magnetron sputtering apparatus, introducing 500 sccm of argon gas, performing plasma treatment at an output of 20 kW, and applying a plasma treatment surface with an inert gas to the surface of the first gas barrier coating film. Then, on the plasma-treated surface, using aluminum as a deposition source and supplying oxygen gas, a vacuum deposition method using an electron beam (EB) heating method and a film thickness of 20 nm under the following deposition conditions A deposited film of aluminum oxide 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: 600 m / min
After that, using another magnetron sputtering apparatus, oxygen gas 500 sccm was introduced, plasma treatment was performed at an output of 3 kW, and the plasma treatment with oxygen gas was performed on the surface of the aluminum oxide deposition film. A surface was formed and wound up.
(4). Next, on the plasma-treated surface of the deposited aluminum oxide film formed above, an initial condensation product of a polyester resin, an epoxy silane coupling agent (8.0 wt%) and an antiblocking agent (1. 0% by weight) and a kneaded primer resin composition is used, and this is coated by a gravure roll coating method so that the film thickness becomes 0.2 g / m ² (dry state). -The primer film was formed to form a barrier film according to the present invention.
(5). Next, after forming a desired printed pattern on the surface of the primer layer of the barrier film produced in the above (4), a two-component curable polyurethane laminate is formed on the entire surface including the printed pattern. A laminating adhesive layer is formed by coating an adhesive for coating to a thickness of 4.0 g / m ² (dry state) using a gravure roll coating method, and then laminating adhesive A biaxially stretched nylon 6 film having a thickness of 15 μm was laminated on the surface of the agent layer with the corona-treated surfaces facing each other, and then both were laminated by dry lamination.
Next, the surface of the biaxially stretched nylon 6 film laminated as described above is subjected to a corona discharge treatment, and then a laminating adhesive layer is formed on the corona treatment surface in the same manner as described above. 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.
(6). 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 food produced above has a packaging bag with excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. It was excellent in barrier properties against oxygen gas, water vapor, etc., and there was no bag breakage or leakage of contents, and it was excellent in functions as a food container, for example, filling / packaging suitability, distribution suitability, storage suitability, etc.

(1). First, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as the base film, and an inert gas was formed on one surface of the base film in the same manner as in Example 1 (1). Next, a 20 nm-thick aluminum oxide vapor deposition film is formed on the plasma treatment surface, and further, a plasma treatment surface with oxygen gas is formed on the aluminum oxide vapor deposition film surface. did.
(2). Next, the gas barrier composition composed of the colorless and transparent barrier coating solution used in (2) of Example 1 was used in the same manner, and in exactly the same manner as (2) of Example 1 above, The first gas barrier coating film was formed on the surface treated with oxygen gas (1). (3). Next, using the base film on which the first gas barrier coating film is formed as described above, this is again mounted on the unwinding roll of the plasma chemical vapor deposition apparatus shown in FIG. 11, and then the line speed is 200 mm. / Min, using a magnetron sputtering apparatus, introducing 600 sccm of argon gas, performing plasma treatment at an output of 20 kW, and applying a plasma treatment surface with an inert gas to the surface of the first gas barrier coating film. Then, a 20 nm-thick silicon oxide vapor deposition film was formed on the plasma-treated surface under the conditions shown below.
(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: 200 m / min
Power: 35kW
Thereafter, using another magnetron sputtering apparatus, oxygen gas 600 sccm was introduced, plasma treatment was performed at an output of 7 kW, and the plasma treatment with oxygen gas was performed on the surface of the silicon oxide vapor deposition film. A surface was formed and wound up.
(4). Next, on the surface of the plasma-treated surface of the deposited silicon oxide film formed above, an initial condensation product of polyurethane resin, epoxy silane coupling agent (8.0 wt%) and antiblocking agent (1. 0% by weight) and a kneaded primer resin composition is used, and this is coated by a gravure roll coating method so that the film thickness becomes 0.2 g / m ² (dry state). -The primer film was formed to form a barrier film according to the present invention.
(5). Next, after forming a desired printed pattern on the surface of the primer layer of the barrier film formed in (4) above, a two-component curable polyurethane laminate is formed on the entire surface including the printed 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 the adhesive for laminating A biaxially stretched nylon 6 film having a thickness of 15 μm was laminated on the surface of the agent layer with the corona-treated surfaces facing each other, and then both were laminated by dry lamination.
Next, the surface of the biaxially stretched nylon 6 film laminated as described above is subjected to a corona discharge treatment, and then a laminating adhesive layer is formed on the corona treatment surface in the same manner as described above. 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.
(6). 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 food produced above has a packaging bag with excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. It was excellent in barrier properties against oxygen gas, water vapor, etc., and there was no bag breakage or leakage of contents, and it was excellent in functions as a food container, for example, filling / packaging suitability, distribution suitability, storage suitability, etc.

