JP2005145491A - Laminated tube container - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated tube container, which has the superior barrier property that prevents the permeation of an oxygen gas, steam, or the like, is highly suitable for packaging and preserving a content, has excellent disposability, and is highly adaptable to the environment. <P>SOLUTION: The laminated tube container is made by using a laminated material, which consists of an orderly laminate of a surface resin layer, an intermediate layer, and an inner resin layer. The intermediate layer is made of a barrier film, which is formed by coating one surface of a base material film with a vapor deposition film, which is an inorganic oxide, and further coating the surface of the vapor deposition film with a gas barrier coating film, which contains at least one or more kinds of alkoxides, which is represented by the general formula of R<SP>1</SP><SB>n</SB>M(OR<SP>2</SP>)<SB>m</SB>, a polyvinyl alcohol resin, and/or a ethylene-vinyl alcohol copolymer, and also includes a gas barrier composition that is obtained by a polycondensation treatment employing a sol-gel method. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a laminate tube container. More specifically, the present invention has strength and the like, and is excellent in heat resistance, heat sealability, pinhole resistance, puncture resistance, transparency, etc., particularly oxygen gas, water vapor, etc. It has excellent barrier properties to prevent permeation of the contents, has the ability to fill and pack the contents, and is suitable for storage, and can form a beautiful printed pattern on the surface and incinerate and dispose of after use. It is related to laminated tube containers that are extremely suitable for disposal, environmental friendliness, etc., and are useful for filling and packaging contents such as toothpaste, foods, cosmetics, pharmaceuticals, etc. .

Conventionally, a laminated tube container has been manufactured by various methods. Usually, at least a surface resin layer, an intermediate layer, and an inner surface resin layer are sequentially laminated to produce a laminated material. Material is used to superimpose the surface resin layer surface and the inner surface resin layer surface at both ends, and the opposite overlapping portions are heat-sealed to produce a cylindrical body, and then the cylindrical A laminated tube container is manufactured by forming a head composed of a mouth portion, a shoulder portion, and the like at one opening of the trunk portion, and further by fitting a cap with the head portion.
Thus, the laminate tube container manufactured as described above, from the other opening of the cylindrical body, for example, toothpaste, mayonnaise, kneaded wasabi, knead, ketchup, and other seasonings, Or, it is filled with contents such as whipped cream and other creams and other foods, cosmetics, pharmaceuticals, etc., and then the opening is hermetically sealed to form a bottom seal, and a laminated tube container Is producing various forms of packaging products. By the way, in the laminated material for manufacturing the laminated tube container as described above, various plastic films are laminated to constitute the laminated material from the viewpoint of protecting the contents filled and packaged in the laminated tube container. Among them, in particular, a barrier material excellent in gas barrier property that prevents permeation of oxygen gas, water vapor, and the like, and further excellent in moisture resistance and the like is laminated.
Thus, the barrier material is usually an aluminum foil or an aluminum vapor-deposited film, a monolayer film of a polyvinylidene chloride resin, a coextruded film using a polyvinylidene chloride resin, or a polyvinylidene chloride. Coated films made of a resin-based resin composition are used.
In addition, as a barrier material, a polyvinyl alcohol-based resin film, an ethylene-vinyl alcohol copolymer film, or the like is also used (for example, see Patent Document 1).
Japanese Patent Laid-Open No. 5-8352 (Claims, Examples, etc.)

In addition, in the laminated tube container as described above, printing that displays predetermined items such as the product name, manufacturer, seller, date of manufacture, etc. along with the desired pattern on the outer surface of the body is usually performed. A pattern layer is formed.
Thus, the printed pattern layer is generally formed in advance by a gravure printing method or the like on the back surface of a raw film such as a resin film that forms the surface resin layer constituting the laminated tube container, and thereafter The laminate material is manufactured by laminating this and the material constituting the intermediate layer, the inner surface resin layer, and the like, and then the laminate tube container is manufactured using the laminate material.

However, as described above, in a laminated tube container using a resin film having an aluminum foil or an aluminum deposited film as a barrier material, the barrier property for preventing permeation of oxygen gas, water vapor, etc. is extremely high. Although it is excellent, it is difficult to see through the contents, and as a laminated tube container, there are problems such as poor so-called air bag property, and the laminated tube container is used as a packaging container. When this is disposed of as waste after use, metal aluminum or the like remains, and there is a problem that it is inferior in environmental suitability due to lack of suitability for disposal and causing problems such as environmental destruction. If discarded by incineration, etc., metal aluminum, etc. will damage the incinerator, etc. There is a problem of lack of suitability.
In addition, as described above, in the laminated tube container using the polyvinylidene chloride resin as the barrier material, the gas barrier property that prevents permeation of oxygen gas, water vapor and the like has an expected effect. When the laminated tube container is used as a packaging container and then disposed of as garbage, for example, when it is disposed of by incineration or the like, since it contains chlorine atoms, at the time of incineration disposal, for example, dioxin This is a cause of generation of toxic gases and the like, and there is a concern about the influence on the human body and the like, and thus there is a problem that it is not suitable for disposal and causes problems such as environmental destruction and lacks environmental suitability.
Further, as described above, in a tube container using a polyvinyl alcohol-based resin film or an ethylene-vinyl alcohol copolymer film as a barrier material, in an absolutely dry state, oxygen gas, water vapor, etc. The gas barrier property that prevents the permeation of water has the desired effect, but in the wet state, the gas barrier property that prevents the permeation of oxygen gas, water vapor, etc., is significantly reduced and can no longer withstand its use. There is a problem that it is.

  Thus, in recent years, as a solution to the above-mentioned problems in the barrier material, for example, a resin film having a deposited aluminum oxide film by vacuum deposition or the like has been developed and proposed. In a laminated tube container using a resin film having an aluminum oxide vapor deposition film formed by a vacuum vapor deposition method or the like as a barrier material, the barrier property has transparency and prevents the permeation of oxygen gas, water vapor, etc. In addition, the aluminum oxide vapor deposition film by vacuum vapor deposition, etc. is simply deposited on the resin film, although it is also excellent in disposal treatment after use. Since it is deposited and laminated, it is vitreous, hard, and lacks flexibility etc., for example, printing, lamination, In post-processing such as bag processing, etc., cracks and the like are easily generated in the deposited film of aluminum oxide, and the barrier property that prevents the permeation of oxygen gas, water vapor, etc. is remarkably impaired. As a container, the so-called squeeze property is inferior.

Further, in the laminated tube container as described above, when the cylindrical body part or the head part is formed, or in a packaging product in which the contents are filled and packaged, the laminated material constituting the laminated tube container However, the laminated material constituting the conventional laminated tube container is slightly lacking in strength, so-called low waist, and the laminated tube container is required to have strength and a certain waist. There is a problem of producing defective products.
Further, in the laminated tube container as described above, when it is displayed directly at the store like a standing tube or the like, a so-called low load stress crack occurs due to stacking during the transportation of the packaged product, and the bottom seal portion is displayed at the time of display. There is also a problem that the content gradually leaks from.
Therefore, the present invention has strength, waist, etc., and is particularly excellent in barrier properties against oxygen gas, water vapor, etc., content resistance, etc., for example, filling packaging of contents such as toothpaste, food, cosmetics, pharmaceuticals, etc. A laminate tube container suitable for the above is provided.

As a result of earnest research to solve the above problems, the present inventor has at least a laminated material in which a surface resin layer, an intermediate layer, and an inner surface resin layer are sequentially laminated. The surface resin layer and the inner surface resin layer of the superposed portion are heat sealed to form a cylindrical body, and further, in one opening of the cylindrical body, laminating provided a head consisting of shoulder and mouth - Tochu - in blanking container, as the surface resin layer of the above, for example, density, polyethylene consisting 0.935g / m ³ ~0.960g / m ³ of A multilayer laminated resin layer including a milk white polyethylene-based resin layer composed of a resin is used, and an inorganic oxide vapor deposition film is provided on one surface of the base film as an intermediate layer, and the inorganic layer On the surface of the oxide deposited film, the general formula R ¹ _n M (OR ² ) _m ( However, in the formula, R ^1, R ² represents an organic group having 1 to 8 carbon atoms, M represents a metal atom, n is an integer of 0 or more, m represents an integer of 1 or more N + m represents the valence of M.) and contains a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer, and a sol-gel method. Using a barrier film provided with a gas barrier coating film made of a gas barrier composition obtained by polycondensation by using, for example, a polyethylene resin layer, for example, as an inner surface resin layer. Then, a desired printed pattern layer is formed on the surface of the laminated material by, for example, flexographic printing using a flexographic printing method, and then a cylindrical cylinder is formed from the laminated material. Part, and Using a cylindrical body, a laminated tube container is manufactured by forming a head composed of a mouth, a shoulder, etc. in one opening thereof, and then from the other opening of the tube container, for example, When a packaged product is manufactured by filling and packaging contents such as toothpaste, etc., the waste of the material used is prevented, and a beautiful printed pattern layer is provided on the surface. It has sufficient strength and waist to withstand the low load stress cracks during the manufacture of tube containers, the manufacture of packaging products that are filled and packed with contents, or the storage and sale of packaging products. It has sufficient resistance, no leakage of contents, etc. is observed, and there is no phenomenon such as delamination, and in particular, it has excellent barrier properties to prevent permeation of oxygen gas, water vapor, etc. Excellent in fragrance retention, preservability, etc. In addition, it does not generate harmful substances when it is disposed of after use, and is extremely suitable for disposal, environmental suitability, etc. The present invention has been completed by finding that a laminated tube container useful for packaging can be produced.

That is, the present invention is composed of a laminated material in which at least a surface resin layer, an intermediate layer, and an inner surface resin layer are sequentially laminated. A laminar in which a layered body and an inner surface resin layer are heat-sealed to form a cylindrical body, and a head composed of a shoulder and a mouth is provided at one opening of the cylindrical body. In the tube container, the above-mentioned surface resin layer is composed of a multilayer laminated resin layer including a milk-white polyethylene-based resin layer, and the above intermediate layer is deposited on one surface of the base film with an inorganic oxide vapor deposition film. Furthermore, on the surface of the inorganic oxide vapor-deposited film, 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. The present invention relates to a laminated tube container comprising a barrier film provided with a gas barrier coating film made of the obtained gas barrier composition, and further having an inner surface resin layer comprising a polyethylene resin layer.

The laminar tube container according to the present invention uses a barrier film made of a base film, a vapor-deposited film of inorganic oxide, and a gas barrier coating film as a barrier material, so that it can transmit oxygen gas, water vapor, and the like. It has excellent gas barrier properties to prevent the above.
The laminar tube container according to the present invention further uses the above-mentioned barrier film as an intermediate layer, and sequentially has a surface resin layer on one side, and an inner surface resin layer on the other side. Since laminated materials for laminated tube containers are manufactured by lamination, they have strength, etc., and have heat resistance, moisture resistance, heat sealability, pinhole resistance, puncture resistance, transparency, etc. It is possible to produce a laminated material having various characteristics.
Furthermore, since the laminar tube container according to the present invention does not use, for example, aluminum foil or polyvinylidene chloride resin as a barrier material, the laminar tube container or the like is used after use. It does not generate harmful substances during incineration and disposal, and is extremely excellent in disposal and environmental suitability.
The laminar tube container according to the present invention having various excellent advantages as described above has filling and packaging suitability, storage suitability and the like for its contents and can produce extremely good packaging products. .

