JP2002087445A - Laminate tube container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate tube container wherein beautiful printed patterns or the like can be formed on a surface, the container has strength, flexibility or the like and is further excellent in barrier properties against an oxygen gas, vapor or the like and in resistance against contents or the like, while the container is suitable for fill-packaging contents including, for example, a toothpaste, food, cosmetics, medical products and others. SOLUTION: The laminate tube container comprises a laminate material which is constituted of at least a surface resin layer, an intermediate layer and an internal resin layer which are sequentially laminated wherein a surface of the outermost surface resin layer and a surface of the innermost internal resin layer at both ends of the laminate material are overlaid and their facing overlaps are heat-sealed to form a cylindrical barrel, and a head including shoulders and a mouth is provided on one of openings of the cylindrical barrel. The surface resin layer comprises a multilayer resin layer containing an opaque polyethylene-based resin layer. The intermediate layer comprises a barrier layer comprising a deposited film of an inorganic oxide formed by vapor phase growing method. Further, the internal resin layer comprises a polyethylene-based resin layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a laminating tube.
More specifically, the container has strength and the like, and is excellent in heat resistance, moisture resistance, heat sealability, pinhole resistance, piercing resistance, transparency and the like. It has excellent barrier properties to prevent the permeation of water vapor, etc., has suitability for filling and packaging the contents, suitability for preservation, etc., and is capable of forming beautiful printed patterns on the surface, and is incinerated after use. No harmful substances are generated during disposal.
The present invention relates to a laminating tube container which is extremely excellent in disposal suitability, environmental suitability and the like, and is useful for filling and packaging contents such as toothpaste, foods, cosmetics, pharmaceuticals and others.

[0002]

2. Description of the Related Art Conventionally, laminating tube containers have been manufactured by various methods. Usually, at least a surface resin layer, an intermediate layer, and an inner resin layer are sequentially laminated to form a laminated material. And then using the laminate,
The surface of the surface resin layer and the surface of the inner resin layer at both ends are overlapped with each other, and the overlapped portions facing each other are heat-sealed to produce a cylindrical body. A head having an opening, a shoulder, and the like is formed in one opening, and a cap is screwed into the opening to manufacture a laminating tube container. Thus, the laminating tube container manufactured as described above is provided with, for example, toothpaste, mayonnaise, paste wasabi, paste, ketchup, etc. from the other opening of the cylindrical body. Seasonings or whipped cream
Filling the contents of foods and drinks such as creams and other products, cosmetics, pharmaceuticals, etc., and then sealing the opening to form a bottom seal, Manufactures various forms of packaging products consisting of laminating tube containers. By the way, in the laminated material for manufacturing the above-mentioned laminate tube container, various plastic films and the like are laminated from the viewpoint of protecting the contents filled and packed in the laminate tube container. Among them, in particular, a barrier material having excellent gas barrier properties for preventing permeation of oxygen gas, water vapor and the like and further having excellent moisture proof properties are laminated. Examples of the barrier material include a resin film having an aluminum foil or an aluminum vapor-deposited film, a resin film having an aluminum oxide vapor-deposited film formed by a vacuum evaporation method, and a polyvinylidene chloride-based resin. Layer film,
Co-extruded film using polyvinylidene chloride resin,
Alternatively, a core with a polyvinylidene chloride-based resin composition
Film is used. In addition, an ethylene-vinyl alcohol copolymer film or the like is used as a barrier material.

[0003] In the above-mentioned laminating tube container, usually, on the outer peripheral surface of its body, a predetermined pattern such as a product name, a manufacturer, a seller, a manufacturing date, etc. Is formed on the printed picture layer. Thus, the above-mentioned printed picture layer is generally formed by laminating.
It is formed in advance by a gravure printing method or the like on the back surface of a raw film such as a resin film forming a front resin layer constituting the tube container, and thereafter, the intermediate layer, the inner resin layer and the like are formed. The laminated material is laminated to produce a laminated material, and then the laminated material is used to produce a laminating tube container.

[0004]

However, as described above, in a laminating tube container using an aluminum foil or a resin film having a vapor-deposited aluminum film as a barrier material, oxygen gas, water vapor, Although it is very excellent in barrier properties and the like for preventing the permeation of the like, it is difficult to see through the contents, and as a laminating tube container, there are problems such as inferior air-bag properties. In addition, when the laminating tube container is used as a packaging container and then discarded as garbage, metallic aluminum and the like remain, which degrades the suitability for disposal and causes problems such as environmental destruction. In addition, there is a problem that it is inferior in environmental suitability, and for example, when discarded by incineration, etc., metal aluminum etc. Scratches, and there is a problem of lack of significantly incineration waste processing aptitude. In addition, as described above, in a laminating tube container using a resin film having a deposited film of aluminum oxide by a vacuum deposition method or the like as a barrier material, it has transparency, and oxygen gas, It is excellent in barrier properties and the like for preventing the permeation of water vapor and the like, and is also excellent in suitability for disposal treatment after use. However, because it is physically attached to the resin film, deposited and laminated, it is vitreous, hard, significantly lacks flexibility and the like, for example, printing, lamination, Bag making process,
Cracks and the like are easily generated in the deposited film of aluminum oxide in post-processing such as others, and the barrier property for preventing the transmission of oxygen gas, water vapor and the like is remarkably impaired. The container has a problem that the so-called squeezability is poor. Further, as described above, a laminating tube container using a polyvinylidene chloride-based resin as a barrier material has an intended effect on gas barrier properties for preventing permeation of oxygen gas, water vapor and the like. However, when the laminating tube container is used as a packaging container and then disposed of as garbage, for example, if it is disposed of by incineration, etc., it contains chlorine atoms. For example, it may cause toxic gas such as dioxin, etc., and may affect the human body. Therefore, it is not only suitable for disposal but also causes problems such as environmental destruction. There is a problem. Further, in a laminating tube container using the above-mentioned ethylene-vinyl alcohol copolymer film as a barrier material, in a completely dry state, a gas barrier property for preventing permeation of oxygen gas, water vapor and the like is required. Although it has the expected effect, in a wet state, oxygen gas,
There is a problem that the gas barrier property for preventing permeation of water vapor or the like is remarkably deteriorated and cannot be used anymore.