(1). First, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as the base film, and an inert gas was formed on one surface of the base film in the same manner as in Example 1 (1). Next, a 20 nm-thick aluminum oxide vapor deposition film is formed on the plasma treatment surface, and further, a plasma treatment surface with oxygen gas is formed on the aluminum oxide vapor deposition film surface. did.
(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 composition prepared in advance 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, using the gas barrier composition produced above on the plasma treated surface with oxygen gas formed in (1) above, this is coated by the gravure roll coating method, and then at 100 ° C. for 30 seconds. Heat treatment was performed to form a first gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state).
(3). Next, using the base film on which the first gas barrier coating film is formed as described above, the surface of the first gas barrier coating film is exactly the same as (3) of Example 1 above. A plasma-treated surface with an inert gas is formed, and then an aluminum oxide vapor-deposited film having a film thickness of 20 nm is formed on the plasma-treated surface. A surface was formed and wound up.
(4). On the other hand, according to the composition shown in Table 1 below, the composition a. Composition prepared in advance in an 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, using the gas barrier composition produced above on the plasma treatment surface with oxygen gas formed in (3) above, this is coated by the gravure roll coating method, and then at 100 ° C. for 30 seconds. Heat treatment was performed to form a second gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state) to produce a barrier film according to the present invention.
(5). Next, after forming a desired printed pattern on the surface of the second gas barrier coating film of the barrier film formed in (4) above, a two-component curable polyurethane system is formed on the entire surface including the printed pattern. The laminating adhesive is coated to a thickness of 4.0 g / m ² (dry state) using a gravure roll coating method to form a laminating adhesive layer, and then the laminating adhesive layer is coated. A biaxially stretched nylon 6 film having a thickness of 15 μm was laminated on the surface of the adhesive layer for the adhesive with the corona-treated surfaces facing each other, and then both were laminated by dry lamination.
Next, the surface of the biaxially stretched nylon 6 film laminated as described above is subjected to a corona discharge treatment, and then a laminating adhesive layer is formed on the corona treatment surface in the same manner as described above. 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.
(6). 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 food produced above has a packaging bag with excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. It was excellent in barrier properties against oxygen gas, water vapor, etc., and there was no bag breakage or leakage of contents, and it was excellent in functions as a food container, for example, filling / packaging suitability, distribution suitability, storage suitability, etc.

(1). First, as a base film, a biaxially stretched nylon 6 film having a thickness of 15 μm was used, and this was mounted on a winding roll of a winding type vacuum vapor deposition apparatus shown in FIG. 10, and then at a line speed of 600 mm / min. Then, using a magnetron sputtering apparatus, argon gas 500 sccm is introduced, plasma treatment is performed at an output of 20 kW, and a plasma treatment surface with an inert gas is formed on one surface of the base film, On the plasma treated surface, an aluminum oxide vapor deposition film having a thickness of 20 nm is formed under the following vapor deposition conditions by using an electron beam (EB) heating method while supplying oxygen gas using aluminum as a vapor deposition source. did.
(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: 600 m / min
Thereafter, using another magnetron sputtering apparatus, oxygen gas is introduced at 1000 sccm, plasma treatment is performed at an output of 5 kW, and the plasma treatment with oxygen gas is performed on the surface of the aluminum oxide deposition film. A surface was formed and wound up.
(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 composition prepared in advance 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, using the gas barrier composition produced above on the plasma treated surface with oxygen gas formed in (1) above, this is coated by the gravure roll coating method, and then at 100 ° C. for 30 seconds. Heat treatment was performed to form a first gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state).
(3). Next, using the base film on which the first gas barrier coating film is formed as described above, this is again mounted on the unwinding roll of the plasma chemical vapor deposition apparatus shown in FIG. 11, and then the line speed is 200 mm. / Min, using a magnetron sputtering apparatus, introducing 600 sccm of argon gas, performing plasma treatment at an output of 20 kW, and applying a plasma treatment surface with an inert gas to the surface of the first gas barrier coating film. Then, a 20 nm-thick silicon oxide vapor deposition film was formed on the plasma-treated surface under the conditions shown below.
(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: 200 m / min
Power: 35kW
Thereafter, using another magnetron sputtering apparatus, oxygen gas 600 sccm was introduced, plasma treatment was performed at an output of 7 kW, and the plasma treatment with oxygen gas was performed on the surface of the silicon oxide vapor deposition film. A surface was formed and wound up.
(4). On the other hand, according to the composition shown in Table 1 below, the composition a. Composition prepared in advance in an 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, using the gas barrier composition produced above on the plasma treatment surface with oxygen gas formed in (3) above, this is coated by the gravure roll coating method, and then at 100 ° C. for 30 seconds. Heat treatment was performed to form a second gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state) to produce a barrier film according to the present invention.
(5). Next, a normal gravure ink composition is used on the corona-treated surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, and a predetermined printing pattern consisting of letters, figures, patterns, etc., by a gravure printing method. Was printed to form a printed pattern layer.
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. Using the coating film to a thickness of 4.0 g / m ² (in a dry state) to form an adhesive layer for laminating, the barrier film produced in (4) above was then formed on the surface of the laminating adhesive layer. The surfaces of the second gas barrier coating film were superposed with each other facing each other, and then both were laminated by dry lamination.
Furthermore, on the surface of the corona-treated surface of the biaxially stretched nylon 6 film of the barrier film laminated as described above, a two-component curable urethane-based adhesive (main agent: polyester polyol, curing agent: aliphatic isocyanate) is added. And using a gravure roll coat method, this is coated to a thickness of 4.0 g / m ² (dry state) to form a laminating adhesive layer, and then on the laminating adhesive layer surface, A non-stretched polypropylene film having a thickness of 60 μm was laminated by dry lamination to produce a laminated material according to the present invention.
(6). Next, two sheets of the laminated material produced above were prepared, and the unstretched polypropylene film faces were overlapped to face each other. A three-sided seal type flexible packaging bag having a seal part and an opening above 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. It was.
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). First, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as the base film, and an inert gas was formed on one surface of the base film in the same manner as in Example 1 (1). Next, a 20 nm-thick aluminum oxide vapor deposition film is formed on the plasma treatment surface, and further, a plasma treatment surface with oxygen gas is formed on the aluminum oxide vapor deposition film surface. did.
(2). Next, the gas barrier composition composed of the colorless and transparent barrier coating solution used in (2) of Example 1 was used in the same manner, and in exactly the same manner as (2) of Example 1 above, The first gas barrier coating film was formed on the surface treated with oxygen gas (1). (3). Next, using the base film on which the first gas barrier coating film is formed as described above, this is again mounted on the unwinding roll of the take-up vacuum deposition apparatus shown in FIG. The surface of the gas barrier coating film 1 is not subjected to plasma treatment with an inert gas, but is supplied with oxygen as an evaporation source, while supplying oxygen gas, and by the vacuum evaporation method using an electron beam (EB) heating method, According to the vapor deposition conditions, a 20 nm-thick 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: 600 m / min
After that, using another magnetron sputtering apparatus, oxygen gas 500 sccm was introduced, plasma treatment was performed at an output of 3 kW, and the plasma treatment with oxygen gas was performed on the surface of the aluminum oxide deposition film. A surface was formed and wound up.
(4). Next, on the plasma-treated surface of the deposited aluminum oxide film formed above, an initial condensation product of a polyester resin, an epoxy silane coupling agent (8.0 wt%) and an antiblocking agent (1. 0% by weight) and a kneaded primer resin composition is used, and this is coated by a gravure roll coating method so that the film thickness becomes 0.2 g / m ² (dry state). -The primer film was formed to form a barrier film according to the present invention.
(5). Next, after forming a desired printed pattern on the surface of the primer layer of the barrier film produced in the above (4), a two-component curable polyurethane laminate is formed on the entire surface including the printed pattern. A laminating adhesive layer is formed by coating an adhesive for coating to a thickness of 4.0 g / m ² (dry state) using a gravure roll coating method, and then laminating adhesive A biaxially stretched nylon 6 film having a thickness of 15 μm was laminated on the surface of the agent layer with the corona-treated surfaces facing each other, and then both were laminated by dry lamination.
Next, the surface of the biaxially stretched nylon 6 film laminated as described above is subjected to a corona discharge treatment, and then a laminating adhesive layer is formed on the corona treatment surface in the same manner as described above. 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.
(6). 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 food produced above has a packaging bag with excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. It was excellent in barrier properties against oxygen gas, water vapor, etc., and there was no bag breakage or leakage of contents, and it was excellent in functions as a food container, for example, filling / packaging suitability, distribution suitability, storage suitability, etc.