The laminating tube container according to the present invention will be described in more detail with reference to the drawings.
First, FIG.1, FIG.2, FIG.3 and FIG.4 are schematic sectional drawings which show an example of the laminated constitution about the laminated material for laminated tube containers which forms the laminated tube container concerning this invention, 5 and 6 are a schematic perspective view and a half sectional view showing the configuration of the laminate tube container according to the present invention manufactured using the laminate material for the laminate tube container shown in FIG. 1, and FIG. FIG. 7 is a schematic perspective view showing an example of a packaged product in which the contents are filled and packaged in the laminated tube container according to the present invention shown in FIGS. 5 and 6.

First, as shown in FIG. 1, at least a surface resin layer 1, an intermediate layer 2, and an inner surface resin layer 3 were sequentially laminated from the outside as a laminated material A forming a laminated tube container according to the present invention. The basic structure is composed of components.
Thus, the laminate material for forming the laminate tube container according to the present invention will be specifically exemplified. As shown in FIG. 2, at least the surface resin layer 1, the intermediate layer 2, and the inner surface resin layer 3 are sequentially provided. Further, the above surface resin layer 1 is composed of a multilayer laminated resin layer 5 including a milk white polyethylene resin layer 4, and the intermediate layer 2 is formed on one surface of the base film 6. An inorganic oxide vapor-deposited film 7 is provided. Further, on the surface of the inorganic oxide vapor-deposited film 7, a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² are carbon atoms) The organic group of the number 1-8 is represented, 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 or more alkoxides represented, polyvinyl alcohol resin and / or ethyl And a vinyl alcohol copolymer, and further comprising a barrier film 9 provided with a gas barrier coating film 8 made of a gas barrier composition obtained by polycondensation by a sol-gel method. There can be exemplified a laminate a ₁ consisting of a polyethylene resin layer 10.

Further, as another specific example of the laminated material forming the laminated tube container according to the present invention, as shown in FIG. 3, at least the surface resin layer 1, the intermediate layer 2, and the inner surface resin layer 3 are sequentially formed. Furthermore, the surface resin layer 1 is composed of a multilayer laminated resin layer 5a in which a transparent polyethylene resin layer 11, a milk white polyethylene resin layer 4a, and a transparent polyethylene resin layer 11a are sequentially laminated. In addition, the intermediate layer 2 is provided with an inorganic oxide vapor deposition film 7 on one surface of the base film 6, and on the surface of the inorganic oxide vapor deposition film 7, the general formula R ¹ _n M ( OR ² ) _m (wherein, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, and m represents 1) It represents the integer above, and n + m represents the valence of M.) Gas barrier coating with a gas barrier composition obtained by polycondensation by a sol-gel method, which contains at least one alkoxide, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. A laminated material A ₂ comprising the barrier film 9 provided with the film 8 and the inner surface resin layer 3 comprising the low density polyethylene resin layer 10a can be exemplified.

Furthermore, when another specific example is illustrated about the laminated material which forms the laminated tube container concerning this invention, as shown in FIG. 4, at least the surface resin layer 1, the intermediate | middle layer 2, and the inner surface resin layer 3 are shown. Further, the surface resin layer 1 is composed of a multilayer laminated resin layer 5a in which a transparent polyethylene resin layer 11, a milk white polyethylene resin layer 4a, and a transparent polyethylene resin layer 11a are sequentially laminated. Further, the intermediate layer 2 is provided with an inorganic oxide vapor deposition film 7 on one surface of the base film 6, and further, on the surface of the inorganic oxide vapor deposition film 7, the general formula R ¹ _n M (OR ² ) _m (wherein, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, and m represents Represents an integer of 1 or more, and n + m represents the valence of M). A gas barrier comprising a gas barrier composition comprising at least one or more alkoxides represented, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and further obtained by polycondensation by a sol-gel method. A laminated material A ₃ comprising a barrier film 9 provided with a conductive coating film 8 and an inner resin layer 3 comprising a two-layer laminated resin layer 12 of a linear low density polyethylene resin layer 11 and a low density polyethylene resin layer 10a. Can be illustrated.

Thus, the above-exemplified laminated materials are just a few of them, and the present invention is not limited to the laminated materials having the configurations exemplified above, and laminated materials having various forms. Can be used.
For example, although not shown, each layer can be provided by optionally laminating a layer made of another other base material depending on the purpose of packaging, packaging application, contents to be filled, etc. As the stacking order, it can be arbitrarily stacked.
Also, for example, although not shown, the inorganic oxide vapor deposition film constituting the intermediate layer made of a barrier film may be laminated so as to face in any direction such as the inner surface side or the outer surface side. It is.

Next, in the present invention, if an example of producing a laminated tube container according to the present invention using the above laminated material is given, FIG. 5 and FIG. 6 show the laminated tube container shown in FIG. It is the schematic perspective view thru | or half sectional view which shows the structure of the laminate tube container concerning this invention manufactured using the laminated material A which forms.
In the present invention, as shown in FIG. 5, first, for example, a flexographic ink composition is used on the surface of the laminate A produced as described above, and characters, figures, symbols, patterns, etc. are used by a flexographic printing method. After forming a printed pattern layer (not shown) by flexographic printing, a laminated material A on which the printed pattern layer is formed is used, and both end portions 13 and 13 'of the laminated material A for laminating tube containers are overlapped. Then, the surface portion of the surface resin layer 1 and the surface of the inner surface resin layer 3 of the polymerization portion are heat sealed to form the heat seal portion 14 to manufacture the cylindrical body portion B. And this cylindrical trunk | drum B is made into the trunk | drum which comprises a laminated tube container.
Next, as shown in FIG. 6, a head portion 17 including a shoulder portion 15 and a mouth portion 16 is formed in one opening portion of the cylindrical body portion B by an ordinary method such as an extrusion molding method. Further, the laminating tube container C according to the present invention can be manufactured by screwing the cap 18 into the mouth portion 16 constituting the head portion 17 formed as described above.
Thus, in the present invention, as shown in FIG. 7, in the laminated tube container C according to the present invention manufactured as described above, for example, from the other opening of the cylindrical body B constituting the same, for example, Laminate according to the present invention in which the content 19 such as toothpaste and others is filled and packaged by an appropriate amount, and then the opening is welded to form the bottom seal portion 20 and the content 19 is filled and packaged. -A packaged product D consisting of a tube tube C can be produced.

The example given above is an example of a laminated tube container according to the present invention, and the present invention is not limited thereby.
For example, although not shown, in the laminated tube container according to the present invention, a desired printed pattern layer is provided on one side and / or both sides of the front and back of the surface resin layer, and then an intermediate layer made of a barrier film And the inner surface resin layer are laminated to produce a laminated material for a laminated tube container according to the present invention, and thereafter, using this, the laminated tube according to the present invention is used in the same manner as described above. It is also possible to produce containers and packaged products using the containers.
Of course, in the present invention, the laminated material shown in FIGS. 3 to 4 is used, and in the same manner as described above, the laminated tube container according to the present invention and the packaging product using the same are manufactured. It goes without saying that you can do it.

Next, in the present invention, a material, a manufacturing method, and the like constituting the laminated material for a laminated tube container, a laminated tube container, a packaged product and the like as described above will be described.
First, in the present invention, as the material constituting the surface resin layer, as described above, the laminated body is overlapped, and the polymerization end part is welded to manufacture the cylindrical body part. It is preferable to use a resin that can be fused to each other, can be extruded, and has a heat sealing property. Further, a gravure printing method, a flexographic printing method, etc. It is desirable to use a heat-sealable resin capable of forming a desired printed pattern layer by the above printing method.
Specifically, examples of the resin having heat sealability include low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), and linear (linear) low density polyethylene. (LLDPE), polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, Acid-modified polyolefin resin, polyacrylonitrile resin, ethylene-vinyl alcohol obtained by acid-modifying a polyolefin resin such as ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyethylene or polypropylene using unsaturated carboxylic acid Copolymer Polyvinyl alcohol resin, the resin of the other, or the like can be used.

Furthermore, in the present invention, an ethylene-α-olefin copolymer polymerized using a metallocene catalyst (single site catalyst) can be used as the material constituting the surface resin layer.
Examples of the ethylene-α / olefin copolymer polymerized using the above metallocene catalyst include, for example, a catalyst obtained by combining a metallocene complex and an alumoxane, such as a catalyst obtained by combining zirconocene dichloride and methylalumoxane, that is, a metallocene catalyst. An ethylene-α · olefin copolymer formed by polymerization can be used.
The above metallocene catalyst is also called a single site catalyst because the current catalyst is called a multi-site catalyst with heterogeneous active sites, while the active sites are uniform.
Specifically, the product name "Kernel" manufactured by Mitsubishi Chemical Corporation, the product name "Epoliyu" manufactured by Mitsui Petrochemical Industry Co., Ltd., and the product name "EXACT" manufactured by Exxon Chemical Company, USA ”, An ethylene-α / olefin copolymer polymerized using a metallocene catalyst such as“ AFFINITY ”or“ ENGAGE ”, manufactured by Dow Chemical Co., USA Can do.

Thus, in the present invention, as the surface resin layer composed of the multilayer laminated resin layer including the milk white polyethylene resin layer, for example, the above-mentioned heat-seal resin is a main component, and a white pigment, other, etc. A white resin composition is prepared by arbitrarily adding the additive, and on the other hand, similarly to the above, a transparent resin composition containing the above-mentioned heat-sealable resin as a main component and not adding a white pigment or the like is used. Then, the white resin composition and the transparent resin composition prepared above can be used, for example, using a molding method such as a T-die method, an inflation method, or the like.
Specifically, using the white resin composition prepared above and a transparent resin composition, for example, a multilayer T die-cast molding method such as a feed block method or a multi-manifold method, or a multilayer inflation molding method, Furthermore, a surface comprising a multilayer laminated resin layer obtained by sequentially coextruding three layers of a transparent polyethylene resin layer, a milk white polyethylene resin layer, and a transparent polyethylene resin layer using a multilayer molding method such as others. A resin layer can be formed.

Thus, in the present invention, by using the multilayer laminated resin layer including the milky white polyethylene resin layer as described above as the surface resin layer, for example, a transparent polyethylene resin layer present on the outermost surface thereof is obtained. The uneven surface called fisheye by the polyethylene-based resin layer constituting the milk-white polyethylene-based resin layer can be smoothed and flattened, thereby improving the printability by a gravure printing method or a flexographic printing method. It is possible to greatly improve, prevent the occurrence of missing ink constituting the printed pattern layer, etc., can form a very beautiful printed pattern layer, etc., and improve the occurrence of defective products due to print quality It is something that can be done.
Further, in the present invention, when forming the surface resin layer, as a polyethylene resin constituting the milky polyethylene resin layer, using a polyethylene resin consisting of density 0.935g / m ³ ~0.960g / m ³ In such a case, there is an advantage that a laminated material excellent in strength, waist and the like can be manufactured.
Furthermore, by using a laminate material with excellent strength, waist, etc. as described above, the contents of the laminated tube container are filled when the cylindrical body part is formed or when the head part is formed. In a packaged packaged product, the occurrence of defective products can be prevented. In the present invention, the film thickness of the surface resin layer is about 25 μm to 300 μm, preferably about 30 μm to 150 μm.
Furthermore, in the present invention, in the surface resin layer comprising a multilayer laminated resin layer obtained by sequentially coextruding three layers of the transparent polyethylene resin layer, the milk white polyethylene resin layer, and the transparent polyethylene resin layer, It is preferable that the film thickness of the transparent polyethylene-based resin layer constituting the back surface and the back surface is about 10 μm to 50 μm, and the film thickness of the milk white polyethylene-based resin layer constituting the middle is about 50 μm to 130 μm.