[0005] In the above-mentioned laminate tube container, a print pattern is formed in advance by a gravure printing method or the like on the back surface of an original film such as a resin film forming a surface resin layer constituting the laminate tube container. When a layer is formed, a print pattern layer is formed on a raw film such as a resin film, and then, the intermediate layer, a material constituting the inner resin layer and the like are laminated, and further, a cylindrical body portion is formed. Since a laminating tube container is manufactured by forming a head and the like, if a defective product is manufactured, for example, at the time of lamination, at the time of forming a tubular body, or at the time of forming a head, a large amount of raw material is required. There is a problem of wasting anti-film and the like. Further, when a printed pattern layer is previously formed on the back surface of an original film such as a resin film forming a surface resin layer constituting a laminating tube container, the laminating tube container using the same is used. There is also a problem that it is not possible to transfer to a laminating tube container composed of the next new form, new product, etc., unless all of this is consumed. Further, in the case of the above-described laminating tube container, when forming the cylindrical body or the head portion, or in the packaged product in which the contents are filled and packed, the laminating tube is used. It is required that the laminated material forming the container has strength and a certain stiffness, and the laminated material forming the conventional laminating tube container is slightly lacking in strength, so-called ,
There is a problem in that the waist is insufficient and a defective product is produced in the laminating tube product. Further, in the case of the above-described laminating tube container, when the packaged product is directly displayed at a store, such as a standing tube, the so-called low-weight stress crack is generated by stacking when the packaged product is transported, and the display is displayed. Sometimes, the contents gradually leak from the bottom seal. Therefore, the present invention is capable of forming a beautiful printed pattern or the like on the surface, and has strength, stiffness, etc., furthermore, excellent barrier properties against oxygen gas, water vapor, etc., excellent content resistance, etc. For example,
An object of the present invention is to provide a laminating tube container suitable for filling and packaging contents such as toothpaste, foods, cosmetics, pharmaceuticals and others.

[0006]

Means for Solving the Problems The present inventor has made intensive studies to solve the above-mentioned problems, and as a result, at least,
A surface resin layer, an intermediate layer, and a laminated material having a configuration in which an inner resin layer is sequentially laminated, and furthermore, an inner resin that is an outermost layer on both ends of the laminated material and an inner resin that is an innermost layer. The surface of the layer is superimposed, and the overlapped portion facing the layer is heat-sealed to form a cylindrical body. Further, one opening of the cylindrical body has a shoulder and a mouth. Lamine with head
In the tube container, for example, the surface resin layer has a density of 0.935 g / cm ^{3 to} 0.960 g /
A multilayer resin layer including an opalescent polyethylene-based resin layer composed of a polyethylene resin having a size of about ³ cm, and a barrier layer including an inorganic oxide vapor-deposited film formed by chemical vapor deposition as an intermediate layer. Further, as the inner surface resin layer, for example, using a polyethylene-based resin layer, thus, to produce a laminated material by sequentially laminating these, then, for example, flexographic printing on the surface of the laminated material Form a desired printing pattern layer by flexographic printing using a method and the like, and then, after manufacturing a cylindrical body from the laminated material,
A laminating tube container is manufactured by using the cylindrical body portion and forming a head portion including a mouth portion, a shoulder portion, and the like at one opening thereof, and then the other of the tube container is manufactured. From the opening, for example, when filling and packaging contents such as toothpaste to produce a packaged product, to prevent waste of materials used, and,
It has a beautiful printed pattern layer on its surface, and also when manufacturing laminated materials, when manufacturing laminating tube containers, when manufacturing packaging products for filling and packing contents, or storing and selling packaging products. At times, it has sufficient strength to withstand, waist, etc., also has sufficient resistance to low load stress cracks, no leakage of contents, etc., and no phenomenon such as delamination In addition, it has excellent barrier properties to prevent permeation of oxygen gas, water vapor, etc.,
It has excellent preservability, and furthermore, it does not generate harmful substances when it is disposed after use.
Extremely environmentally friendly, for example, toothpaste, food,
The present invention has been completed by finding that a laminating tube container useful for filling and packaging contents such as cosmetics, pharmaceuticals and others can be produced.

That is, the present invention relates to a laminated material having a structure in which at least a surface resin layer, an intermediate layer, and an inner resin layer are sequentially laminated, and furthermore, a surface which is an outermost layer at both ends of the laminated material. The surface of the resin layer and the surface of the innermost resin layer, which is the innermost layer, are overlapped with each other, and the overlapped portions facing each other are heat-sealed to form a cylindrical body. In a laminating tube container provided with an opening, a shoulder, and a head consisting of a mouth, the surface resin layer comprises a multilayer resin layer including a milky polyethylene-based resin layer, and an intermediate layer, The present invention relates to a laminating tube container comprising a barrier layer comprising a vapor deposited film of an inorganic oxide formed by a chemical vapor deposition method, and further comprising an inner resin layer comprising a polyethylene resin layer.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The above-mentioned present invention will be described below in more detail with reference to the drawings and the like. First, the configuration of the laminate tube container according to the present invention will be described with reference to the drawings. FIGS. 1, 2, 3 and 4 show a laminated material forming the laminate tube container according to the present invention. FIG. 4 is a schematic sectional view showing a few examples of the layer configuration of FIG.
FIG. 2 is a schematic half sectional view showing a configuration of a laminating tube container according to the present invention manufactured using the laminated material shown in FIG. 1.

First, as a laminated material A for forming a laminating tube container according to the present invention, as shown in FIG.
The basic structure is such that at least a surface resin layer 1, an intermediate layer 2, and an inner resin layer 3 are sequentially laminated from the outside. Specifically, the laminated material forming the laminating tube container according to the present invention is specifically exemplified as shown in FIG. 2, at least a surface resin layer 1, an intermediate layer 2, and an inner resin layer. 3 and the surface resin layer 1 is composed of a multilayer resin layer 5 including an opalescent polyethylene-based resin layer 4, and the intermediate layer 2 is composed of inorganic oxide by chemical vapor deposition. consists barrier layer 6 containing the vapor deposited film of an object, further, it can be the inner surface resin layer 3, using the laminate a ₁ consisting of a polyethylene resin layer 7. Further, the laminating composition of the present invention
A more specific example of the laminated material forming the tube container is as shown in FIG. 3, which comprises a structure in which at least a surface resin layer 1, an intermediate layer 2, and an inner resin layer 3 are sequentially laminated. Further, the surface resin layer 1 comprises a transparent polyethylene resin layer 8, a milky polyethylene resin layer 4a,
The intermediate layer 2 is composed of a barrier layer 6 including a vapor-deposited film of an inorganic oxide formed by a chemical vapor deposition method. the resin layer 3 is one that can use a laminate a ₂ consisting of low-density polyethylene resin layer 7a.

Still another specific example of the laminated material forming the laminating tube container according to the present invention is shown in FIG. 4. As shown in FIG. 4, at least the surface resin layer 1, the intermediate layer 2, The inner surface resin layer 3 is sequentially laminated, and the surface resin layer 1 is further laminated with a transparent polyethylene resin layer 8, a milky polyethylene resin layer 4a, and a transparent polyethylene resin layer 8 sequentially. The intermediate layer 2 is composed of a barrier layer 6 including a vapor-deposited film of an inorganic oxide formed by chemical vapor deposition, and the inner resin layer 3 is composed of a linear low-density polyethylene resin. it can be used laminate a ₃ consisting of two layers of the layer 7b and the low-density polyethylene resin layer 7a. Thus,
The laminated materials exemplified above are only a few examples, and the present invention is not limited to the laminated materials having the above-described configurations, and various forms of laminated materials may be used. it can. For example, although not shown, a layer made of another material can be provided between each layer depending on the use, the content to be filled, and the like.
They can be arbitrarily laminated.