(1). First, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as the base film, and an inert gas was formed on one surface of the base film in the same manner as in Example 1 (1). Next, a 20 nm-thick aluminum oxide vapor deposition film is formed on the plasma treatment surface, and further, a plasma treatment surface with oxygen gas is formed on the aluminum oxide vapor deposition film surface. did.
(2). Next, the gas barrier composition composed of the colorless and transparent barrier coating solution used in (2) of Example 1 was used in the same manner, and in exactly the same manner as (2) of Example 1 above, The first gas barrier coating film was formed on the surface treated with oxygen gas (1). (3). Next, using the base film on which the first gas barrier coating film is formed as described above, this is again mounted on the unwinding roll of the plasma chemical vapor deposition apparatus shown in FIG. A silicon oxide vapor deposition film having a thickness of 20 nm was formed on the surface of the gas barrier coating film 1 under the following conditions without performing plasma treatment with an inert gas.
(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: 200 m / min
Power: 35kW
Thereafter, using another magnetron sputtering apparatus, oxygen gas 600 sccm was introduced, plasma treatment was performed at an output of 7 kW, and the plasma treatment with oxygen gas was performed on the surface of the silicon oxide vapor deposition film. A surface was formed and wound up.
(4). Next, on the surface of the plasma-treated surface of the deposited silicon oxide film formed above, an initial condensation product of polyurethane resin, epoxy silane coupling agent (8.0 wt%) and antiblocking agent (1. 0% by weight) and a kneaded primer resin composition is used, and this is coated by a gravure roll coating method so that the film thickness becomes 0.2 g / m ² (dry state). -The primer film was formed to form a barrier film according to the present invention.
(5). Next, after forming a desired printed pattern on the surface of the primer layer of the barrier film formed in (4) above, a two-component curable polyurethane laminate is formed on the entire surface including the printed 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 the adhesive for laminating A biaxially stretched nylon 6 film having a thickness of 15 μm was laminated on the surface of the agent layer with the corona-treated surfaces facing each other, and then both were laminated by dry lamination.
Next, the surface of the biaxially stretched nylon 6 film laminated as described above is subjected to a corona discharge treatment, and then a laminating adhesive layer is formed on the corona treatment surface in the same manner as described above. 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.
(6). 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 food produced above has a packaging bag with excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. It was excellent in barrier properties against oxygen gas, water vapor, etc., and there was no bag breakage or leakage of contents, and it was excellent in functions as a food container, for example, filling / packaging suitability, distribution suitability, storage suitability, etc.