Next, in the present invention, the material constituting the inner surface resin layer can be melted by heat and fused to each other in the same manner as the material constituting the surface resin layer described above, and can be extruded. For example, low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear (linear) low density polyethylene (LLDPE), polypropylene, ethylene-vinyl acetate copolymer Acrylic resin such as ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene or polypropylene. Acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid Acid-modified polyolefin resin, polyvinyl acetate resin, polyester resin, polystyrene resin, polyacrylonitrile resin, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, modified with itaconic acid, etc. A resin composed of one or more of a series resin and other resins can be used.
Furthermore, in the present invention, as a material constituting the inner surface resin layer, ethylene-α. Polymerized using a metallocene catalyst is used in the same manner as the material constituting the surface resin layer. Olefin copolymers can be used as well.

Thus, in the present invention, the inner surface resin layer composed of a polyethylene resin layer, for example, contains one or more of the above-mentioned resins as a main component, and a desired additive is optionally added thereto. A resin composition is prepared, and then the resin composition prepared above can be used, for example, using a molding method such as a T-die method, an inflation method, or the like.
In the present invention, as the inner surface resin layer composed of a polyethylene resin layer, specifically, a low density polyethylene resin or a linear low density polyethylene resin is a main component, and a desired additive is optionally added thereto. To prepare a low density polyethylene resin composition or a linear low density polyethylene resin composition, and then use the low density polyethylene resin composition or linear low density polyethylene resin composition prepared above, For example, a low density polyethylene resin layer or a linear low density polyethylene resin layer produced using a molding method such as a T-die method, an inflation method, or the like can be used.
Furthermore, in the present invention, as the inner surface resin layer composed of the polyethylene resin layer, if another specific example is given, the low density polyethylene resin composition and the linear low density polyethylene resin composition prepared above are used. For example, a linear low-profile produced by coextrusion lamination using a multilayer T die-cast molding method such as a feed block method or a multi-manifold method, a multilayer inflation molding method, or other molding methods. An inner surface resin layer composed of a two-layer laminated resin layer of a density polyethylene resin layer and a low density polyethylene resin layer can be used.
In the above, the low density polyethylene resin layer constituting the inner resin layer is excellent in low odor to the contents, and the linear low density polyethylene resin layer constituting the inner resin layer is excellent in strength and the like. Etc. can be improved.
Therefore, when using an inner surface resin layer composed of a two-layer laminated resin layer of the linear low density polyethylene resin layer and the low density polyethylene resin layer, the side where the low density polyethylene resin layer is in contact with the contents It is preferable to arrange in the above.

Furthermore, in the present invention, especially when a linear low density polyethylene resin is used as the resin constituting the inner surface resin layer as described above, the linear low density polyethylene resin has adhesiveness. Therefore, it has the advantage of improving impact resistance with less propagation of breakage, and the inner layer is always in contact with the contents, etc., so it is also effective in preventing degradation of environmental stress cracking resistance. It has the advantage that it is.
In the present invention, other resins can be blended with the linear low density polyethylene resin. For example, by blending an ethylene-butene copolymer or the like, the resin is slightly inferior in heat resistance and sealed in a high temperature environment. Although the stability tends to deteriorate, there is an advantage that the tearability is improved and it contributes to easy opening.
Furthermore, in the present invention, as the linear low density polyethylene resin as the resin having heat sealability as described above, specifically, an ethylene-α / olefin copolymer polymerized using the metallocene catalyst described above is used. Can be used.

Next, in the present invention, the laminate tube container according to the present invention and the intermediate layer constituting the laminated material forming the laminate will be described. First, as a base film for forming the barrier film constituting the intermediate layer Since this is provided with a vapor-deposited film of an inorganic oxide, it has excellent properties in mechanical, physical, chemical, etc., and is particularly strong and tough, and has heat resistance. It is possible to use a resin film or sheet that can withstand the conditions for forming a vapor-deposited film of inorganic oxide and can satisfactorily maintain the characteristics of the vapor-deposited film of inorganic oxide without impairing the properties of the vapor-deposited film of inorganic oxide.
Specifically, in the present invention, as the base film, for example, polyethylene resin, polypropylene resin, cyclic polyolefin resin, fluorine resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile Ru-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate, polyethylene naphthalate Polyester resins such as various polyamide resins such as nylon, polyimide resins, polyamideimide resins, polyaryl phthalate resins, silicone resins, polysulfone resins, polyphenylene sulfide resins, polyethersulfones Resin, polyurethane resin, AS - Le resins, cellulose - scan resin, various resins other such film or sheet - may be used and.
In the present invention, it is particularly preferable to use a film or sheet of polypropylene resin, polyester resin, or polyamide resin.

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, a film or sheet of various resins 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 tubular 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 100 μm, more preferably about 9 to 50 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, general additives include, for example, colorants such as lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, antistatic agents, lubricants, antiblocking agents, dyes, pigments and the like. Others can be arbitrarily used, and further, a modifying resin or the like can be used.

In the present invention, the surface of the above-mentioned various resin films or sheets may be preliminarily desired as necessary in order to improve close adhesion with an inorganic oxide vapor deposition film described later. The surface treatment layer can be provided.
In the present invention, as the surface treatment layer, for example, corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc., For example, a corona treatment layer, an ozone treatment layer, a plasma treatment layer, an oxidation treatment layer, or the like can be formed and provided by optionally performing other pretreatments.
The surface pretreatment is carried out as a method for improving the close adhesion between various resin films or sheets and an inorganic oxide vapor deposition film described later. In addition, for example, a primer coat agent layer, an undercoat agent layer, an anchor coat agent layer, adhesion on the surface of various resin films or sheets in advance. An agent layer, a deposition anchor coating agent layer, or the like can be arbitrarily formed to form a surface treatment layer.
Examples of the pretreatment coating agent layer include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, A resin composition containing a polyolefin resin such as polyethylene or polypropylene, or a copolymer or modified resin thereof, a cellulose resin, or the like as a main component of the vehicle can be used.

  Next, in the present invention, an inorganic oxide vapor-deposited film that forms the barrier film constituting the intermediate layer according to the present invention will be described. As the inorganic oxide vapor-deposited film, for example, chemical vapor deposition, Alternatively, a physical vapor deposition method, or a combination of the two, can be produced by forming a single-layer film consisting of one layer of an inorganic oxide vapor-deposited film, or a multilayer film or composite film consisting of two or more layers. It can be done.

In the present invention, the inorganic oxide vapor-deposited film by the chemical vapor deposition method will be further described. Examples of the inorganic oxide vapor-deposited film by the chemical vapor deposition method include, for example, plasma chemical vapor deposition and thermochemistry. An inorganic oxide vapor-deposited film can be formed by using a chemical vapor deposition method (chemical vapor deposition method, CVD method) such as a vapor deposition method or a photochemical vapor deposition method.
In the present invention, specifically, a vapor deposition monomer gas such as an organosilicon compound is used as a raw material on one surface of a base film, and an inert gas such as argon gas or helium gas is used as a carrier gas. Furthermore, it is possible to form a vapor deposition film of an inorganic oxide such as silicon oxide by using a low temperature plasma chemical vapor deposition method using an oxygen gas or the like as an oxygen supply gas and using a low temperature plasma generator or the like. .
In the above, for example, a high-frequency plasma, a pulse wave plasma, a microwave plasma, or the like can be used as the low-temperature plasma generator. Thus, in the present invention, a 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. It is a schematic block diagram of the low temperature plasma chemical vapor deposition apparatus which shows the outline | summary about the formation method of a vapor deposition film.
In the present invention, as shown in FIG. 8, the base film 6 is fed out from the unwinding roll 23 disposed in the vacuum chamber 22 of the plasma chemical vapor deposition apparatus 21. Are transferred onto the circumferential surface of the cooling / electrode drum 25 through the auxiliary roll 24 at a predetermined speed.
Thus, in the present invention, oxygen gas, inert gas, a monomer gas for vapor deposition such as an organosilicon compound, and the like are supplied from the gas supply devices 26 and 27, the raw material volatilization supply device 28, and the like. The vapor deposition mixed gas composition was introduced into the vacuum chamber 22 through the raw material supply nozzle 29 without adjusting the vapor deposition mixed gas composition, and was conveyed onto the cooling / electrode drum 25 peripheral surface. Plasma is generated by the glow discharge plasma 30 on the base film 6 and irradiated to form a deposited film of an inorganic oxide such as silicon oxide.
In the present invention, at that time, the cooling / electrode drum 25 is applied with a predetermined power from the power source 31 disposed outside the vacuum chamber 22, and the cooling / electrode drum 25 is disposed in the vicinity of the cooling / electrode drum 25. The generation of plasma is promoted by arranging the magnet 32.
Next, the base film 6 on which the vapor-deposited film of inorganic oxide such as silicon oxide is formed is wound on the winding roll 34 via the auxiliary roll 33, and the plasma chemical vapor phase according to the present invention is applied. A vapor-deposited film of an inorganic oxide can be formed by a growth method.
In the figure, 35 represents a vacuum pump.
The above exemplification is an example, and it is needless to say that the present invention is not limited thereby.
Although not shown, in the present invention, the inorganic oxide vapor deposition film may be not only one layer of the inorganic oxide vapor deposition film but also a multilayer film in which two or more layers are laminated, and is used. The material may be used alone or as a mixture of two or more, and an inorganic oxide vapor deposition film mixed with different materials may be formed.

In the above, the inside of the vacuum chamber is depressurized by a vacuum pump and adjusted to a vacuum degree of 1 × 10 ⁻¹ to 1 × 10 ⁻⁸ Torr, preferably a vacuum degree of 1 × 10 ⁻³ to 1 × 10 ⁻⁷ Torr. It is desirable to do.
In the raw material volatilization supply device, the organic silicon compound as the raw material is volatilized and mixed with oxygen gas, inert gas, etc. supplied from the gas supply device, and this mixed gas is supplied to the vacuum chamber through the raw material supply nozzle. It is introduced in the inside.
In this case, the content of the organosilicon compound in the mixed gas is about 1 to 40%, the content of oxygen gas is about 10 to 70%, and the content of inert gas is about 10 to 60%. For example, the mixing ratio of the organosilicon compound, oxygen gas, and inert gas can be about 1: 6: 5 to 1:17:14.
On the other hand, since a predetermined voltage is applied to the cooling / electrode drum from the power source, glow discharge plasma is generated in the vicinity of the opening of the raw material supply nozzle in the vacuum chamber and the cooling / electrode drum. The glow discharge plasma is derived from one or more gas components in the mixed gas. In this state, the substrate film is conveyed at a constant speed, and the glow discharge plasma is used to cool the electrode drum peripheral surface. A vapor deposition film of an inorganic oxide such as silicon oxide can be formed on the upper base film.
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.

Further, in the plasma chemical vapor deposition apparatus, the formation of deposited film of an inorganic oxide of such as silicon oxide, on a substrate film, a plasma raw material gas in the form of SiO _X while oxidized with oxygen gas Since it is formed in a thin film, the formed deposited film of inorganic oxide such as silicon oxide is a dense, flexible, continuous layer with few gaps. The barrier property of the inorganic oxide vapor deposition film is much higher than that of the inorganic oxide vapor deposition film such as silicon oxide formed by the conventional vacuum vapor deposition method. It can be obtained.
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 substrate 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 vapor deposition film of silicon oxide formed using a vapor deposition monomer gas such as an organosilicon compound chemically reacts with a vapor deposition monomer gas such as an organic silicon compound and oxygen gas, and the reaction product. Is closely bonded to one surface of the base film to form a dense, flexible thin film, and is generally represented by the general formula SiO _x (where X represents a number from 0 to 2). Is a continuous thin film mainly composed of silicon oxide.
Thus, the silicon oxide vapor-deposited film is represented by the general formula SiO _x (where X represents a number from 1.3 to 1.9) from the viewpoint of transparency and barrier properties. A thin film mainly composed of a deposited silicon oxide film is preferable.
In the above, the value of X varies depending on the molar ratio of the vapor-deposited monomer gas and oxygen gas, the energy of the plasma, etc. Generally, the gas permeability decreases as the value of X decreases, but the film itself Becomes yellowish and the transparency is poor.