Next, in the present invention, an example of manufacturing a laminating tube container according to the present invention using the above-described laminated material will be described. FIG. 5 shows the tube shown in FIG. FIG. 2 is a schematic half-sectional view showing a configuration of a laminating tube container according to the present invention manufactured using a laminated material A forming a tube container. In the present invention, first, as shown in FIG.
After using a flexographic ink composition to form a print pattern layer (not shown) by flexographic printing of characters, figures, symbols, patterns, etc. by a flexographic printing method, a laminated material A on which the print pattern layer is formed And the surface of the surface resin layer as the outermost layer at both ends of the laminated material A and the surface of the inner resin layer as the innermost layer are overlapped, and the overlapped end is welded to form a welded portion 11. Thus, the cylindrical body 12 is manufactured, and the cylindrical body 12 is used as a body constituting a laminating tube container. Next, in the present invention, a head 15 comprising a shoulder portion 13, a mouth portion 14 and the like constituting a tube container is formed in a conventional manner above one opening of the cylindrical body portion 12, Thereafter, a sealing cap 16 is attached to the mouth portion 14 of the head 15 formed as described above to manufacture the laminating tube container R according to the present invention.
In addition, the laminating tube container R manufactured as described above is filled with an appropriate amount of contents 17 such as toothpaste from the other opening of the cylindrical body 12 and then packed. To form a bottom welded portion 18 to manufacture a packaged product Ra composed of a laminating tube container R filled with the contents 18. The above-mentioned examples are merely examples of the laminating tube container of the present invention, and the present invention is not limited thereby. Of course, in the present invention, FIG.
It is needless to say that the laminating tube container according to the present invention can be produced in the same manner as described above using the laminated material shown in FIG.

Next, in the present invention, the materials constituting the laminated material, the laminating tube container and the like as described above, the manufacturing method, and the like will be described. First, in the present invention, as a material constituting the surface resin layer, as described above, since the laminated material is rolled and the overlapped end portion thereof is welded to produce a cylindrical body, the material is melted by heating and mutually fused. It is preferable to use a heat-sealing resin that can be extruded, and is particularly preferably formed by a gravure printing method, a flexographic printing method, or the like. It is desirable to use a resin having heat-sealing properties capable of forming a resin. Specifically, the above-mentioned heath
Examples of the resin having properties include low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear (linear) low-density polyethylene (LLDPE), polypropylene, and ethylene-acetic acid. Vinyl copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-
Acid-modified polyolefin resin obtained by acid-modifying a polyolefin resin such as methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyethylene or polypropylene using an unsaturated carboxylic acid; As the acrylonitrile-based resin and ethylene-vinyl alcohol, polymers, polyvinyl alcohol-based resins, and other resins can be used.

Further, in the present invention, an ethylene-α-olefin copolymer polymerized by using a metallocene catalyst can be used as a 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. Ethylene-α-olefin copolymers obtained by polymerization can be used. The metallocene catalyst is a so-called multi-site catalyst in which the active sites are non-uniform and the current catalyst is called a single-site catalyst because the active sites are uniform. Specifically, the product name “Kernel” manufactured by Mitsubishi Chemical Corporation, the product name “Evolu” manufactured by Mitsui Petrochemical Industry Co., Ltd., and the product name “Exact” manufactured by Exxon Chemical Co., USA (EXACT) ", an ethylene-α-olefin polymerized using a metallocene catalyst such as" Affinity "(trade name, manufactured by DOW CHEMICAL, Inc.," ENGAGE "(trade name), manufactured by DOW CHEMICAL, USA) Copolymers can be used.

In the present invention, the surface resin layer composed of the multilayer resin layer including the milky white polyethylene resin layer contains, for example, the above-mentioned heat-sealing resin as a main component,
To this, a white pigment and other additives are optionally added to prepare a white resin composition. On the other hand, in the same manner as above, the heat-sealing resin is used as a main component, and the white pigment is added thereto. A transparent resin composition without the addition of a transparent resin composition, and then using the white resin composition and the transparent resin composition prepared above, for example, a molding method such as a T-die method, an inflation method, and the like. It can be manufactured using In particular,
Using the white resin composition prepared above and a transparent resin composition, for example, a feed block method, a multi-manifold
Using a multi-layer T die-casting method such as a mold method, a multi-layer inflation molding method, and other molding methods, a transparent polyethylene resin layer, a milky polyethylene resin layer, and a transparent polyethylene resin 3 of resin layer
A surface resin layer composed of a laminate in which the layers are sequentially co-extruded in multiple layers can be formed.

In the present invention, by using a multilayer resin layer including the above-mentioned milky polyethylene resin layer as the surface resin layer, for example, a transparent polyethylene resin existing on its outermost surface can be used. The layer can smoothen and flatten the uneven surface called fisheye by the polyethylene resin layer constituting the milky polyethylene resin layer, thereby printing by the gravure printing method or the flexo printing method or the like. The suitability can be greatly improved, the occurrence of the ink constituting the print pattern layer can be prevented, the extremely beautiful print pattern layer can be formed, and the occurrence of defective products due to print quality is improved. Is what you can do. Furthermore, in the present invention, when the surface resin layer is formed, the density of the polyethylene resin constituting the milky white polyethylene resin layer is 0.935 g.
/ Cm ³ when using the polyethylene resin consisting ～0.960G / cm ^3, the strength, those having the advantage of being able to produce a good laminate to the waist or the like. Furthermore, by using a laminated material having excellent strength and stiffness as described above, the laminating tube container can be formed at the time of forming a tubular body or at the time of forming a head or the like, or at the time of forming the contents. In a packaged product in which a product is filled and packed, it is possible to prevent the occurrence of defective products and the like. In the present invention, the thickness of the surface resin layer is about 25 μm to 300 μm, preferably 30 μm to 150 μm.
The order of μm is desirable. Further, in the present invention,
In the surface resin layer composed of a laminate in which three layers of the transparent polyethylene resin layer, the milky polyethylene resin layer, and the transparent polyethylene resin layer are sequentially co-extruded in multiple layers, the front surface and the back surface are configured. Preferably, the thickness of the transparent polyethylene resin layer is about 10 μm to 50 μm, and the thickness of the intermediate milky polyethylene resin layer is about 50 μm to 130 μm.