(1). First, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as the base film, and an inert gas was formed on one surface of the base film in the same manner as in Example 1 (1). Next, a 20 nm-thick aluminum oxide vapor deposition film is formed on the plasma treatment surface, and further, a plasma treatment surface with oxygen gas is formed on the aluminum oxide vapor deposition film surface. did.
(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 composition prepared in advance 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, using the gas barrier composition produced above on the plasma treated surface with oxygen gas formed in (1) above, this is coated by the gravure roll coating method, and then at 100 ° C. for 30 seconds. Heat treatment was performed to form a first gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state).
(3). Next, using the base film on which the first gas barrier coating film is formed as described above, this is again mounted on the unwinding roll of the take-up vacuum deposition apparatus shown in FIG. The surface of the gas barrier coating film 1 is not subjected to plasma treatment with an inert gas, but is supplied with oxygen as an evaporation source, while supplying oxygen gas, and by the vacuum evaporation method using an electron beam (EB) heating method, According to the vapor deposition conditions, a 20 nm-thick 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: 600 m / min
After that, using another magnetron sputtering apparatus, oxygen gas 500 sccm was introduced, plasma treatment was performed at an output of 3 kW, and the plasma treatment with oxygen gas was performed on the surface of the aluminum oxide deposition film. A surface was formed and wound up.
(4). On the other hand, according to the composition shown in Table 3 below, the prepared composition a. A pre-prepared composition b. A hydrolyzed solution composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water was added and stirred 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 9.259
Isopropyl alcohol 8.888
Aluminum acetylacetone 0.018
H ₂ O 16.493
Total 100.000 (wt%)
Next, using the gas barrier composition produced above on the plasma treatment surface with oxygen gas formed in (3) above, this is coated by the gravure roll coating method, and then at 100 ° C. for 30 seconds. Heat treatment was performed to form a second gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state) to produce a barrier film according to the present invention.
(5). Next, after forming a desired printed pattern on the surface of the second gas barrier coating film of the barrier film formed in (4) above, a two-component curable polyurethane system is formed on the entire surface including the printed pattern. The laminating adhesive is coated to a thickness of 4.0 g / m ² (dry state) using a gravure roll coating method to form a laminating adhesive layer, and then the laminating adhesive layer is coated. A biaxially stretched nylon 6 film having a thickness of 15 μm was laminated on the surface of the adhesive layer for the adhesive with the corona-treated surfaces facing each other, and then both were laminated by dry lamination.
Next, the surface of the biaxially stretched nylon 6 film laminated as described above is subjected to a corona discharge treatment, and then a laminating adhesive layer is formed on the corona treatment surface in the same manner as described above. 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.
(6). 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 food produced above has a packaging bag with excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. It was excellent in barrier properties against oxygen gas, water vapor, etc., and there was no bag breakage or leakage of contents, and it was excellent in functions as a food container, for example, filling / packaging suitability, distribution suitability, storage suitability, etc.

(1). First, as a base film, a biaxially stretched nylon 6 film having a thickness of 15 μm was used, and this was mounted on a winding roll of a winding type vacuum vapor deposition apparatus shown in FIG. 10, and then at a line speed of 600 mm / min. Then, using a magnetron sputtering apparatus, argon gas 500 sccm is introduced, plasma treatment is performed at an output of 20 kW, and a plasma treatment surface with an inert gas is formed on one surface of the base film, On the plasma treated surface, an aluminum oxide vapor deposition film having a thickness of 20 nm is formed under the following vapor deposition conditions by using an electron beam (EB) heating method while supplying oxygen gas using aluminum as a vapor deposition source. did.
(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: 600 m / min
Thereafter, using another magnetron sputtering apparatus, oxygen gas is introduced at 1000 sccm, plasma treatment is performed at an output of 5 kW, and the plasma treatment with oxygen gas is performed on the surface of the aluminum oxide deposition film. A surface was formed and wound up.
(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 composition prepared in advance 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, using the gas barrier composition produced above on the plasma treated surface with oxygen gas formed in (1) above, this is coated by the gravure roll coating method, and then at 100 ° C. for 30 seconds. Heat treatment was performed to form a first gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state).
(3). Next, using the base film on which the first gas barrier coating film is formed as described above, this is again mounted on the unwinding roll of the plasma chemical vapor deposition apparatus shown in FIG. A silicon oxide vapor deposition film having a thickness of 20 nm was formed on the surface of the gas barrier coating film 1 under the conditions shown below without plasma treatment with an inert gas.
(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: 200 m / min
Power: 35kW
Thereafter, using another magnetron sputtering apparatus, oxygen gas 600 sccm was introduced, plasma treatment was performed at an output of 7 kW, and the plasma treatment with oxygen gas was performed on the surface of the silicon oxide vapor deposition film. A surface was formed and wound up.
(4). On the other hand, according to the composition shown in Table 3 below, the prepared composition a. A pre-prepared composition b. A hydrolyzed solution composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water was added and stirred 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 9.259
Isopropyl alcohol 8.888
Aluminum acetylacetone 0.018
H ₂ O 16.493
Total 100.000 (wt%)
Next, using the gas barrier composition produced above on the plasma treatment surface with oxygen gas formed in (3) above, this is coated by the gravure roll coating method, and then at 100 ° C. for 30 seconds. Heat treatment was performed to form a second gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state) to produce a barrier film according to the present invention.
(5). Next, a normal gravure ink composition is used on the corona-treated surface of a 20 μm thick biaxially stretched polypropylene film, and a predetermined printing pattern consisting 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. Using the coating film to a thickness of 5.0 g / m ² (in a dry state) to form an adhesive layer for laminating, the barrier film produced in (2) above was then formed on the surface of the laminating adhesive layer. The surfaces of the second gas barrier coating film were made to face each other, and then both were laminated by dry lamination.
Furthermore, on the surface of the corona-treated surface of the biaxially stretched nylon 6 film of the barrier film laminated as described above, a two-component curable urethane-based adhesive (main agent: polyester polyol, curing agent: aliphatic isocyanate) is added. This 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, An unstretched polypropylene film having a thickness of 60 μm was laminated by dry lamination to produce a laminate according to the present invention.
(6). Next, two sheets of the laminated material produced above were prepared, the surfaces of the unstretched polypropylene film were opposed to each other, and then the outer peripheral edge was sealed in a three-way heat seal. A three-sided seal-type flexible packaging bag having an opening and an upper opening was produced.
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. It was.
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. .