In addition, the silicon oxide vapor-deposited film is mainly composed of silicon oxide, and further, at least one kind of compound composed of one kind of carbon, hydrogen, silicon, or oxygen, or two or more kinds thereof is chemically used. It consists of 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 hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl, SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol.
In addition to the above, the type, amount, etc., of the compound contained in the deposited film of silicon oxide can be changed by changing the conditions of the vapor deposition process.
Thus, the content of the above compound in the deposited film of silicon oxide is about 0.1 to 50%, preferably about 5 to 20%.
In the above, if the content is less than 0.1%, the impact resistance, spreadability, flexibility, etc. of the deposited silicon oxide film become insufficient, and scratches, cracks, etc. are likely to occur due to bending. It is difficult to stably maintain a high barrier property, and if it exceeds 50%, the barrier property is lowered, which is not preferable.
Furthermore, in the present invention, in the silicon oxide vapor deposition film, the content of the above-mentioned compound is preferably decreased from the surface of the silicon oxide vapor deposition film in the depth direction. On the surface, the impact resistance and the like can be enhanced by the above compound and the like. On the other hand, at the interface with the base film, the content of the above compound is small. This has the advantage that the tight adhesion of the material becomes strong.

Thus, in the present invention, the above silicon oxide vapor deposition film is subjected to surface analysis such as an X-ray photoelectron spectrometer (Xray Photoelectron Spectroscopy, XPS), a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS), etc. 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 film thickness of the above-described silicon oxide vapor deposition film is preferably about 50 to 4000 mm, and specifically, the film thickness is preferably about 100 to 1000 mm. In the above, if it is thicker than 1000 mm, and more preferably 4000 mm, it is not preferable because cracks and the like are likely to occur in the film, and if it is less than 100 mm, further less than 50 mm, there is an effect of barrier properties. Is not preferable because it becomes difficult.
In the above, the film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Corporation. In the above, as means for changing the film thickness of the silicon oxide vapor deposition film, the volume velocity of the vapor deposition film is increased, that is, the method of increasing the amount of monomer gas and oxygen gas and the vapor deposition rate. This can be done by a method of slowing down.

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

Next, in the present invention, the inorganic oxide vapor-deposited film by the physical vapor deposition method will be described in more detail. Examples of the inorganic oxide vapor-deposited film by the physical vapor deposition method include vacuum vapor deposition and sputtering. A vapor deposition film of an inorganic oxide can be formed by a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a method, an ion plating method, or an ion cluster beam method.
In the present invention, specifically, a metal or metal oxide is used as a raw material, this is heated and vaporized, and this is vapor-deposited on one of the substrate films, or a raw material is metal or metal. Using an oxidation reaction deposition method in which oxygen is introduced and oxidized by introducing oxygen and deposited on one side of the base film, and further a plasma-assisted oxidation reaction deposition method in which the oxidation reaction is supported by plasma, etc. A vapor deposition film can be formed.
In the above, as a heating method of the vapor deposition material, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method (EB), or the like can be used.

In the present invention, specific examples of a method for forming a thin film of an inorganic oxide by physical vapor deposition are given. FIG. 9 is a schematic configuration diagram showing an example of a take-up vacuum deposition apparatus.
As shown in FIG. 9, the base film 6 fed out from the unwinding roll 43 in the vacuum chamber 42 of the wind-up type vacuum vapor deposition apparatus 41 is cooled through the guide rolls 44 and 45. -Guided to the dating drum 46;
Thus, the deposition source 48 heated by the crucible 47, for example, metal aluminum or aluminum oxide is evaporated on the base film 6 guided on the cooled coating drum 46, Further, if necessary, an oxygen gas or the like is ejected from the oxygen gas outlet 49 and an inorganic oxide vapor deposition film such as aluminum oxide is formed through the masks 50 and 50 while supplying the oxygen gas. Next, in the above, for example, the base film 6 on which a deposited film of an inorganic oxide such as aluminum oxide is formed is sent out through the guide rollers 51 and 52 and wound up on the winding roller 53, thereby An inorganic oxide vapor-deposited film can be formed by physical vapor deposition according to the invention.
In the present invention, the first-layer inorganic oxide vapor deposition film is first formed using the above-described take-up vacuum vapor deposition apparatus, and then the inorganic oxide vapor deposition film is formed in the same manner. Further, an inorganic oxide vapor deposition film is formed on the substrate, or by using the above-described take-up vacuum vapor deposition apparatus, these are connected in series, and the inorganic oxide vapor deposition is continuously performed. By forming the film, it is possible to form a vapor-deposited film of an inorganic oxide composed of two or more multilayer films.

In the above, as the deposited film of metal or inorganic oxide, basically, any thin film on which a metal oxide is deposited can be used. For example, silicon (Si), aluminum (Al), magnesium (Mg ), Calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), etc. Oxide deposited films can be used.
Thus, preferable examples include vapor-deposited films of metal oxides such as silicon (Si) and aluminum (Al).
Thus, the metal oxide vapor-deposited film can be referred to as a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide, and the like, for example, SiO _x , AlO _x , MgO _x, etc., and MO _X (wherein M represents a metal element, and the value of X varies depending on the metal element).
Moreover, as a range of said X value, silicon (Si) is 0-2, aluminum (Al) is 0-1.5, magnesium (Mg) is 0-1, calcium (Ca) is 0 to 1, potassium (K) is 0 to 0.5, tin (Sn) is 0 to 2, sodium (Na) is 0 to 0.5, boron (B) is 0 to 1, 5, Titanium (Ti) can take values in the range of 0 to 2, lead (Pb) in the range of 0 to 1, zirconium (Zr) in the range of 0 to 2, and yttrium (Y) in the range of 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. Those with values in the range of -1.5 can be used.
In the present invention, the film thickness of the inorganic oxide vapor-deposited film as described above varies depending on the metal used or the type of metal oxide, but is, for example, about 50 to 2000 mm, preferably 100 to 1000 mm. It is desirable to select and form arbitrarily within the range.
Moreover, in this invention, as a vapor deposition film of an inorganic oxide, as a metal or metal oxide to be used, it is used by 1 type, or 2 or more types of mixtures, and vapor deposition of the inorganic oxide mixed by the dissimilar material A membrane can also be constructed.

By the way, in the present invention, as the inorganic oxide vapor deposition film according to the present invention, for example, two or more layers of different inorganic oxide vapor deposition films using both physical vapor deposition and chemical vapor deposition are combined. It is also possible to form and use a composite film.
Thus, as a composite film composed of two or more layers of the above-mentioned different types of inorganic oxide vapor-deposited films, first, on the base film, it is dense and flexible by chemical vapor deposition. An inorganic oxide vapor deposition film capable of preventing the occurrence of cracks is provided, and then an inorganic oxide vapor deposition film formed by physical vapor deposition is provided on the inorganic oxide vapor deposition film to form two or more layers. It is desirable to constitute an inorganic oxide vapor-deposited film made of a composite film made of
Of course, in the present invention, contrary to the above, an inorganic oxide vapor-deposited film is first provided on the base film by physical vapor deposition, and then dense by chemical vapor deposition. It is also possible to provide an inorganic oxide vapor deposition film composed of a composite film composed of two or more layers by providing an inorganic oxide vapor deposition film that is highly flexible and can relatively prevent the occurrence of cracks. is there.

Next, in the present invention, the gas barrier coating film for forming the barrier film constituting the intermediate layer according to the present invention will be described. As the gas barrier coating film, the general formula R ¹ _n M (OR ² ) _m ( However, in the formula, R ^1, R ² represents an organic group having 1 to 8 carbon atoms, M represents a metal atom, n is an integer of 0 or more, m represents an integer of 1 or more , N + m represents the valence of M.) and contains a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer, and a sol-gel method. A step of preparing a gas barrier composition that is polycondensed by a sol-gel method in the presence of a catalyst, an acid, water, and an organic solvent, and an inorganic oxide vapor deposition film provided on one surface of the base film. In addition, the above sol-gel method Therefore, the step of applying a gas barrier composition that undergoes polycondensation to provide a coating film, the base film provided with the above-described coating film, at 20 ° C. to 150 ° C. and below the melting point of the base film The process of forming the gas barrier coating film by said gas barrier property composition on the vapor deposition film | membrane of the inorganic oxide provided in one side of said base film by heat-processing for 30 seconds-10 minutes at the temperature of this Can be produced by a production process including

Alternatively, in the present invention, the gas barrier coating film forming the gas barrier film constituting the intermediate layer according to the present invention may be represented by the general formula R ¹ _n M (OR ² ) _m (wherein 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 a valence of M. At least one alkoxide represented by formula (II)), a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer, a sol-gel catalyst, an acid, water, and an organic solvent. A step of preparing a gas barrier composition that undergoes polycondensation by the sol-gel method in the presence of the above, polycondensation by the sol-gel method on the inorganic oxide vapor-deposited film provided on one surface of the base film Gas barrier composition The step of coating and coating two or more layers of the coating film, the substrate film provided with the coating film having the above two or more layers laminated, is 20 ° C. to 150 ° C. and below the melting point of the above substrate film Heat treatment is performed at a temperature of 30 seconds to 10 minutes, and two or more gas barrier coating films made of the gas barrier composition are formed on the inorganic oxide vapor deposition film provided on one surface of the base film. It can be manufactured by a manufacturing process including a process of forming a multilayered composite polymer layer.

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

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

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

Thus, in the present invention, as the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , for example, it is preferable to use an alkoxysilane in which M is Si.
The alkoxysilane is represented by the general formula Si (ORa) ₄ (wherein Ra represents a lower alkyl group).
In the above, as Ra, methyl group, ethyl group, n-propyl group, n-butyl group, and others are used.
Specific examples of the above alkoxysilane include, for example, tetramethoxysilane Si (OCH ₃ ) ₄ , tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane Si (0C ₃ H ₇ ) ₄ , tetrabutoxysilane Si (OC ₄ H ₉ ) ₄ , etc. can be used.

In the present invention, examples of the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m include, for example, the general formula Rb _n Si (ORc) _4-m (where n is 0 The above-mentioned integer is represented, m represents an integer of 1, 2, and 3, and Rb and Rc represent a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and the like. Alkoxysilanes can be used.
Specific examples of the above-mentioned alkylalkoxysilane include, for example, methyltrimethoxysilane CH ₃ Si (OCH ₃ ) ₃ , methyltriethoxysilane CH ₃ Si (OC ₂ H ₅ ) ₃ , dimethyldimethoxysilane (CH ₃ ) ₂ Si (OCH ₃ ) ₂ , dimethyldiethoxysilane (CH ₃ ) ₂ Si (OC ₂ H ₅ ) ₂ , etc. can be used.
Said alkoxysilane, alkylalkoxysilane, etc. can be used individually or in mixture of 2 or more types.
In the present invention, a polycondensation product of the above alkoxysilane can also be used. Specifically, for example, 2 to 6-mer polytetramethoxysilane, polytetraemethoxysilane, and the like are used. be able to.

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

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

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

In the present invention, the above alkoxides may be used 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 when the base film is coated, the gas barrier coating film tends to peel off, which is not preferable. is there.