Next, in the present invention, the material constituting the inner resin layer is, similarly to the material constituting the above-mentioned surface resin layer, a material which can be melted and fused to each other by heat. As long as molding is possible, 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, ionomer resin, ethylene -Ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyolefin resin such as polyethylene or polypropylene is converted to acrylic acid, methacrylic acid. Acid-modified polyolefin resin, polyvinyl acetate resin, polyester resin, polystyrene resin, polyacrylonitrile resin modified with unsaturated carboxylic acids such as carboxylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc. , Ethylene-vinyl Alcohol - Le both polymers, polyvinyl alcohol - can be used Le resin, one or resin comprising more resins other like. Further, in the present invention, as a material constituting the inner resin layer,
Similarly to the above-mentioned material constituting the surface resin layer, an ethylene-α-olefin copolymer polymerized using a metallocene catalyst can be used in the same manner.

In the present invention, for example, the inner resin layer composed of a polyethylene-based resin layer contains, as a main component, one or more of the above resins, and optionally contains desired additives. To prepare a resin composition,
Using the resin composition prepared above, it can be produced by a molding method such as a T-die method, an inflation method and the like. In the present invention, the inner resin layer composed of a polyethylene resin layer is, specifically, a low-density polyethylene resin or a linear low-density polyethylene resin as a main component, and optionally adding a desired additive thereto. To prepare a low-density polyethylene-based resin composition or a linear low-density polyethylene-based resin composition, and then using the low-density polyethylene-based resin composition or the linear low-density polyethylene-based resin composition prepared above, For example, a low-density polyethylene resin layer or a linear low-density polyethylene resin layer produced by a molding method such as a T-die method, an inflation method, or the like can be used. Further, in the present invention, as another example, the low-density polyethylene resin composition and the linear low-density polyethylene resin composition prepared above are used as the inner resin layer composed of the polyethylene resin layer. For example, a multilayer T die-casting method such as a feed block method or a multi-manifold method, or a multilayer inflation molding method,
An inner resin layer composed of two layers, a linear low-density polyethylene resin layer and a low-density polyethylene resin layer, which are manufactured by co-extrusion and lamination into multiple layers using other molding methods, can be used. In the above, the low-density polyethylene-based resin layer constituting the inner resin layer is excellent in low odor of the contents, and the linear low-density polyethylene-based resin layer constituting the inner resin layer is excellent in strength and the like. Etc. can be improved. Therefore, when using the inner resin layer composed of two layers of the linear low-density polyethylene resin layer and the low-density polyethylene resin layer, the low-density polyethylene resin layer is disposed on the side in contact with the contents. Is preferred.

Furthermore, in the present invention, particularly when a linear low-density polyethylene resin is used as the resin constituting the inner resin layer as described above, the linear low-density polyethylene resin has an adhesive property. In order to prevent the deterioration of the environmental stress cracking resistance, there is an advantage that the propagation of the fracture is small and the impact resistance is improved because of having, and the inner layer is always in contact with the contents etc. This has the advantage that it is also effective. Further, 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 heat resistance is slightly inferior in high temperature environments. Although there is a tendency that the seal stability is deteriorated, there is an advantage that the tearing property is improved and it contributes to easy opening. Further, in the present invention, the linear low-density polyethylene-based resin as the resin having heat sealability as described above includes, specifically, ethylene-polymerized using the above-described metallocene catalyst.
α-Olefin copolymer can be used.

Next, in the present invention, a barrier layer including a vapor-deposited inorganic oxide film formed by chemical vapor deposition as a material constituting the intermediate layer will be described. , And specifically, for example, by a chemical vapor deposition method such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, or a photochemical vapor deposition method. De
It can be formed using a position method, a CVD method, or the like. More specifically, on one surface of a resin film, a monomer gas for vapor deposition such as an organic silicon compound is used as a raw material, and an inert gas such as an argon gas or a helium gas is used as a carrier gas. A vapor-deposited film of an inorganic oxide such as silicon oxide can be formed by using a low-temperature plasma-enhanced chemical vapor deposition method using an oxygen gas or the like as an oxygen supply gas and a low-temperature plasma generator or the like. In the above description, as the low-temperature plasma generator, for example, a generator such as a high-frequency plasma, a pulse wave plasma, or a microwave plasma can be used. Thus, in the present invention, a highly active and stable plasma is obtained. For this purpose, it is desirable to use a generator using a high-frequency plasma method.

More specifically, an example of a method of forming a deposited film of an inorganic oxide by the above-described plasma enhanced chemical vapor deposition method will be described. FIG. FIG. 1 is a schematic configuration diagram of a low-temperature plasma chemical vapor deposition apparatus showing an outline of a method for forming a deposited film of a substance. As shown in FIG. 6, in the present invention, the vacuum chamber-2 of the plasma enhanced chemical vapor deposition apparatus 21 is used.
The resin film 24 is unwound from an unwinding roll 23 disposed in the inside of the drum 2, and the resin film 24 is cooled at a predetermined speed via an auxiliary roll 25.
It is transported on six peripheral surfaces. In the present invention, oxygen gas, an inert gas, a monomer gas for vapor deposition of an organic silicon compound, and the like are supplied from the gas supply devices 27 and 28 and the raw material volatilization supply device 29, and the like. While adjusting the mixed gas composition for vapor deposition, the mixed gas composition for vapor deposition was introduced into the vacuum chamber 22 through the raw material supply nozzle 30 and was transferred onto the peripheral surface of the cooling / electrode drum 26 described above. Plasma is generated by the glow discharge plasma 31 on the resin film 24, and this is irradiated to form a deposited film of an inorganic oxide such as silicon oxide, thereby forming a film. In the present invention, at this time, a predetermined power is applied to the cooling / electrode drum 26 from a power supply 32 disposed outside the chamber.
In the vicinity of 6, a magnet 33 is disposed to promote the generation of plasma, and then the resin film 24 on which the deposited film of an inorganic oxide such as silicon oxide is formed is guided to a guide roll 34 or the like. The resin film having the inorganic oxide vapor-deposited film according to the present invention can be manufactured by winding the film on a winding roll 35 or the like. In the figure, 36
Represents a vacuum pump. The above exemplification is merely an example, and it goes without saying that the present invention is not limited thereby. Although not shown, in the present invention, as a deposited film of the inorganic oxide,
Not only one layer of the deposited film of the inorganic oxide but also a multilayer film in which two or more layers are laminated may be used, and the material to be used may be used in one kind or in a mixture of two or more kinds. It is also possible to form a deposited film of an inorganic oxide mixed with materials.