[Comparative Example 1]
(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 winding type vacuum deposition apparatus shown in FIG. Conveyed in min, using a magnetron sputtering apparatus, introduced argon gas 500 sccm, performed plasma treatment at an output of 20 kW, and formed a plasma treatment surface with an inert gas on one surface of the base film, A 20 nm-thick aluminum oxide vapor deposition film is formed under the following vapor deposition conditions by a vacuum vapor deposition method using an electron beam (EB) heating method while supplying oxygen gas to the plasma processing surface using aluminum as a vapor deposition source. 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: 600 m / min
In addition, the plasma treatment by oxygen gas was not performed on the surface of the aluminum oxide vapor deposition film.
(2). On the other hand, according to the composition shown in Table 1 below, the composition a. Composition prepared in advance in an 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 surface of the aluminum oxide vapor deposition film formed in the above (1), the gas barrier composition produced above is used, and this is coated by the gravure roll coating method, and then at 100 ° C. for 30 seconds. Then, a heat treatment was performed to form a first gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state).
(3). Next, using the base film on which the first gas barrier coating film is formed as described above, this is again mounted on the unwinding roll of the take-up vacuum deposition apparatus shown in FIG. 10, and then the line speed is 600 mm. / Min, using a magnetron sputtering apparatus, introducing 500 sccm of argon gas, performing plasma treatment at an output of 20 kW, and applying a plasma treatment surface with an inert gas to the surface of the first gas barrier coating film. Then, on the plasma-treated surface, using aluminum as a deposition source and supplying oxygen gas, a vacuum deposition method using an electron beam (EB) heating method and a film thickness of 20 nm under the following deposition conditions A deposited film of aluminum oxide 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: 600 m / min
In addition, the plasma treatment by oxygen gas was not performed on the surface of the aluminum oxide vapor deposition film.
(4). Next, on the surface of the vapor-deposited aluminum oxide film formed above, an initial condensation product of a polyester-based resin, an epoxy-based silane coupling agent (8.0% by weight) and an anti-blocking agent (1.0% by weight) Is added and kneaded sufficiently, and this is coated by a gravure roll coating method to a film thickness of 0.2 g / m ² (dry state). A primer film was formed to produce a barrier film.
(5). Next, after forming a desired printed pattern on the surface of the primer layer of the barrier film produced in the above (4), a two-component curable polyurethane laminate is formed on the entire surface including the printed pattern. A laminating adhesive layer is formed by coating an adhesive for coating to a thickness of 4.0 g / m ² (dry state) using a gravure roll coating method, and then laminating adhesive A biaxially stretched nylon 6 film having a thickness of 15 μm was laminated on the surface of the agent 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 A laminated material was produced by dry laminating and laminating an unstretched polypropylene film having a thickness of 60 μm on the laminating adhesive layer surface.
(6). 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. Retort packaged food was manufactured.

[Comparative Example 2]
(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 winding type vacuum deposition apparatus shown in FIG. Conveyed in min, using a magnetron sputtering apparatus, introduced argon gas 500 sccm, performed plasma treatment at an output of 20 kW, and formed a plasma treatment surface with an inert gas on one surface of the base film, A 20 nm-thick aluminum oxide vapor deposition film is formed under the following vapor deposition conditions by a vacuum vapor deposition method using an electron beam (EB) heating method while supplying oxygen gas to the plasma processing surface using aluminum as a vapor deposition source. 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: 600 m / min
In addition, the plasma treatment by oxygen gas was not performed on the surface of the aluminum 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 composition prepared in advance 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, on the surface of the aluminum oxide vapor deposition film formed in the above (1), the gas barrier composition produced above is used, and this is coated by the gravure roll coating method, and then at 100 ° C. for 30 seconds. Then, a heat treatment was performed to form a first gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state).
(3). Next, using the base film on which the first gas barrier coating film is formed as described above, this is again mounted on the unwinding roll of the take-up vacuum deposition apparatus shown in FIG. 10, and then the line speed is 600 mm. / Min, using a magnetron sputtering apparatus, introducing 500 sccm of argon gas, performing plasma treatment at an output of 20 kW, and applying a plasma treatment surface with an inert gas to the surface of the first gas barrier coating film. Then, on the plasma-treated surface, using aluminum as a deposition source and supplying oxygen gas, a vacuum deposition method using an electron beam (EB) heating method and a film thickness of 20 nm under the following deposition conditions A deposited film of aluminum oxide 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: 600 m / min
In addition, the plasma treatment by oxygen gas was not performed on the surface of the aluminum oxide vapor deposition film.
(4). On the other hand, according to the composition shown in Table 1 below, the composition a. Composition prepared in advance in an 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 surface of the aluminum oxide vapor deposition film formed in (3) above, the gas barrier composition produced above is used, and this is coated by the gravure roll coating method, and then at 100 ° C. for 30 seconds. Then, a heat treatment was performed to form a second gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state), and a barrier film according to the present invention was manufactured.
(5). Next, after forming a desired printed pattern on the surface of the second gas barrier coating film of the barrier film formed in (4) above, a two-component curable polyurethane system is formed on the entire surface including the printed pattern. The laminating adhesive is coated to a thickness of 4.0 g / m ² (dry state) using a gravure roll coating method to form a laminating adhesive layer, and then the laminating adhesive layer is coated. A biaxially stretched nylon 6 film having a thickness of 15 μm was laminated on the surface of the adhesive layer for the adhesive 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 A laminated material was produced by dry laminating and laminating an unstretched polypropylene film having a thickness of 60 μm on the laminating adhesive layer surface.
(6). 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. Retort packaged food was manufactured.