Next, as the polyvinyl alcohol-based resin and / or ethylene / vinyl alcohol copolymer forming the gas barrier coating film constituting the gas barrier film according to the present invention, polyvinyl alcohol-based resin or ethylene The vinyl alcohol copolymer can be used alone, or can be used in combination with a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer. In the above, by using a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, the gas barrier properties, water resistance, weather resistance, and other physical properties of the gas barrier coating film can be remarkably improved. Is.
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, exceeding 500 parts by weight is not preferable because the brittleness of the gas barrier coating film is increased, and the water resistance and weather resistance of the resulting gas barrier laminated film tend to decrease. If it is below, the gas barrier property is lowered, which is not preferable.

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

In the present invention, as the ethylene-vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer should be used. Can do.
Specific examples include partial saponification products in which several tens mol% of acetic acid groups remain to complete saponification products in which acetic acid groups remain only a few mol% or no acetic acid groups remain. However, it is desirable to use a saponification degree that is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties. The content of repeating units derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. Is preferably used.
Specific examples of the ethylene / vinyl alcohol copolymer include Kuraray Co., Ltd., Eval EP-F101 (ethylene content: 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content: 29 mol%). ) Etc. can be used.

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

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

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

Further, in the gas barrier composition, water can be used in an amount of 0.1 to 100 mol, preferably 0.8 to 2 mol, relative to 1 mol of the total molar amount of the alkoxide.
When the amount of water exceeds 2 mol, the polymer obtained from the alkoxysilane and the metal alkoxide becomes spherical particles, and the spherical particles are three-dimensionally cross-linked, resulting in low density and porosity. Therefore, such a porous polymer is not preferable because the gas barrier property of the gas barrier laminate film cannot be improved.
Moreover, when the amount of the water is less than 0.8 mol, it is not preferable because the hydrolysis reaction tends to hardly proceed.

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

Next, in the present invention, the gas barrier film according to the present invention is specifically produced as follows, for example.
First, an alkoxide such as alkoxysilane, a silane coupling agent, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, a sol-gel catalyst, an acid, water, an organic solvent, and, if necessary, A metal alkoxide or the like is mixed to prepare a gas barrier composition (coating liquid).
Next, a polycondensation reaction gradually proceeds in the gas barrier composition (coating liquid).
Next, the above gas barrier composition (coating liquid) is applied by an ordinary method on 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 liquid is at a temperature of about 20 ° C. to 150 ° C. and below the melting point of the base film, preferably at a temperature in the range of about 50 ° C. to 120 ° C. A gas barrier coating film of the above gas barrier composition (coating liquid) is formed on one layer of the inorganic oxide vapor-deposited film formed on one surface of the base film by heat treatment for 30 seconds to 10 minutes. Two or more layers can be formed to produce the gas barrier film according to the present invention.
The gas 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. In addition, the gas barrier laminate film according to the present invention produced by performing drying and heat treatment has an advantage that the gas barrier property after hot water treatment such as boil treatment and retort treatment is further improved.

  Furthermore, in the present invention, as described above, when ethylene vinyl alcohol copolymer or polyvinyl alcohol resin and ethylene vinyl alcohol copolymer are not used in combination, that is, only polyvinyl alcohol resin is used. And when manufacturing the gas barrier laminated film concerning this invention, in order to improve the gas barrier property after a hot-water process, for example, the gas barrier composition which uses polyvinyl alcohol-type resin beforehand is applied. Then, a first coating layer is formed, and then a gas barrier composition containing an ethylene / vinyl alcohol copolymer is coated on the coating layer to form a second coating layer. By forming these composite layers, the gas barrier properties of the gas barrier film according to the present invention can be improved. It is intended.

  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 by multiple layers is also an effective means for improving the gas barrier properties of the gas barrier film according to the present invention.

Next, the operation of the gas barrier film manufacturing 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 with 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 the 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) to form Si—O—Si. It is considered that a composite polymer having a bond, for example, represented by the following formula (IV), or a copolymerized composite polymer represented by the following formulas (V) and (VI) is generated.

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

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

In the present invention, the inorganic oxide vapor-deposited film and the gas barrier coating film form, for example, a chemical bond, a hydrogen bond, or a coordinate bond by hydrolysis / co-condensation reaction, and the like. And the gas barrier coating film can be improved, and the synergistic effect of the two layers can provide a better gas barrier effect.
As a method of 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 dipping, 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, and further, under a normal environment, 50 to 300 ° C., Preferably, condensation is performed by heating and drying at a temperature of 70 to 200 ° C. for 0.005 to 60 minutes, preferably 0.01 to 10 minutes, and the gas barrier coating film of the present invention is formed. can do.
If necessary, when applying the gas barrier composition of the present invention, a primer agent or the like can be applied on the inorganic oxide vapor-deposited film in advance, and corona discharge treatment or A pretreatment such as plasma treatment or the like can be optionally performed.

    As described above, the present invention is, for example, a base film such as a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, an inorganic oxide vapor-deposited film on the base film, and an inorganic oxide vapor-deposited film. A gas barrier coating film made of a gas barrier composition comprising an alkoxysilane, a polyvinyl alcohol and / or an ethylene vinyl alcohol copolymer, and a silane coupling agent added as necessary, is sequentially provided. The barrier film according to the above can be produced.

Next, in the present invention, an inorganic oxide vapor-deposited film is provided on one surface of the surface resin layer and the base film as described above, and the general formula is formed on the surface of the inorganic oxide vapor-deposited film. R ¹ _n M (OR ² ) _m (wherein, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, 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. In addition, an intermediate layer composed of a barrier film provided with a gas barrier coating film by a gas barrier composition obtained by polycondensation by a sol-gel method and an inner surface resin layer are sequentially laminated, Method for producing a laminated material for a laminated tube container according to the invention For example, for example, a dry lamination method or an anchor coat in which the surface resin layer, the intermediate layer, and the inner surface resin layer are laminated via a laminating adhesive layer or the like, for example. -Lamination for laminating tube containers according to the present invention consisting of various forms by laminating using a melt extrusion laminating method in which various resins are melt-extruded and laminated through a coating agent layer, etc. The material can be manufactured.
In the present invention, other base materials may be arbitrarily laminated between the surface resin layer, the intermediate layer, and the inner surface resin layer according to the purpose of use, use form, application, etc. Thus, the tube container packaging material according to the present invention having various forms can be designed and manufactured.
In the present invention, when performing the above-described lamination, for example, plasma treatment or corona discharge treatment may be applied to the lamination surface such as the surface resin layer, the intermediate layer, the inner surface resin layer, and other base materials. Pretreatment such as flame treatment, ozone treatment, and others can be arbitrarily performed.

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

Furthermore, in the present invention, examples of the melt-extruded resin in the melt-extrusion lamination method include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, and metallocene catalyst. Polymerized ethylene-α-olefin copolymer, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, Acid-modified polyolefin resins obtained by modifying polyolefin resins such as ethylene-propylene copolymers, methylpentene polymers, polyethylene, and polypropylene with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, etc. Etc. can be used
In the present invention, when melt extrusion lamination is performed, an anchor coating agent such as an isocyanate type, a polyethyleneimine type, or the like can be arbitrarily used.
Furthermore, 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, since packaging containers are usually subjected to severe physical and chemical conditions, the laminated materials constituting the packaging containers are required to have strict packaging suitability, deformation prevention strength, drop impact. Various conditions such as strength, pinhole resistance, heat resistance, sealability, quality maintenance, workability, hygiene, etc. are required. For this reason, in the present invention, in addition to the above materials, In addition, other analysis materials satisfying 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, methyl Pentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylonitrile resin, polystyrene resin, Acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol resin, ethylene-vinyl acetate copolymer A film or sheet of a known resin such as saponified product, fluorine-based resin, gen-based resin, polyacetal-based resin, polyurethane-based resin, nitrocellulose, or the like can be arbitrarily selected and used.
In addition, for example, synthetic paper or the like can also be used.
In the present invention, the film or sheet may be any of unstretched, uniaxially or biaxially stretched.
The thickness is arbitrary, but can be selected from a range of several μm to 300 μm.
Furthermore, in the present invention, the film or sheet may be a film having any property such as extrusion film formation, inflation film formation, and coating film.

Further, in the present invention, the other base material has, for example, a mechanical, physical, chemical, etc. excellent property as a basic material constituting a laminated tube container, and particularly has strength. Thus, a tough and heat-resistant resin film or sheet can be used.
Specifically, for example, a polyester resin, a polyamide resin, a polyaramid resin, a polyolefin resin, a polycarbonate resin, a polyacetal resin, a fluorine resin, a tough resin film or sheet, or the like is used. can do.
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.
The thickness of the film is about 5 μm to 100 μm, preferably about 10 μm to 50 μm.

In the present invention, as the other base material, for example, a light-shielding material having a property of shielding light such as sunlight or a water-resistant material having a property of not transmitting water vapor, water, or the like is used. This may be a single substrate, or a composite substrate formed by combining two or more substrates.
Specifically, for example, water resistant materials having barrier properties such as water vapor and water include, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer. A film or sheet of a resin such as a coalescence can be used, and as a light-shielding material, for example, a colorant such as a pigment, and other desired additives such as a pigment are added to the resin and kneaded. Various colored resin films or sheets having light-shielding properties 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 addition, as the above-mentioned other base material, specifically, there is little adsorption of a fragrance component contained in the contents to be packed and packed, and it is rich in aroma retaining property, and further, does not cause a taste change or a strange odor And a resin that can be extruded can be used.
Specifically, for example, polyacrylic resin, polymethacrylic resin, polyacrylonitrile resin, polymethacrylonitrile resin, polystyrene resin, polycarbonate resin, polyethylene terephthalate resin or its ethylene component and / or terephthalate component A part of the resin is copolymerized or modified with other di- or higher polyhydric alcohol components or di-carponic acid components, or polyester resins such as polyethylene naphthalate resins, polyamide resins, and ethylene-vinyl acetate copolymers. Resins such as saponified products, polyvinyl alcohol resins, polyvinyl chloride resins, polyvinylidene chloride resins, and the like can be used.
Therefore, in the present invention, among the above-mentioned resins, it is desirable to use a resin having a fragrance retention property and a barrier property against oxygen gas or water vapor. Specifically, for example, ethylene-vinyl acetate copolymer is used. It is desirable to use a saponified polymer, a polyamide-based resin, a polyacrylonitrile-based resin, a polyester-based resin, or the like, which is rich in aroma retention and barrier properties.

Thus, in the present invention, a method for producing a laminated material for a laminated tube container according to the present invention using the above-described base material will be described. As such a method, a normal packaging material is produced. Laminating method sometimes used, for example, wet lamination method, dry lamination method, solventless dry lamination method, extrusion lamination method, T-die coextrusion molding method, coextrusion lamination method, inflation method, etc. It can be carried out.
Thus, in the present invention, when performing the above-mentioned lamination, if necessary, pretreatment such as corona treatment and ozone treatment can be applied to the film, and for example, an isocyanate (urethane) Anchor coating agents such as polyethyleneimine, polybutadiene, and organic titanium, or polyurethane, polyacrylic, polyester, epoxy, polyvinyl acetate, cellulose, and other adhesives for laminates, etc. are known. An anchor coating agent, a laminating adhesive, and the like can be arbitrarily used.
Further, in the present invention, any one of the substrates constituting the laminated material for a laminate tube container according to the present invention, for example, before the lamination, for example, gravure printing method, offset printing method, letterpress printing method, silk screen A desired printing pattern can be formed using a printing method, a flexographic printing method, or the like.
Specifically, in the present invention, a desired printed pattern or the like can be formed on a substrate constituting the surface polyolefin resin layer or a substrate film having an inorganic oxide vapor-deposited film. .