In the above, the inside of the vacuum chamber 22 is
The pressure is reduced by the empty pump 36 and the degree of vacuum is 1 × 10^-1~ 1 × 1
0^-8Torr level, preferably vacuum degree 1 × 10^-3~ 1 ×
10 ^-7It is desirable to adjust to the Torr position.
You. Further, in the raw material volatile supply device 29,
And the gas supply devices 27 and 28
Mixed with oxygen gas, inert gas, etc. supplied from
Vacuum gas through the raw material supply nozzle 30
−22. In this case, the mixed gas
The content of the organic silicon compound in the
Content is about 10-70%, inert gas content
Can be in the range of about 10-60%, for example,
The mixing ratio of organic silicon compound, oxygen gas and inert gas
The ratio can be about 1: 6: 5 to 1:17:14.
On the other hand, the cooling / electrode drum 26
Since the voltage is applied, the source in the vacuum chamber 22 is
Between the opening of the feed nozzle 30 and the cooling / electrode drum 26
Glow discharge plasma 31 is generated in the vicinity, and this glow discharge plasma 31 is generated.
The discharge plasma 31 is composed of one or more gas components in a mixed gas.
Is derived from the minute, in this state, the resin
The film 24 is transported at a constant speed, and the glow discharge
The resin on the peripheral surface of the cooling / electrode drum 26 is
Of inorganic oxide such as silicon oxide on the film 24
A film can be formed. At this time,
The degree of vacuum in the vacuum chamber is 1 × 10^-1~ 1 × 10
^-FourTorr level, preferably vacuum degree 1 × 10^-1~ 1 × 1
0^-2It is desirable to prepare at the Torr position, and the resin
The transport speed of the film 24 is about 10 to 300 m / min,
Preferably, it is desirable to adjust to 50 to 150 m / min.
It is good.

The above-mentioned plasma chemical vapor deposition apparatus 2
In (1), a vapor-deposited film of an inorganic oxide such as silicon oxide is formed on the resin film 24 in the form of a thin film in the form of SiO _X while oxidizing a plasma-converted raw material gas with oxygen gas. The formed deposited film of an inorganic oxide such as silicon oxide is a continuous layer that is dense, has few gaps, and is highly flexible. The property is much higher than that of a deposited film of an inorganic oxide such as silicon oxide formed by a conventional vacuum deposition method or the like, and a sufficient barrier property can be obtained with a thin film thickness. In the present invention,
The surface of the resin film 24 is formed by the SiO _X plasma.
Since the resin film 24 is cleaned and polar groups and free radicals are generated on the surface of the resin film 24, a film having a high adhesion between the deposited film of the inorganic oxide such as silicon oxide and the resin film is required. This has the advantage of becoming Furthermore,
As described above, the degree of vacuum at the time of forming a continuous film of an inorganic oxide such as silicon oxide is about 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, and preferably 1 × 10 ⁻¹ to 1 × 10 ^−2. Since the pressure is adjusted to the Torr level, the degree of vacuum in forming a deposited film of an inorganic oxide such as silicon oxide by a conventional vacuum deposition method is 1 × 10 ⁻⁴ to 1 ×.
Since the degree of vacuum is lower than that of 10 ^-5 Torr,
It is possible to shorten the time required to set a vacuum state when exchanging the resin film or sheet 24, so that the degree of vacuum is easily stabilized and the film forming process is stabilized.

In the present invention, a deposited silicon oxide film formed by using a vaporized monomer gas such as an organic silicon compound is chemically reacted with a vaporized monomer gas such as an organic silicon compound and oxygen gas. the reaction product is closely deposited on one surface of the resin film, dense, and forms a thin film rich in flexibility or the like, usually, the general formula SiO _X (provided that, X
Represents a number of 0 to 2), and is a continuous thin film mainly composed of silicon oxide. Thus, from the viewpoints of transparency, barrier properties, etc., the silicon oxide deposited film of the general formula Si
O _X (provided that, X represents represents. A number of 1.3 to 1.9) is intended is preferably a thin film mainly composed of vapor-deposited film of silicon oxide represented by. In the above description, the value of X changes depending on the molar ratio of the vaporized monomer gas to oxygen gas, the energy of the plasma, and the like. Is yellowish,
Transparency worsens.

The silicon oxide deposited film is mainly composed of silicon oxide, and further contains at least one compound of one or more of carbon, hydrogen, silicon or oxygen. It is characterized by comprising a deposited film containing the kind by chemical bonding or the like. For example,
When the compound having a C—H bond, the compound having a Si—H bond, or the carbon unit is in the form of graphite, diamond, fullerene, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained due to chemical bonding or the like. To give a specific example, CH
Hydrocarbon with _three sites, SiH ₃ silyl, Si
Examples thereof include hydrosilica such as H ₂ silylene and hydroxyl derivative such as SiH ₂ OH silanol. In addition to the above, by changing the conditions and the like in the vapor deposition process, the type, amount, and the like of the compound contained in the vapor-deposited silicon oxide film can be changed. Thus, the content of the above compound in the deposited silicon oxide film is 0.1 to 5%.
About 0%, preferably about 5 to 20% is desirable. In the above, when the content is less than 0.1%,
The impact resistance, spreadability, flexibility, etc. of the deposited film of silicon oxide become insufficient, and due to bending, scratches, cracks, etc. are easily generated, and it becomes difficult to stably maintain high barrier properties, and If it exceeds 50%, the barrier properties are undesirably reduced. Furthermore, in the present invention, the content of the above compound in the silicon oxide vapor deposition film is preferably reduced in the depth direction from the surface of the silicon oxide vapor deposition film, whereby the silicon oxide vapor deposition film is formed. On the surface of the resin, the impact resistance and the like can be enhanced by the above-described compounds, and on the other hand, at the interface with the resin film, since the content of the above-mentioned compound is small, the resin film and the silicon oxide deposited film Has the advantage that the tight adhesion of the polymer becomes strong.

Thus, in the present invention, the above-mentioned deposited film of silicon oxide may be, for example, an X-ray photoelectron spectrometer (Xr
ay Photoelectron Spectros
copy, XPS), secondary ion mass spectrometer (Sec.)
onion Ion Mass Spectrosc
The above physical properties are confirmed by performing elemental analysis of a deposited silicon oxide film using a method of performing ion etching in the depth direction or the like using a surface analysis device such as an S.O. can do. In the present invention, the thickness of the deposited silicon oxide film is desirably about 50 to 4000 °, and specifically, the thickness is desirably about 100 to 1000 °. Then, in the above, 1000 °, furthermore, 40
When the thickness is more than 00 °, cracks and the like are easily generated in the film, which is not preferable.
When the angle is less than 0 °, it is not preferable because it is difficult to exhibit the barrier effect. In the above description, the film thickness can be measured, for example, by a fundamental parameter method using a fluorescent X-ray analyzer (model name: RIX2000 type) manufactured by Rigaku Corporation. Further, in the above, as means for changing the thickness of the deposited film of silicon oxide, increasing the volume velocity of the deposited film, that is, a method of increasing the amount of the monomer gas and the oxygen gas or the rate of the deposition. It can be performed by a method of slowing down.

Next, in the above description, as a monomer gas for vapor deposition of an organic silicon compound or the like for forming a vapor deposition film of an inorganic oxide such as silicon oxide, for example, 1.1.3.3-tetramethyldisiloxane, Hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxy Silane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, and the like can be used. In the present invention, among the organic silicon compounds as described above, the use of 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is advantageous in terms of handleability and formed continuous film. It is a particularly preferable raw material in view of its properties and the like. In the above, for example, an argon gas, a helium gas, or the like can be used as the inert gas.