[Comparative Example 3]
(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 winding type vacuum deposition apparatus shown in FIG. Conveyed in min, using a magnetron sputtering apparatus, introduced argon gas 500 sccm, performed plasma treatment at an output of 20 kW, and formed a plasma treatment surface with an inert gas on one surface of the base film, A 20 nm-thick aluminum oxide vapor deposition film is formed under the following vapor deposition conditions by a vacuum vapor deposition method using an electron beam (EB) heating method while supplying oxygen gas to the plasma processing surface using aluminum as a vapor deposition source. 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: 600 m / min
Thereafter, using another magnetron sputtering apparatus, oxygen gas 1000 sccm was introduced, plasma treatment was performed at an output of 5 kW, and the plasma treatment surface with oxygen gas was applied to the surface of the aluminum oxide vapor deposition film. Was formed and wound up.
(2). On the other hand, according to the composition shown in Table 1 below, the composition a. Composition prepared in advance in an 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, using the gas barrier composition produced above on the plasma treated surface with oxygen gas formed in (1) above, this is coated by the gravure roll coating method, and then at 100 ° C. for 30 seconds. A heat treatment was performed to form a first gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state) to produce a barrier film.
(3). Next, after forming a desired printed pattern on the surface of the first gas barrier coating film of the barrier film produced in the above (2), a two-component curable polyurethane system is formed on the entire surface including the printed pattern. The laminating adhesive is coated to a thickness of 4.0 g / m ² (in a dry state) using a gravure roll coating method to form a laminating adhesive layer, and then the laminating adhesive layer is formed. A biaxially stretched nylon 6 film having a thickness of 15 μm was laminated on the surface of the adhesive layer for the adhesive 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 A laminated material was produced by dry laminating and laminating an unstretched polypropylene film having a thickness of 60 μm on the laminating adhesive layer surface.
(4). 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. Retort packaged food was manufactured.

[Experimental example]
About the barrier film manufactured in said Examples 1-8 and Comparative Examples 1-3, oxygen permeability and water vapor permeability were measured.
Moreover, about the packaging bag manufactured by bag-making and manufacturing the laminated material manufactured using the barrier film manufactured in Examples 1 to 8 and Comparative Examples 1 to 3, oxygen permeability before and after the retort treatment, Water vapor permeability, laminating strength after retorting, and water resistant laminating strength were measured.
(1). Measurement of oxygen permeability This was measured with a measuring instrument (model name, OXTRAN) manufactured by MOCON, USA, under conditions of a temperature of 23 ° C. and a humidity of 90% RH.
(2). Measurement of water vapor transmission rate 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 and Water-resistant Laminate Strength Laminate strength was measured using a Tensilon measuring instrument with a test piece of 15 mm and a peeling rate of 50 min.
Similarly to the above, the water-resistant laminating strength is measured by using a Tensilon measuring device, dropping a drop of water with a dropper on the peeling interface at a test piece of 15 mm and a peeling speed of 50 min, and starting measurement after 10 seconds. did.
The measurement results are shown in Table 4 and Table 5 below.

(Table 4)
┌────┬───────┬────────┐ │ │ Oxygen permeability │ Water vapor permeability │ ├────┼───────┼─── ─────┤ │Example 1│ 0.33 │ 0.34 │ ├────┼───────┼────────┤ │Example 2│ 0.41 │ 0.38 │ ├────┼───────┼────────┤ │Example 3│ 0.14 │ 0.12 │ ├────┼─── ────┼────────┤ │Example 4│ 0.09 │ 0.10 │ ├────┼───────┼────────┤ │Example 5│ 0.33 │ 0.34 │ ├────┼───────┼────────┤ │Example │ 0.41 │ 0.38 │ ├ ────┼───────┼────────┤ │Example 7│ 0.14 │ 0.12 │ ├────┼ ───────┼────────┤ │Example 8│ 0.09 │ 0.10 │ ├────┼───────┼─────── ──┤ │Comparative Example 1│ 0.55 │ 0.34 │ ├───┼┼──────┼────────┤ │Comparative Example 2 | 0.92 │ １． 58 │ ├────┼───────┼────────┤ │Comparative Example 3│ 0.70 │ 0.87 │ └────┴─────── ─┴────────┘ In Table 4 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 5)
┌────┬───────────┬───────────┐ │ │ Oxygen permeability │ Water vapor permeability │ │ ├ ─────┬── ───┼─────┬ ─────┤ │ │Before retort │After retort │Before retort │After retort │ ├────┼─────┼─────┼── ───┼─────┤ │Example 1│0.30 │0.52 │0.20 │0.78 │ ├────┼─────┼─────┼── ────┼─────┤ │Example 2│0.35 │0.55 │0.24 │0.72 │ ├────┼─────┼─────┼ ─────┼─────┤ │Example 3│0.12 │0.58 │0.05 │0.75 │ ├────┼─────┼─────実 施 ─────┼─────┤ │Example 4│0.05 │0.71 │0.05 │0.50 │ ────┼─────┼─────┼─────┼─────┤ │Example 5│0.30 │0.72 │0.32 │0.63 │ ├────┼─────┼─────┼─────┼─────┤ │Example 6│0.35 │0.82 │0.37 │0.68 │ ├────┼─────┼─────┼─────┼─────┤ │Example 7│0.12 │0.58 │0.12 │0. 55 │ ├────┼─────┼─────┼─────┼─────┤ │Example 8│0.09 │0.45 │0.11 │0 77 │ ├────┼─────┼─────┼─────┼─────┤ │Comparative Example 1│0.66 │1.22 │0.28 │ 1.10 │ ├────┼─────┼─────┼─────┼─────┤ │Comparative Example 2│0.84 │1. 5 │1.20 │2.31 │ ├────┼────┼┼─────┼─────┼─────┤ │Comparative Example 3 | 0.53 │1 18 │0.67 │1.20 │ └────┴─────┴─────┴─────┴─────┘
┌────┬───────────┬───────────┐ │ │ Laminate Strength │ Water-resistant Laminate Strength │ │ ├───── ──────┼───────────┤ │ │ After retorting │ After retorting │ ├────┼───────────┼───── ──────┤ │Example 1│ 350 │ 210 │ ├────┼───────────┼───────────┤ │Example 2 │ 345 │ 200 │ ├────┼───────────┼───────────┤ │Example │ 352 │ 220 │ ├────┼ ───────────┼───────────┤ │Example 4│ 370 │ 220 │ ├────┼──────────── ┼───────────┤ │Example 5│ 350 │ 210 │ ├────┼── ────────┼───────────┤ │Example 6│ 340 │ 200 │ ├────┼───────────┼── ─────────┤ │Example 7│ 352 │ 220 │ ├────┼───────────┼───────────┤ │ Example 8 │ 370 │ 220 │ ┼────┼───────────┼───────────┤ │Comparative Example 1 │ 345 │ 200 │ ├── ──┼───────────┼───────────┤ │Comparative Example 2│ 370 │ 220 │ ├ ─────┼───────── ───┼───────────┤ │Comparative Example 3│ 350 │ 210 │ └────┴───────────┴──────── ────┘ In Table 5 above, the unit of oxygen permeability is [cc / m ² / day / atm · 23 ° C./90% RH], the unit of water vapor permeability is [g / m ² / day · 40 ° C./90% RH], and the units of laminating strength and water resistant laminating strength are: [Gf / 15 mm].