  Next, in the present invention, when manufacturing the laminated tube container according to the present invention, for example, as a method of heat sealing when manufacturing a cylindrical body, for example, a bar seal, a rotary roll seal, a belt It can be performed by a known method such as sealing, impulse sealing, high-frequency sealing, ultrasonic sealing, or flame sealing.

Next, in the present invention, the laminate material for a laminated tube container manufactured as described above is used. First, a gravure printing method, a flexographic printing method, or the like is applied to the surface of the laminated material for a laminate tube container. Using ink, flexo ink, etc., print and form a printed pattern layer consisting of characters, figures, symbols, patterns, etc. Then, the cylindrical end portion of the laminated tube container is manufactured by welding the overlapping end portion, and then, for example, using high-density polyethylene or the like above the cylindrical barrel portion. For example, an injection molding method, a compression molding method, or other molding methods are formed and welded to form a head portion including a shoulder portion and a mouth portion. Polypro Attach the cap produced by molding by injection molding or the like using a lens resins, according lamination to the present invention - can be produced Tochubu container.
Thus, in the present invention, the contents to be filled and packed are filled from the opening at the lower end of the laminated tube container manufactured above, and then the opening is heat sealed to form the bottom seal portion. Thus, it is possible to manufacture a packaged product including the laminated tube container according to the present invention.
In the above, examples of the contents to be filled and packaged include toothpaste, cosmetics, glue, paste, paste wasabi, cream, paint, ointment, pharmaceutical, and the like.
In the above, in addition to the above-described high-density polyethylene, the above metallocene catalyst is used as a material for constituting the head composed of the shoulder, mouth and the like of the laminated tube container according to the present invention. It is also possible to use an ethylene-α-olefin copolymer.

In the above, flexographic printing is a type of letterpress printing, using a flexible resin or rubber letterpress, and using solvent-dried flexographic ink, and is made of characters, figures, symbols, patterns, etc. A printed pattern layer is formed by printing.
In addition, as the flexographic ink, it is possible to use an evaporation-drying ink mainly composed of an alcoholic or water-based vehicle, an ultraviolet curable ink, or the like that does not relatively invade rubber letterpress.
Thus, in the present invention, by using a flexographic printing method or the like, a laminated material for a laminated tube container is manufactured in a plain state, and the laminated material for a plain laminated tube container or a plain cylindrical same part is produced. The desired printed pattern layer can be formed by printing directly on the surface of the material, making it possible to produce a batch of raw materials, increasing its production efficiency, reducing manufacturing loss, etc. Accordingly, since only the necessary quantity is printed, the manufacturing loss can be reduced and the delivery time can be shortened.
That is, usually, a desired printed picture layer is formed by printing on a raw film such as a plastic film, and then another plastic film or the like is laminated thereon to produce a laminated material with a printed picture. For this reason, the lead time from receiving an order becomes longer, and the raw fabric lot is known for each pattern, which makes the manufacturing process and manufacturing cost extremely disadvantageous. However, the present invention eliminates such problems. It has the advantage of obtaining.

Next, the present invention will be described more specifically with reference to examples.
(1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used as the base film. First, the above-mentioned biaxially stretched polyethylene terephthalate film is mounted on a feeding roll of a plasma chemical vapor deposition apparatus, and then this is fed out. On the corona-treated surface of the biaxially stretched polyethylene terephthalate film, a silicon oxide vapor deposition film having a thickness of 200 mm was formed under the following vapor deposition conditions.
(Deposition conditions)
Reaction gas mixing ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 11: 10 (unit: Slm)
Degree of vacuum in the vacuum chamber; 5.2 × 10 ⁻⁶ mbar
Degree of vacuum in the deposition chamber; 5.1 × 10 ^-2 mbar
Cooling and electrode drum power supply: 35 kW
Film transport speed: 90 m / min
Next, immediately after forming the silicon oxide vapor deposition film having a thickness of 200 mm as described above, a glow discharge plasma generator is used on the surface of the silicon oxide vapor deposition film, and the power is 9 kw, oxygen gas. (O ₂ ): Argon gas (Ar) = 7.0: 2.5 (unit: Slm) is used, and the mixed gas pressure is 6.0 × 10 ⁻² mba, and the processing speed is 420 m / min. / A mixed gas plasma treatment was performed to form a plasma-treated surface in which the surface tension of the deposited film surface of silicon oxide was improved by 54 dyne / cm or more.
(2). On the other hand, according to the composition shown in Table 1 below, the composition a. Composition prepared in advance in an EVOH solution prepared by dissolving an ethylene-vinyl alcohol copolymer (EVOH, ethylene copolymerization ratio 29%) in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzate consisting 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 resin 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 gas barrier composition.
(Table 1)
Composition a: EVOH (ethylene copolymerization ratio 29%) 0.610 (wt%)
Isopropyl alcohol 3.294
H ₂ O 2.196
Composition b: Ethyl silicate 40 11.460
Isopropyl alcohol 17.662
Aluminum acetylacetone 0.020
H ₂ O 13.752
Composition c: Polyvinyl alcohol resin 1.520
Silane coupling agent 0.050
Isopropyl alcohol 13.844
H ₂ O 35.462
Acetic acid 0.130
Total 100.000 (wt%)
Next, on the plasma-treated surface formed in the above (1), the gas barrier composition produced above is used, and this is coated by a gravure roll coating method, and then heated at 100 ° C. for 30 seconds. The gas barrier coating film having a thickness of 0.4 g / m ² (in the dry operation state) was formed to produce a barrier film according to the present invention.
(3). Next, a two-component curable polyurethane laminating adhesive is used on the entire surface including the gas barrier coating film constituting the barrier film produced as described above, and this is applied to the gravure roll coat in the same manner as described above. By this method, coating was performed so as to have a film thickness of 4.0 g / m ² (dry operation state) to form an adhesive layer for laminating.
Next, a 12 μm-thick biaxially stretched polyethylene terephthalate film was superimposed on the surface of the laminating adhesive layer formed above with the corona-treated surfaces facing each other, and then both were laminated by dry lamination.
Furthermore, a two-component curable urethane anchor coating agent is used on the biaxially stretched polyethylene terephthalate film layer laminated as described above, and this is coated with a film thickness of 0.4 g / m ² (dry) by a gravure roll coat method. The anchor coating agent layer is formed by coating so as to be in the (operating state), and then the surface of the anchor coating agent layer is melt-extruded to a thickness of 35 μm using low density polyethylene, and the thickness is 80 μm. The low density polyethylene film was extrusion laminated.
(4). On the other hand, a resin composition mainly composed of linear low-density polyethylene resin polymerized by a single-site catalyst and a low-pressure high-density polyethylene resin (density = 0.951, melt index, MI = 1.0) are the main components. Using a white resin composition containing 8% by weight of white pigment, multilayer inflation molding is performed by a multilayer inflation method, a transparent linear low density polyethylene resin layer having a thickness of 30 μm, and a thickness of 80 μm. A multi-layer laminated resin layer having a thickness of 140 μm consisting of a milky white low-density polyethylene resin layer and a transparent linear low-density polyethylene resin layer having a thickness of 30 μm is manufactured, and further, corona discharge treatment is applied to one surface thereof. And a corona discharge treated surface was formed.
Next, a low-density polyethylene film having a thickness of 60 μm was extrusion laminated to the corona discharge treated surface of the multilayer laminated resin layer produced above using a low-density polyethylene resin while being melt-extruded to 35 μm.
(5). Next, a two-component curing type polyurethane-based laminating adhesive is used on the surface of the low-density polyethylene film laminated by extrusion lamination as described above, and this is applied to a film thickness of 4.0 g / m ² (drying) by a gravure roll coating method. An adhesive layer for laminating was formed by coating so as to be in an operation state.
Next, the surface of the biaxially stretched polyethylene terephthalate film constituting the barrier film laminated in the above (3) is overlapped with the surface of the adhesive layer for laminating formed as described above, and then both are laminated. The laminated material which comprises the laminated tube container concerning this invention by dry-laminating was manufactured.
Furthermore, after the corona discharge treatment is performed on the surface of the transparent linear low density polyethylene resin layer having a film thickness of 30 μm located on the outermost surface of the laminated material constituting the laminated tube container manufactured as described above, the ultraviolet curing type is applied to the corona treatment surface. Using the flexographic ink composition, a desired printed pattern layer was formed by a flexographic printing method to produce a laminated material constituting the laminated tube container according to the present invention.
(6). Next, using the laminated material constituting the laminated tube container produced above, first, the laminated material constituting the laminated tube container is punched to produce a blank plate, and then the blank plate is rolled up The back end of the polymerized end is rate-sealed at 215 ° C. for 3 seconds under a thermal welding condition of 3 Kg / cm ² to produce a cylindrical body serving as the body of a laminated tube container having a diameter of 35 mm and a height of 160 mm. did.
Next, the cylindrical body manufactured as described above is mounted on a mandrel for forming a laminated tube container, and then, at one end of the cylindrical body, a frustoconical shoulder portion and a narrow neck mouth and neck continuous with the shoulder portion are formed in a conventional manner. Using a high-density polyethylene composition in which 98.0 parts by weight of high-density polyethylene and 2.0 parts by weight of milky white pigment are added, the head is formed by compression molding at a resin temperature of 245 ° C. A laminated tube container according to the present invention was produced.
Next, a cap made of polypropylene resin is spirally wound on the mouth and neck of the cylindrical body having the above-mentioned head, and then 150 g of kneaded wasabi is filled from the other opening of the cylindrical body. The opening was heat-sealed to form a bottom seal portion, and a packaged product made of a laminated tube container according to the present invention was manufactured.
The packaged product consisting of the laminated tube container produced above is excellent in barrier properties against oxygen gas, water vapor, etc., is excellent in laminate strength, etc., withstands distribution in the market, and is excellent in storage and preservation. there were.
Moreover, there was no particular problem even if the used laminating tube container or the like was incinerated and discarded.