Next, in the present invention, the resin film constituting the resin film provided with the above-mentioned inorganic oxide vapor-deposited film has excellent chemical or physical strength,
A base material can be used, which can withstand the conditions for forming a deposited film of an inorganic oxide or the like and can favorably maintain the properties of the deposited film of an inorganic oxide without impairing the properties. In the present invention, as the resin film, specifically, for example, a polyolefin resin such as a polyethylene resin or a polypropylene resin, a cyclic polyolefin resin, a polystyrene resin, an acrylonitrile-styrene copolymer (AS resin) ), Acrylonitrile-butadiene-styrene copolymer (ABS resin), poly (meth) acrylic resin, polycarbonate resin, polyester resin such as polyethylene terephthalate, polyethylene naphthalate, etc. Films or sheets of various resins such as polyamide resin such as nylon, polyurethane resin, acetal resin, cellulose resin and others can be used. In the present invention, among the resin films or sheets described above, it is particularly preferable to use a polyester resin, a polyolefin resin, or a polyamide resin film or sheet.

In the present invention, as the film or sheet of the above-mentioned various resins, for example, one or more of the above-mentioned various resins are used, and are extruded, cast-formed, T-die-processed, and cut. A method of forming the above various resins alone using a film forming method such as an inflation method, an inflation method, or the like, or a multi-layer coextrusion film forming using two or more kinds of various resins. A film or sheet of various resins is manufactured by a method of forming two or more resins, and a method of mixing and forming a film before forming a film. For example, various resin films or sheets stretched in a uniaxial or biaxial direction using a tenter method or a tuber method can be used. In the present invention, the film thickness of various resin films or sheets is 6 to 200 μm.
And more preferably about 9 to 100 μm.

When one or more of the various resins described above are used and the film is formed, for example, the processability, heat resistance, weather resistance, mechanical properties, dimensional stability,
For the purpose of improving or modifying the antioxidant properties, slip properties, mold release properties, flame retardancy, anti-mold properties, electrical properties, strength, etc., various plastic additives and additives can be added. Can,
The addition amount can be arbitrarily added from a very small amount to several tens% depending on the purpose. In the above, as a general additive, for example, a lubricant, a crosslinking agent,
An antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, and the like can be used, and further, a modifying resin and the like can be used.

In the present invention, the surface of the film or sheet of various resins may have a desired surface in advance, if necessary, in order to improve, for example, the tight adhesion with the inorganic oxide vapor-deposited film. A 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 a chemical, etc., Pretreatment such as others can be arbitrarily performed, and for example, a corona treatment layer, an ozone treatment layer, a plasma treatment layer, an oxidation treatment layer, and the like can be formed and provided. The above-mentioned surface pretreatment is carried out as a method for improving the tight adhesion between the film or sheet of various resins and the deposited film of the inorganic oxide. In addition, for example, a primer coat agent layer, an undercoat agent layer, an anchor coat agent layer, an adhesive layer may be previously formed on the surface of various resin films or sheets. Alternatively, a surface-treated layer may be formed by arbitrarily forming a vapor-deposited anchor coating agent layer or the like. Examples of the coating agent layer in the above pretreatment include polyester resin, polyamide resin, polyurethane resin, epoxy resin, phenol resin, (meth) acrylic resin, polyvinyl acetate resin, A resin composition containing, as a main component of the vehicle, a polyolefin resin such as polyethylene aliha polypropylene or a copolymer or modified resin thereof, a cellulose resin, or the like can be used.

Furthermore, in the present invention, as a material constituting the intermediate layer, for example, a mechanical, physical, chemical,
A resin film or sheet having excellent properties in others and the like, and particularly having strength and toughness and having heat resistance can be used. Specifically, for example, polyester resin, polyamide resin, polyaramid resin, polyolefin resin, polycarbonate resin, polyacetal resin, fluorine resin, and other tough resin films or Sheets, etc. can be used. As the resin film or sheet, any of an unstretched film and a stretched film stretched in a uniaxial or biaxial direction can be used. The thickness of the film is about 5 μm to 100 μm, preferably about 10 μm.
The order of μm to 50 μm is desirable.

In the present invention, examples of the material constituting the intermediate layer include a material having a barrier property against oxygen gas and water vapor, a material having a light-shielding property against sunlight and the like, and a property having a scent-retaining property against contents. And the like can be used. Specifically, as the material, for example, for example, polyvinylidene chloride-based resin, polyester-based resin, MXD polyamide-based resin, ethylene-vinyl acetate copolymer (vinyl acetate is about 79 to 92 wt%)
A film or sheet of a resin having a high gas barrier property such as an ethylene-vinyl alcohol copolymer having an ethylene content of 25 to 50 mol%, a polyvinyl alcohol, a polyacrylonitrile resin, etc. , A coating film can be used.

Next, in the present invention, as a material constituting the intermediate layer, specifically, for example, as a water-resistant material having a barrier property such as water vapor and water, for example,
Low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene copolymer and other resin films or sheets can be used, and as a light-shielding material For example, the use of various colored resin films or sheets having a light-shielding property obtained by adding a colorant such as a pigment to a resin and further adding other desired additives and kneading to form a film. Can be. These materials can be used alone or in combination of two or more.
The thickness of the above-mentioned film or sheet is optional, but is usually about 5 μm to 300 μm, and more preferably about 10 μm to 300 μm.
μm to about 100 μm is desirable.

The above-mentioned other materials, specifically, have a low level of adsorption of perfume components and the like contained in the contents to be filled and packaged, and are rich in fragrance retention and the like, and furthermore, they give rise to unpleasant taste and unpleasant odor. It is possible to use a resin having no properties and capable of being extruded. Specifically, for example, polyacrylic resin, polymethacrylic resin, polyacrylonitrile resin, polymethacrylonitrile resin, polystyrene resin, polycarbonate resin, polyethylene terephthalate resin or the like Polyester resins such as a resin obtained by copolymerizing or modifying a part of an ethylene component and / or a terephthalate component with another di- or more polyhydric alcohol component or dicarboxylic acid component, or a polyethylene naphthalate resin. Resins such as resins, polyamide resins, saponified ethylene-vinyl acetate copolymers, polyvinyl alcohol resins, polyvinyl chloride resins, polyvinylidene chloride resins, and the like can be used. Thus, in the present invention, among the above resins, it is desirable to use a resin having a scent-retaining property and a barrier property against oxygen gas or water vapor, and specifically, for example, ethylene-vinyl acetate It is desirable to use a saponified copolymer, a polyamide-based resin, a polyacrylonitrile-based resin, or a resin rich in fragrance retention and barrier properties, such as a polyester-based resin.