As is apparent from the measurement results shown in Table 4 and Table 5 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 and water-resistant laminate strength were excellent, and further, it had transparency and excellent visibility of the contents.
On the other hand, those according to Comparative Examples 1 to 3 were inferior in water vapor permeability, laminating strength, water resistant laminating strength, and the like.

  The barrier film according to the present invention and the laminated material using the same, and the packaging bag made using the same are excellent in barrier properties for preventing permeation of oxygen gas, water vapor, etc., in particular, in water vapor barrier properties. Furthermore, it has excellent adhesion to the laminated material, 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. For example, it is useful for filling and packaging various foods and beverages such as cooked foods, marine products, frozen foods, boiled foods, rice cakes, liquid soups, seasonings, drinking water, etc. It is excellent in filling and packing of contents and quality maintenance.

It is a schematic sectional drawing which shows an example of the layer structure about the barrier film which concerns on this invention. It is a schematic sectional drawing which shows an example of the layer structure about the barrier film which concerns on this invention. It is a schematic sectional drawing which shows an example of the layer structure about the barrier film which concerns on this invention. It is a schematic sectional drawing which shows an example of the layer structure about the barrier 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 barrier 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 barrier 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 barrier film which concerns on this invention. It is a schematic perspective view which shows an example of the structure about the packaging bag based on this invention which manufactured the bag using the laminated material shown in FIG. 5, and manufactured this. It is a schematic perspective view which shows an example of the structure about the packaging bag based on this invention which manufactured the bag using the laminated material shown in FIG. 5, and manufactured this. It is a schematic block diagram which shows the outline | summary of the example about a winding-type vacuum evaporation system. It is a schematic block diagram which shows the outline | summary of the example about a plasma chemical vapor deposition apparatus.

Explanation of symbols

A A ₁ , A ₂ , A ₃ Barrier film B, B ₁ , B ₂ Laminated material C Packaging bag D Packaging semi-finished product E Packaging product 1 Base film 2 Plasma treatment surface 3 Deposition film of inorganic oxide 4 Plasma treatment Surface 5 First gas barrier coating film 6 Deposition film of inorganic oxide 7 Plasma processing surface 8 Primer layer 9 Second gas barrier coating film 10 Plasma processing surface 11 Heat seal resin layer 12 Intermediate substrate 13 Plastic base material 21 Heat seal part 22 Opening part 23 Contents 24 Upper seal part

Claims (22)