(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 feeding roll of a plasma chemical vapor deposition apparatus. A vapor-deposited film of silicon oxide having a thickness of 200 mm was formed on the corona-treated surface.
(Deposition conditions)
Reaction gas mixing ratio: Hexamethyldisiloxane: Oxygen gas: Helium = 1.2: 5.0: 2.5 (Unit: Slm)
Ultimate pressure: 5.0 × 10 ^-5 mbar
Film forming pressure: 7.0 × 10 ⁻² mbar
Line speed: 150 m / min
Power; 35kw
Next, immediately after forming the silicon oxide vapor-deposited film having a thickness of 200 mm, a glow discharge plasma generator is used on the surface of the silicon oxide vapor-deposited film, and the power is 9 kW, oxygen gas (O ₂ ): argon Using a mixed gas consisting of gas (Ar) = 7.0: 2.5 (unit: Slm), oxygen / argon mixed gas plasma treatment at a mixed gas pressure of 6.0 × 10 ⁻² mba and a processing speed of 420 m / min. Was performed to form a plasma-treated surface in which the surface tension of the deposited silicon oxide film surface was improved by 54 dyne / cm or more.
(2). On the other hand, according to the composition shown in Table 2 below, composition a. Composition prepared in advance in an EVOH solution dissolved in a mixed solvent of ethylene-vinyl alcohol copolymer (EVOH, ethylene copolymerization ratio 29%), isopropyl alcohol and ion-exchanged water b. A hydrolyzate consisting 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 resin solution, acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent gas barrier composition.
(Table 2)
Composition a: EVOH (ethylene copolymerization ratio 29%) 0.122 (wt%)
Isopropyl alcohol 0.659
H ₂ O 0.439
Composition b: Ethyl silicate 40 9.146
Isopropyl alcohol 8.780
Aluminum acetylacetone 0.018
H ₂ O 16.291
Composition c: Polyvinyl alcohol resin 1.220
Isopropyl alcohol 19.893
H ₂ O 43.329
Acetic acid 0.103
Total 100.000 (wt%)
Next, on the plasma-treated surface formed in the above (1), the gas barrier composition produced above is used, and this is coated by a gravure roll coating method, and then heated at 100 ° C. for 30 seconds. The gas barrier coating film having a thickness of 0.4 g / m ² (in the dry operation state) was formed to produce a barrier film according to the present invention.
(3). Next, a two-component curable polyurethane laminating adhesive is used on the entire surface including the gas barrier coating film constituting the barrier film produced as described above, and this is applied to the gravure roll coat in the same manner as described above. By this method, coating was performed so as to have a film thickness of 4.0 g / m ² (dry operation state) to form an adhesive layer for laminating.
Next, a 12 μm-thick biaxially stretched polyethylene terephthalate film was superimposed on the surface of the laminating adhesive layer formed above with the corona-treated surfaces facing each other, and then both were laminated by dry lamination.
Furthermore, a two-component curable urethane anchor coating agent is used on the biaxially stretched polyethylene terephthalate film layer laminated as described above, and this is coated with a film thickness of 0.4 g / m ² (dry) by a gravure roll coat method. The anchor coating agent layer is formed by coating so as to be in the (operating state), and then the surface of the anchor coating agent layer is melt-extruded to a thickness of 35 μm using low density polyethylene, and the thickness is 80 μm. The low density polyethylene film was extrusion laminated.
(4). On the other hand, a resin composition mainly composed of linear low-density polyethylene resin polymerized by a single-site catalyst and a low-pressure high-density polyethylene resin (density = 0.951, melt index, MI = 1.0) are the main components. Using a white resin composition containing 8% by weight of white pigment, multilayer inflation molding is performed by a multilayer inflation method, a transparent linear low density polyethylene resin layer having a thickness of 30 μm, and a thickness of 80 μm. A multi-layer laminated resin layer having a thickness of 140 μm consisting of a milky white low-density polyethylene resin layer and a transparent linear low-density polyethylene resin layer having a thickness of 30 μm is manufactured, and further, corona discharge treatment is applied to one surface thereof. And a corona discharge treated surface was formed.
Next, a low-density polyethylene film having a thickness of 60 μm was extrusion laminated to the corona discharge treated surface of the multilayer laminated resin layer produced above using a low-density polyethylene resin while being melt-extruded to 35 μm.
(5). Next, a two-component curing type polyurethane-based laminating adhesive is used on the surface of the low-density polyethylene film laminated by extrusion lamination as described above, and this is applied to a film thickness of 4.0 g / m ² (drying) by a gravure roll coating method. An adhesive layer for laminating was formed by coating so as to be in an operation state.
Next, the surface of the biaxially stretched polyethylene terephthalate film constituting the barrier film laminated in the above (3) is overlapped with the surface of the adhesive layer for laminating formed as described above, and then both are laminated. The laminated material which comprises the laminated tube container concerning this invention by dry-laminating was manufactured.
Furthermore, after the corona discharge treatment is performed on the surface of the transparent linear low density polyethylene resin layer having a film thickness of 30 μm located on the outermost surface of the laminated material constituting the laminated tube container manufactured as described above, the ultraviolet curing type is applied to the corona treatment surface. Using the flexographic ink composition, a desired printed pattern layer was formed by a flexographic printing method to produce a laminated material constituting the laminated tube container according to the present invention.
(6). Next, using the laminated material constituting the laminated tube container produced above, first, the laminated material constituting the laminated tube container is punched to produce a blank plate, and then the blank plate is rolled up The back end of the polymerized end is rate-sealed at 215 ° C. for 3 seconds under a thermal welding condition of 3 Kg / cm ² to produce a cylindrical body serving as the body of a laminated tube container having a diameter of 35 mm and a height of 160 mm. did.
Next, the cylindrical body manufactured as described above is mounted on a mandrel for forming a laminated tube container, and then, at one end of the cylindrical body, a frustoconical shoulder portion and a narrow neck mouth and neck continuous with the shoulder portion are formed in a conventional manner. Using a high-density polyethylene composition in which 98.0 parts by weight of high-density polyethylene and 2.0 parts by weight of milky white pigment are added, the head is formed by compression molding at a resin temperature of 245 ° C. A laminated tube container according to the present invention was produced.
Next, a cap made of polypropylene resin is spirally wound on the mouth and neck of the cylindrical body having the above-mentioned head, and then 150 g of toothpaste is filled from the other opening of the cylindrical body. The opening was heat-sealed to form a bottom seal portion, and a packaged product made of a laminated tube container according to the present invention was manufactured.
The packaged product consisting of the laminated tube container produced above is excellent in barrier properties against oxygen gas, water vapor, etc., is excellent in laminate strength, etc., withstands distribution in the market, and is excellent in storage and preservation. there were.
Moreover, there was no particular problem even if the used laminating tube container or the like was incinerated and discarded.

  In Example 1 above, instead of extrusion laminating a low-density polyethylene film having a thickness of 80 μm on the surface of the biaxially stretched polyethylene terephthalate film, first, a linear low-density polyethylene resin polymerized with a single-site catalyst is used. A linear low density polyethylene resin layer having a film thickness of 70 μm is formed by performing multilayer inflation molding by a multilayer inflation method using a resin composition having a main component and a resin composition having a high pressure method low density polyethylene resin as a main component. A two-layer laminated resin layer having a film thickness of 100 μm consisting of two layers with a high-pressure method low-density polyethylene resin layer having a film thickness of 30 μm is manufactured, and then this is used in place of a low-density polyethylene film having a thickness of 80 μm. Except for this, the laminate was the same as in Example 1 above, and the same laminate as in Example 1 above. Laminated materials, laminated tube containers and packaged products constituting the tube containers were manufactured.

(1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used as the base film. First, the above-mentioned biaxially stretched polyethylene terephthalate film is mounted on a take-up roll of a take-up vacuum deposition apparatus, and then this is fed out. The film thickness of the biaxially stretched polyethylene terephthalate film is as follows according to the following vapor deposition conditions by using an electron beam (EB) heating method while supplying oxygen gas using aluminum as a vapor deposition source. A 200-mm aluminum oxide vapor deposition film was formed.
(Deposition conditions)
Degree of vacuum in the deposition chamber; 2 × 10 ^-4 mbar
Degree of vacuum in winding chamber; 2 × 10 ^-2 mbar
Electron beam power: 25 kW
Film transport speed: 240 m / min
Vapor deposition surface; Corona treatment surface Next, immediately after forming the 200 nm thick aluminum oxide vapor deposition film, a plasma treatment surface was formed on the aluminum oxide vapor deposition film surface in the same manner as in Example 1 above. did.
(2). On the other hand, according to the composition shown in Table 3 below, composition a. Composition prepared in advance in an EVOH solution prepared by dissolving an ethylene-vinyl alcohol copolymer (EVOH, ethylene copolymerization ratio 29%) in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzate consisting 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 resin 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 gas barrier composition.
(Table 3)
Composition a: EVOH (ethylene copolymerization ratio 29%) 0.610 (wt%)
Isopropyl alcohol 3.294
H ₂ O 2.196
Composition b: Ethyl silicate 40 11.460
Isopropyl alcohol 17.662
Aluminum acetylacetone 0.020
H ₂ O 13.752
Composition c: Polyvinyl alcohol resin 1.520
Silane coupling agent 0.050
Isopropyl alcohol 13.844
H ₂ O 35.462
Acetic acid 0.130
Total 100.000 (wt%)
Next, on the plasma-treated surface formed in the above (1), the gas barrier composition produced above is used, and this is coated by a gravure roll coating method, and then heated at 100 ° C. for 30 seconds. The gas barrier coating film having a thickness of 0.4 g / m ² (in the dry operation state) was formed to produce a barrier film according to the present invention.
(3). Next, a two-component curable polyurethane laminating adhesive is used on the entire surface including the gas barrier coating film constituting the barrier film produced as described above, and this is applied to the gravure roll coat in the same manner as described above. By this method, coating was performed so as to have a film thickness of 4.0 g / m ² (dry operation state) to form an adhesive layer for laminating.
Next, a 12 μm-thick biaxially stretched polyethylene terephthalate film was superimposed on the surface of the laminating adhesive layer formed above with the corona-treated surfaces facing each other, and then both were laminated by dry lamination.
Furthermore, a two-component curable urethane anchor coating agent is used on the biaxially stretched polyethylene terephthalate film layer laminated as described above, and this is coated with a film thickness of 0.4 g / m ² (dry) by a gravure roll coat method. The anchor coating agent layer is formed by coating so as to be in the (operating state), and then the surface of the anchor coating agent layer is melt-extruded to a thickness of 35 μm using low density polyethylene, and the thickness is 80 μm. The low density polyethylene film was extrusion laminated.
(4). On the other hand, a resin composition mainly composed of linear low-density polyethylene resin polymerized by a single-site catalyst and a low-pressure high-density polyethylene resin (density = 0.951, melt index, MI = 1.0) are the main components. Using a white resin composition containing 8% by weight of white pigment, multilayer inflation molding is performed by a multilayer inflation method, a transparent linear low density polyethylene resin layer having a thickness of 30 μm, and a thickness of 80 μm. A multi-layer laminated resin layer having a thickness of 140 μm consisting of a milky white low-density polyethylene resin layer and a transparent linear low-density polyethylene resin layer having a thickness of 30 μm is manufactured, and further, corona discharge treatment is applied to one surface thereof. And a corona discharge treated surface was formed.
Next, a low-density polyethylene film having a thickness of 60 μm was extrusion laminated to the corona discharge treated surface of the multilayer laminated resin layer produced above using a low-density polyethylene resin while being melt-extruded to 35 μm.
(5). Next, a two-component curing type polyurethane-based laminating adhesive is used on the surface of the low-density polyethylene film laminated by extrusion lamination as described above, and this is applied to a film thickness of 4.0 g / m ² (drying) by a gravure roll coating method. An adhesive layer for laminating was formed by coating so as to be in an operation state.
Next, the surface of the biaxially stretched polyethylene terephthalate film constituting the barrier film laminated in the above (3) is overlapped with the surface of the adhesive layer for laminating formed as described above, and then both are laminated. The laminated material which comprises the laminated tube container concerning this invention by dry-laminating was manufactured.
Furthermore, after the corona discharge treatment is performed on the surface of the transparent linear low density polyethylene resin layer having a film thickness of 30 μm located on the outermost surface of the laminated material constituting the laminated tube container manufactured as described above, the ultraviolet curing type is applied to the corona treatment surface. Using the flexographic ink composition, a desired printed pattern layer was formed by a flexographic printing method to produce a laminated material constituting the laminated tube container according to the present invention.
(6). Next, using the laminated material constituting the laminated tube container produced above, first, the laminated material constituting the laminated tube container is punched to produce a blank plate, and then the blank plate is rolled up The back end of the polymerized end is rate-sealed at 215 ° C. for 3 seconds under a thermal welding condition of 3 Kg / cm ² to produce a cylindrical body serving as the body of a laminated tube container having a diameter of 35 mm and a height of 160 mm. did.
Next, the cylindrical body manufactured as described above is mounted on a mandrel for forming a laminated tube container, and then, at one end of the cylindrical body, a frustoconical shoulder portion and a narrow neck mouth and neck continuous with the shoulder portion are formed in a conventional manner. Using a high-density polyethylene composition in which 98.0 parts by weight of high-density polyethylene and 2.0 parts by weight of milky white pigment are added, the head is formed by compression molding at a resin temperature of 245 ° C. A laminated tube container according to the present invention was produced.
Next, a cap made of polypropylene resin is spirally wound on the mouth and neck of the cylindrical body having the above-mentioned head, and then 150 g of toothpaste is filled from the other opening of the cylindrical body. The opening was heat-sealed to form a bottom seal portion, and a packaged product made of a laminated tube container according to the present invention was manufactured.
The packaged product consisting of the laminated tube container produced above is excellent in barrier properties against oxygen gas, water vapor, etc., is excellent in laminate strength, etc., withstands distribution in the market, and is excellent in storage and preservation. there were.
Moreover, there was no particular problem even if the used laminating tube container or the like was incinerated and discarded.