By the way, usually, packaging containers are subjected to severe physical and chemical conditions. Therefore, strict packaging suitability is required for a laminated material constituting the packaging container.
Various conditions such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealing property, quality maintenance, workability, hygiene, etc. are required. For this reason, in the present invention, In addition to such materials, other materials that satisfy the above conditions can be used arbitrarily. 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, methylpentene 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 Coalesce (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol
Resin, saponified ethylene-vinyl acetate copolymer,
Fluorine resin, diene resin, polyacetal resin,
A known resin film or sheet such as a polyurethane resin, nitrocellulose, or the like can be arbitrarily selected and used. In addition, for example, synthetic paper can be used. In the present invention, the above-mentioned film or sheet may be any of unstretched and uniaxially or biaxially stretched. The thickness is arbitrary, but is from several μm to 300 μm.
It can be used by selecting from a range of positions. Further, in the present invention, the film or sheet may be any film such as an extruded film, an inflation film, or a coating film.

Next, in the present invention, as a method of laminating at least the front surface resin layer, the intermediate layer, and the rear surface resin layer, for example, lamination is performed via a primer agent layer and a laminating adhesive layer. Lamination can be performed by a dry lamination method or a melt extrusion lamination method in which lamination is performed via a primer agent layer and a melt extruded resin layer.

In the above, as the primer agent layer,
First, a polyurethane-based resin is used as a main component of the vehicle, and a silane coupling agent is used in an amount of about 0.05 to 10% by weight, preferably 0.1 to 30% by weight, based on 1 to 30% by weight of the polyurethane-based resin.
About 1% to 5% by weight, filler about 0.1 to 20% by weight,
Preferably, it is added at a ratio of about 1 to 10% by weight,
If necessary, add additives such as stabilizers, curing agents, cross-linking agents, lubricants, ultraviolet absorbers, etc., add solvents, diluents, etc. and mix well to adjust the polyurethane resin composition Thus, the polyurethane-based resin composition is used, for example, roll coat, gravure coat,
The above-mentioned inorganic oxide vapor-deposited film is coated by knife coating, dip coating, spray coating, or another coating method, and then the coating film is dried to form a solvent, The diluent and the like can be removed, and if necessary, an aging treatment or the like can be performed to form the primer agent layer according to the present invention. In the present invention, the thickness of the primer agent layer is, for example, 0.1 g / m ^2.
It is preferably about 1.0 g / m ² (dry state). Thus,
In the present invention, the above-mentioned primer agent layer improves the close adhesiveness and the like and the elongation degree of the primer agent layer by, for example, laminating or bag forming. It is intended to improve workability and prevent the occurrence of cracks and the like in the deposited film of the inorganic oxide during post-processing.

In the above description, as the polyurethane resin constituting the polyurethane resin composition, for example, a polyurethane resin obtained by reacting a polyfunctional isocyanate with a hydroxyl group-containing compound can be used. Specifically, for example, tolylene diisocyanate
Aromatic polyisocyanate such as diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, or hexamethylene diisocyanate
And polyfunctional isocyanates such as aliphatic polyisocyanates such as xylylene diisocyanate and hydroxyl group-containing compounds such as polyether polyols, polyester polyols, polyacrylate polyols and the like. One- or two-component curing type polyurethane resins obtained by the reaction can be used. Thus, in the present invention, the use of the above-mentioned polyurethane-based resin improves the close-adhesion property and the like, and at the same time, improves the primer property.
It improves the elongation of the agent layer, for example, laminating, or improving post-processing suitability such as bag making, and prevents the occurrence of cracks and the like in the inorganic oxide deposited film during post-processing. is there.

Next, in the above, as the silane coupling agent constituting the polyurethane resin composition,
Binary reactive organofunctional silane monomers can be used, for example, γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy)
Silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, N -Β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-
β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, aqueous solution of γ-aminopropylsilicone, etc. Seeds or more can be used.

In the silane coupling agent as described above, a functional group at one end of the molecule, usually, a chloro, alkoxy, or acetoxy group, is hydrolyzed to form a silanol group (SiOH). , A metal constituting the deposited film of the inorganic oxide, or an active group on the surface of the deposited film of the inorganic oxide, for example, by any action with a functional group such as a hydroxyl group, for example, causing a reaction such as a dehydration condensation reaction. The silane coupling agent is modified by a covalent bond or the like on the surface of the deposited inorganic oxide film, and a strong bond is formed on the surface of the deposited inorganic oxide film of the silanol group itself by adsorption or hydrogen bonding. . On the other hand, the other end of the silane coupling agent vinyl, methacryloxy, amino, epoxy, or
An organic functional group such as mercapto is formed on a thin film of the silane coupling agent, for example, reacts with a material constituting an adhesive layer for lamination, a melt-extruded resin layer, other layers, etc., and becomes strong. A strong bond is formed through the adhesive layer for laminating, the melt-extruded resin layer, etc., and the laminating strength is increased. Is to form a strong laminated structure having high laminate strength. In the present invention, utilizing the inorganic and organic properties of the silane coupling agent,
Improving the tight adhesion between the front or back surface polyolefin resin layer through the inorganic oxide deposited film, the laminating adhesive layer, the melt-extruded resin layer, etc., thereby increasing the laminating strength, etc. Is to increase.

Next, in the present invention, examples of the filler constituting the above-mentioned polyurethane resin composition include calcium carbonate, barium sulfate, alumina white, silica, talc, glass frit, resin powder, and the like. Can be used. Thus, the above filler is
The viscosity and the like of the polyurethane resin composition liquid are adjusted to improve the coating aptitude, and the polyurethane resin as a binder resin is bonded via a silane coupling agent to improve the cohesive force of the coating film. It is to let.

Next, in the present invention, examples of the laminating adhesive constituting the laminating adhesive layer include a polyvinyl acetate-based adhesive, ethyl acrylate, and the like.
Homopolymers such as butyl and 2-ethylhexyl esters, or polyacrylate adhesives, cyanoacrylate adhesives composed of copolymers of these with methyl methacrylate, acrylonitrile, styrene, etc., ethylene and vinyl acetate Ethylene copolymer adhesive, cellulose adhesive, polyester adhesive, polyamide adhesive, polyimide adhesive consisting of copolymers with monomers such as ethyl acrylate, acrylic acid, methacrylic acid, etc. , Urea resin or melamine resin, amino resin adhesive, phenol resin adhesive, epoxy adhesive, polyurethane adhesive, reactive (meth) acrylic adhesive, chloroprene rubber, nitrile rubber, styrene -Rubber adhesives composed of butadiene rubber, etc., silicone-
It is possible to use an inorganic adhesive such as an inorganic adhesive, an alkali metal silicate, a low-melting glass, or the like, and other adhesives. 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 properties thereof include a film sheet, a powder, and a solid. Any form may be used, and the bonding mechanism may be any form such as a chemical reaction type, a solvent volatilization type, a heat melting type, and a heat pressure type. Thus, in the present invention, the laminating adhesive is applied to one surface of both layers to be laminated, for example, by a roll coat method, a gravure roll coat method, a kiss coat method, or the like. Coating method such as
Alternatively, the adhesive may be applied by a printing method or the like, and then a solvent or the like may be dried to form an adhesive layer for laminating.
/ M ² (dry state).