A plasma-treated surface with an inert gas is provided on one surface of the base film, and then a vapor-deposited film of an inorganic oxide by physical vapor deposition is provided on the surface of the plasma-treated surface. A surface treated with oxygen gas is provided on the surface of the vapor-deposited film, and then a general formula R ¹ _n M (OR ² ) _m (where R ¹ and R ² are Represents an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M. And a gas barrier composition obtained by polycondensation by a sol-gel method, containing at least one alkoxide represented by formula (II)), a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. A first gas barrier coating film is provided, and the first gas barrier coating film is further provided. A plasma treatment surface with an inert gas is provided on the surface of the gas barrier coating film , and then an inorganic oxide vapor deposition film by a physical vapor deposition method or a chemical vapor deposition method is provided on the plasma treatment surface. In addition, a plasma-treated surface with oxygen gas is provided on the surface of the inorganic oxide vapor-deposited film, and then the 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 second gas barrier coating film made of the gas barrier composition A barrier film characterized by being provided. A plasma-treated surface with an inert gas is provided on one surface of the base film, and then a vapor-deposited film of an inorganic oxide by physical vapor deposition is provided on the surface of the plasma-treated surface. A surface treated with oxygen gas is provided on the surface of the vapor-deposited film, and then a general formula R ¹ _n M (OR ² ) _m (where R ¹ and R ² are Represents an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M. And a gas barrier composition obtained by polycondensation by a sol-gel method, containing at least one alkoxide represented by formula (II)), a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. A first gas barrier coating film is provided, and the first gas barrier coating film is further provided. A plasma treatment surface with an inert gas is provided on the surface of the gas barrier coating film , and then an inorganic oxide vapor deposition film by a physical vapor deposition method or a chemical vapor deposition method is provided on the plasma treatment surface. In addition, a plasma-treated surface with oxygen gas is provided on the surface of the vapor-deposited film of the inorganic oxide, and then a primer made of a composition comprising a polyester-based resin or a polyurethane-based resin as a main component of the vehicle is formed on the surface of the plasma-treated surface. -Barrier film characterized by providing an agent layer. The base film is made of a biaxially stretched polyester resin film, a biaxially stretched polyamide resin film, or a biaxially stretched polyolefin resin film, according to any one of claims 1 and 2 , Barrier film to be described. The barrier according to any one of claims 1 to 3 , wherein the plasma-treated surface with an inert gas is a plasma-treated surface with an inert gas or a mixed gas of an inert gas and oxygen gas. Sex film. The barrier film according to any one of claims 1 to 4 , wherein the plasma-treated surface with oxygen gas is a plasma-treated surface with oxygen gas or a mixed gas of oxygen gas and inert gas. . The barrier film according to any one of claims 1 to 5 , wherein the inorganic oxide vapor-deposited film formed by physical vapor deposition comprises an aluminum oxide vapor-deposited film formed by physical vapor deposition. . The barrier film according to any one of claims 1 to 6 , wherein the vapor-deposited film of the inorganic oxide by the chemical vapor deposition method comprises a vapor-deposited film of silicon oxide by the chemical vapor deposition method. . The above-mentioned claim 1, wherein M in the general formula R ¹ _n M (OR ² ) _m constituting the first or second gas barrier coating film is made of silicon, zirconium, titanium, or aluminum. 8. The barrier film according to any one of 7 to 7 . The barrier film according to any one of claims 1 to 8 , wherein the alkoxide constituting the first or second gas barrier coating film is composed of alkoxysilane. The alkoxide constituting the first or second gas barrier coating film is composed of an alkoxide hydrolyzate or an alkoxide hydrolysis condensate according to any one of claims 1 to 9 above. Barrier film to be described. The barrier film according to any one of claims 1 to 10 , wherein the gas barrier composition constituting the first or second gas barrier coating film contains a silane coupling agent. The gas barrier composition constituting the first or second gas barrier coating film has a general formula R ¹ _n M (OR ² ) _m (where R ¹ and R ² are organic having 1 to 8 carbon atoms) Represents a group, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M. It contains the above alkoxide, a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer, and is further layered by a sol-gel method in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent. barrier film as described in any one of the above claims 1 to 11, characterized in that it consists of a gas barrier composition to condensation. The barrier film according to any one of claims 1 to 12 , wherein the first or second gas barrier coating film is composed of a composite polymer layer in which one layer or two or more layers are laminated. The first or second gas barrier coating film is a base film provided with a coating film by applying a gas barrier composition at a temperature of 20 ° C. to 150 ° C. and below the melting point of the base film. barrier film described in any one of the above claims 1 to 13, characterized in that a cured film was heated for 30 seconds to 10 minutes at temperature. The sol-gel catalyst in the gas barrier composition constituting the first or second gas barrier coating film is characterized by comprising a tertiary amine that is substantially insoluble in water and soluble in an organic solvent. The barrier film according to any one of claims 1 to 14. The tertiary amine in the gas barrier composition constituting the first or second gas barrier coating film is composed of N, N-dimethylbenzylamine, as described in any one of the above items 1 to 15. The barrier film described in 1. The water in the gas barrier composition constituting the first or second gas barrier coating film is used in a proportion of 0.1 to 100 mol with respect to 1 mol of alkoxide. 16. The barrier film according to any one of 16 above. 18. The winner package according to any one of claims 1 to 17 , wherein the primer layer comprises a coating layer of a resin composition comprising a polyester resin or a polyurethane resin as a main component of a vehicle. Wood. A plasma-treated surface with an inert gas is provided on one surface of the base film, and then a vapor-deposited film of an inorganic oxide by physical vapor deposition is provided on the surface of the plasma-treated surface. A surface treated with oxygen gas is provided on the surface of the vapor-deposited film, and then a general formula R ¹ _n M (OR ² ) _m (where R ¹ and R ² are Represents an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M. And a gas barrier composition obtained by polycondensation by a sol-gel method, containing at least one alkoxide represented by formula (II)), a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. A first gas barrier coating film is provided, and the first gas barrier coating film is further provided. A plasma treatment surface with an inert gas is provided on the surface of the gas barrier coating film , and then an inorganic oxide vapor deposition film by a physical vapor deposition method or a chemical vapor deposition method is provided on the plasma treatment surface. In addition, a plasma-treated surface with oxygen gas is provided on the surface of the inorganic oxide vapor-deposited film, and then the 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 second gas barrier coating film made of the gas barrier composition A laminate material comprising: a barrier film having a structure to be provided, and a heat seal resin layer laminated on a surface of a second gas barrier coating film constituting the barrier film. A plasma-treated surface with an inert gas is provided on one surface of the base film, and then a vapor-deposited film of an inorganic oxide by physical vapor deposition is provided on the surface of the plasma-treated surface. A surface treated with oxygen gas is provided on the surface of the vapor-deposited film, and then a general formula R ¹ _n M (OR ² ) _m (where R ¹ and R ² are Represents an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M. And a gas barrier composition obtained by polycondensation by a sol-gel method, containing at least one alkoxide represented by formula (II)), a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. A first gas barrier coating film is provided, and the first gas barrier coating film is further provided. A plasma treatment surface with an inert gas is provided on the surface of the gas barrier coating film , and then an inorganic oxide vapor deposition film by a physical vapor deposition method or a chemical vapor deposition method is provided on the plasma treatment surface. In addition, a plasma-treated surface with oxygen gas is provided on the surface of the vapor-deposited film of the inorganic oxide, and then a primer made of a composition comprising a polyester-based resin or a polyurethane-based resin as a main component of the vehicle is formed on the surface of the plasma-treated surface. -A laminated material characterized by using a barrier film having a constitution in which an agent layer is provided, and laminating a heat seal resin layer on the surface of the primer agent layer constituting the barrier film. 21. The plastic substrate according to any one of claims 19 to 20 , wherein a plastic substrate is laminated on the other surface of the substrate film , that is, the surface on which the plasma treatment surface with an inert gas is not provided. Laminated material. The laminated material according to any one of claims 20 to 21 , wherein an intermediate base material is laminated between the barrier film and the heat-seal resin layer.

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