[Experimental example]
About the laminated material which comprises the laminated tube container concerning this invention manufactured in said Examples 1-4, oxygen permeability, water vapor permeability, the suitability of a hand, and a temporal test were measured. (1). Measurement of Oxygen Permeability This is for a laminated material under the conditions of a temperature of 23 ° C. and a humidity of 90% RH, using a measuring instrument manufactured by Mocon, USA (model name: OX-TRAN 2/20). It was measured.
(2). Measurement of water vapor transmission rate This is the measurement of the laminate material under the conditions of a temperature of 40 ° C. and a humidity of 90% RH, manufactured by MOCON, USA [model name, PERMATRAN 3/31]. Measured and evaluated.
(3). Measurement of hand grip suitability This was evaluated by measuring the oxygen permeability and water vapor permeability of the laminated material after 1000 hand grinds and 5000 times later in the same manner as described above.
(Four ). Measurement of aging test This is to fill a tube container (45φ) with the contents of vinegar: oil = 1: 1, leave it at 40 ° C., 90% RH for 3 months, take out the contents, and Similarly, oxygen permeability and water vapor permeability were measured and evaluated.
The measurement results are shown in Table 4, Table 5, and Table 6 below.

(Table 4)
┌────┬────────────┐ │ │ Laminate │ │ ├─────┬──────┤ │ │ Oxygen permeability │ Water vapor permeability │ ├ ────┼─────┼──────┤ │Example 1│ 0.02│ 0.004│ ├────┼─────┼──────┤ │Example 2│ 0.04│ 0.004│ ├────┼────┼──────┤ │Example 3│ 0.03│ 0.004│ ├────実 施 ─────┼──────┤ │Example 4│ 0.03│ 0.003│ └────┴─────┴──────┘

(Table 5)
┌────┬─────────────────────────┐ │ │ Suitable for handling │ │ ├ ─────────── ──┬────────────┤ │ │ 1000 times │ 5000 times │ │ ├ ────┬┬──────┼─────┬───── ─┤ │ │Oxygen permeability │Water vapor permeability │Oxygen permeability │Water vapor permeability│ ├────┼─────┼──────┼─────┼───── ─┤ │Example 1│ 0.02│ 0.004│ 0.04│ 0.007│ ├────┼─────┼──────┼─────┼── ────┤ │Example 2│ 0.03│ 0.005│ 0.06│ 0.008│ ├────┼────┼┼──────┼─────実 施 ──────┤ │Example 3│ 0.04│ 0.004│ 0.05│ 0.008│ ├── ─┼─────┼──────┼─────┼──────┤ │Example 4│ 0.05│ 0.003│ 0.05│ 0.005│ └ ────┴─────┴──────┴─────┴┴──────┘

(Table 6)
┌────┬─────────────────────────┐ │ │ Aging test │ │ ├ ──────────── ─┬────────────┤ │ │ Initial │ Three months later │ │ ├─────┬──────┼─────┬─────── │ │ │ Oxygen permeability │ Water vapor permeability │ Oxygen permeability │ Water vapor permeability │ ├────┼─────┼──────┼─────┼─────── ┤ │Example 1│ 0.02│ 0.004│ 0.02│ 0.005│ ├────┼─────┼──────┼─────┼─── ───┤ │Example 2│ 0.04│ 0.004│ 0.05│ 0.006│ ├────┼─────┼──────┼─────┼ ──────┤ │Example 3│ 0.03│ 0.004│ 0.03│ 0.005│ ├────┼─ ───┼──────┼─────┼──────┤ │Example 4│ 0.03│ 0.003│ 0.03│ 0.004│ └──── ┴─────┴──────┴─────┴──────┘

  In Tables 4, 5 and 6, the unit of oxygen permeability is [cc / package / day · 23 ° C · 90% RH], and the unit of water vapor permeability is [g / Package / day · 40 ° C. · 90% RH].

  As is clear from the measurement results shown in Table 4, Table 5, and Table 6, the laminated material for a laminated tube container according to the present invention is excellent in oxygen barrier properties, water vapor barrier properties, etc. It was excellent in hand-grip aptitude, aging test, etc., and could sufficiently withstand use as a laminated tube container for filling and packaging various contents.

  The present invention has strength and the like, and is excellent in heat resistance, moisture resistance, heat seal property, pin hole resistance, puncture resistance, transparency, etc., and in particular, permeation of oxygen gas and water vapor head. It has excellent gas barrier properties, has good packing and storage suitability for its contents, storage suitability, etc., and is also suitable for disposal, environmental suitability, etc. without generating harmful substances when incinerated after treatment. The present invention also relates to a laminar tube container which is extremely excellent.

It is a schematic sectional drawing which shows an example of the layer structure about the laminated material which manufactures the laminated tube container concerning this invention. It is a schematic sectional drawing which shows an example of the layer structure about the laminated material which manufactures the laminated tube container concerning this invention. It is a schematic sectional drawing which shows an example of the layer structure about the laminated material which manufactures the laminated tube container concerning this invention. It is a schematic sectional drawing which shows an example of the layer structure about the laminated material which manufactures the laminated tube container concerning this invention. It is a schematic perspective view which shows the structure of the laminate tube container concerning this invention manufactured using the laminated material for laminate tube containers shown in FIG. It is a schematic perspective view which shows the structure of the laminate tube container concerning this invention manufactured using the laminated material for laminate tube containers shown in FIG. FIG. 7 is a schematic perspective view showing an example of a packaged product in which contents are filled and packaged in a laminated tube container according to the present invention shown in FIGS. 5 and 6. It is a schematic block diagram which shows an example of a low temperature plasma chemical vapor deposition apparatus. It is a schematic block diagram which shows an example of a winding-type vacuum deposition apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Surface resin layer 2 Intermediate | middle layer 3 Inner surface resin layer 4 Milk white polyethylene-type resin layer 5, 5a Multilayer laminated resin layer 6 Base film 7 Deposition film | membrane of inorganic oxide 8 Gas barrier coating film 9 Barrier film 10, 10a Polyethylene resin Layer 11, 11a Transparent polyethylene-based resin layer 12 Two-layer laminated resin layer 13, 13 ′ End portion 14 Heat seal portion 15 Shoulder portion 16 Mouth portion 17 Head portion 18 Cap 19 Contents 20 Bottom seal portion A, A ₁ , A ₂ , A ₃ laminated material B Tubular body C Tube container D Packaging

Claims (20)

At least a surface resin layer, an intermediate layer, and an inner surface resin layer are sequentially laminated, and further, the both ends of the laminated material are overlapped to form a polymerization portion of the surface resin layer and the inner surface resin layer. In a laminar tube container in which a cylindrical body is formed by heat sealing, and a head including a shoulder and a mouth is provided at one opening of the cylindrical body. The surface resin layer is composed of a multilayer laminated resin layer including a milk white polyethylene-based resin layer, and the intermediate layer is provided with a vapor deposition film of an inorganic oxide on one surface of the base film, On the surface of the inorganic oxide vapor-deposited film, 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 is a metal N represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents the valence of M. A gas barrier comprising a gas barrier composition comprising at least one alkoxide represented by the formula, a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer, and further obtained by polycondensation by a sol-gel method. A laminar tube container comprising a barrier film provided with a conductive coating film, and the inner surface resin layer comprising a polyethylene resin layer. The laminar tube container according to claim 1, wherein the surface resin layer has a printed pattern layer on one side thereof. The surface resin layer is composed of a multi-layer laminated resin layer in which a transparent polyethylene resin layer, a milk white polyethylene resin layer, and a transparent polyethylene resin layer are sequentially laminated. 2. A laminar tube container according to item 1. Opacifying polyethylene resin layer, above which is characterized in that it consists of milk white polyethylene resin layer mainly composed of polyethylene resin consisting of density 0.935g / cm ³ ~0.960g / cm ³ of the preceding claims A laminar tube container according to any one of the preceding claims. 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 to 4, Laminate tube container as described. The laminated film according to any one of claims 1 to 5, wherein the vapor-deposited film of inorganic oxide comprises a vapor-deposited film of inorganic oxide by chemical vapor deposition or physical vapor deposition. Tote container. The laminated tube container according to any one of claims 1 to 6, wherein the inorganic oxide vapor deposition film is a silicon oxide vapor deposition film formed by a chemical vapor deposition method. 8. The laminated tube container according to claim 1, wherein the inorganic oxide vapor-deposited film is a vapor-deposited aluminum oxide film formed by physical vapor deposition. The laminating tube according to any one of claims 1 to 8, wherein M in the general formula R ¹ _n M (OR ² ) _m is composed of silicon, zirconium, titanium, or aluminum. -A container. The laminar tube container according to any one of claims 1 to 9, wherein the alkoxide is an alkoxysilane. The laminar tube container according to any one of claims 1 to 10, wherein the alkoxide comprises a hydrolyzate of alkoxide or a hydrolysis condensate of alkoxide. The laminar tube container according to any one of claims 1 to 11, wherein the gas barrier composition contains a silane coupling agent. The gas barrier composition has the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M 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 a valence of M.), a polyvinyl alcohol-based resin, and / or Or an ethylene-vinyl alcohol copolymer, and further comprising a gas barrier composition that undergoes polycondensation by the sol-gel method in the presence of a sol-gel method catalyst, acid, water, and an organic solvent. The laminar tube container according to any one of claims 1 to 12. The laminar tube container according to any one of claims 1 to 13, wherein the gas barrier coating film comprises a composite polymer layer in which one layer or two or more layers are laminated. The base film in which the gas barrier coating film is coated with the gas barrier composition and provided with the coating film is 30 ° C. to 10 seconds at a temperature of 20 ° C. to 150 ° C. and below the melting point of the base film. The laminar tube container according to any one of claims 1 to 14, wherein the laminar tube container comprises a cured film that is heat-treated for a minute. The laminating tube according to any one of claims 13 to 15, wherein the sol-gel catalyst comprises a tertiary amine that is substantially insoluble in water and soluble in an organic solvent. -A container. The laminar tube container according to any one of claims 13 to 16, wherein the tertiary amine comprises N, N-dimethylbenzylamine. The laminar tube container according to any one of claims 13 to 17, wherein water is used at a ratio of 0.1 to 100 moles per mole of alkoxide. The inner resin layer is composed of a low-density polyethylene resin layer, a linear low-density polyethylene resin layer, or a two-layer laminated resin layer of a linear high-density polyethylene resin layer and a low-density polyethylene resin layer. The laminar tube container according to any one of claims 1 to 18. 20. The surface resin layer, the intermediate layer, and the inner surface resin layer are dry-laminated through an adhesive layer for laminating, according to any one of the above 1 to 19 features. Laminate tube container.

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