In the present invention, examples of the melt-extruded resin constituting the above-mentioned melt-extruded resin layer include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, and metallocene. Ethylene-α-olefin copolymer, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene- Methacrylic acid copolymer, ethylene-propylene copolymer,
Use an acid-modified polyolefin-based resin obtained by modifying a polyolefin-based resin such as methylpentene polymer, polyethylene, or polypropylene with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, and the like. be able to. Further, in the present invention, when the melt extrusion lamination, isocyanate system,
Anchor coating agents such as polyethyleneimine and others can be arbitrarily used. Furthermore, in the present invention, when performing the above-mentioned lamination, if necessary, for example, a pretreatment such as a corona treatment, an ozone treatment, or a framing treatment is optionally performed on the surface of the base material to be laminated. be able to.

In the present invention, the laminating method for producing the laminating tube container according to the present invention as described above includes a laminating method used when producing ordinary packaging materials. For example, a wet lamination method, a dry lamination method, a solventless dry lamination method
A method such as an extrusion method, an extrusion lamination method, a T-die coextrusion molding method, a coextrusion lamination method, an inflation method, and the like can be arbitrarily performed. Thus, in the present invention, when performing the above lamination, as described above, if necessary, for example, corona treatment,
Pretreatment such as ozone treatment can be applied to the film. For example, anchor coating agents such as isocyanate (urethane), polyethyleneimine, polybutadiene, and organic titanium, or polyurethane-based ,
Any known anchor coating agent such as polyacrylic, polyester, epoxy, polyvinyl acetate, cellulose, and other laminating adhesives, laminating adhesives, etc. Can be used.

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

Next, in the present invention, a laminated material for forming the laminating tube container manufactured as described above is used. First, a gravure printing method, a flexographic printing method, or the like is used on the surface of the laminated material. Using gravure ink, flexo ink, etc., print and form a print pattern layer consisting of characters, figures, symbols, patterns, etc. Then, a cylindrical body constituting an extruded tube is manufactured, and then, for example, high-density polyethylene or the like is formed above the cylindrical body by injection molding, compression molding, or other molding methods. A head comprising a shoulder and a mouth is formed by welding, and then a cap is attached to the mouth constituting the head, whereby the laminating tube container according to the present invention can be manufactured. Therefore, in the present invention, the contents to be filled and packed are filled from the opening at the lower end of the laminating tube container manufactured as described above, and then the opening is heat-sealed to form a bottom welding portion. To form a packaged product comprising a laminating tube container. In the above, the contents to be filled and packaged include, for example, toothpaste, cosmetics, paste, paste, paste wasabi, cream, paint, ointment, medicine, and the like. In the above, in addition to the high-density polyethylene as described above, ethylene further polymerized using the above-described metallocene catalyst is used as a material constituting the head portion of the laminating tube container including the shoulder and the mouth. An α-olefin copolymer or the like can also be used. In the above, instead of performing gravure printing, flexo printing, or the like on the surface of the plain laminated material, it is also possible to perform printing on the surface of the plain tubular portion by offset printing or the like.

In the above description, flexographic printing is a type of letterpress printing, in which a flexible resin or rubber letterpress is used, and a solvent-dried type flexographic ink is used to form letters, figures, symbols, pictures, and other patterns. The desired printed pattern layer is formed by printing. In addition, as the above-mentioned flexo ink, an evaporative drying ink mainly containing an alcohol or water-based vehicle, which does not relatively invade a rubber letterpress or the like, or an ultraviolet curable ink can be used. is there. Thus, in the present invention, by using a flexographic printing method or the like, a laminated material is manufactured in a plain state, and is directly printed on the surface of the plain laminated material or the plain cylindrical portion to obtain a desired material. Since the print pattern layer can be formed, batch production of the raw material is possible, and the production efficiency can be increased, the production loss can be reduced, and the required quantity can be printed according to the order. In addition, manufacturing loss can be reduced and a short delivery time can be achieved. That is, usually, a desired printed picture layer is formed by printing on a raw film such as a plastic film, and thereafter, another plastic film or the like is laminated thereon,
Since we manufacture laminated materials with printed pictures, the lead time from receiving orders becomes longer, and the raw material lot is identified for each picture, which significantly disadvantages the production process and production costs. The present invention has an advantage that such a problem can be solved.

[0048]

EXAMPLES Next, the present invention will be described more specifically with reference to examples. Example 1 (1). As a base film, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used.
The above biaxially stretched polyethylene terephthalate film was mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus, and then unwound. Under the conditions, a deposited film of silicon oxide having a thickness of 200 ° was formed. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 11: 10 (unit: slm) Degree of vacuum in vacuum chamber: 5.2 × 10 ⁻⁶ mbar In evaporation chamber Degree of vacuum: 5.1 × 10 ^-2 mbar Cooling / electrode drum supply power: 60 w / min / m ² Film transport speed: 90 m / min Vapor deposition surface: corona treated surface Immediately after forming the deposited film, the surface of the deposited silicon oxide film was subjected to power of 9 kW, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2 by using a glow discharge plasma generator. 5 (unit: slm) using a mixed gas pressure of 6
× 10 ^-2 mbar, oxygen /
An argon mixed gas plasma treatment was performed to form a plasma treatment surface in which the surface tension of the surface of the deposited silicon oxide film was improved by 54 dyne / cm or more, thereby producing a barrier film. (2). Next, an epoxy-based silane coupling agent (8.0% by weight) and an anti-blocking agent ( 1.0% by weight) and sufficiently kneaded, and a gravure roll coat method is used to obtain a primer composition having a thickness of 0.4 g / m ² (dry state). Then, a primer agent layer was formed. Further, a two-component curable polyurethane-based laminating adhesive is used on the entire surface including the primer agent layer formed as described above, and the adhesive is applied by a gravure roll coating method in the same manner as described above. 4.0 g / m
² Laminate by coating so that it is dry
An adhesive layer was formed. Then, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is laminated on the laminating adhesive layer surface formed above with the corona-treated surface facing the film, and then both are laminated with dry laminating. did. Further, on the surface of the biaxially stretched polyethylene terephthalate film laminated as described above, a two-component curable urethane-based anchor coating agent was used. / M ² (dry state) to form an anchor-coating agent layer, and then apply low-density polyethylene to the surface of the anchor-coating agent layer. While being melt-extruded to a thickness of 35 μm, a low-density polyethylene film having a thickness of 80 μm was extruded and laminated by lamination. (3). On the other hand, a resin composition mainly composed of a linear low density polyethylene resin polymerized by a single-site catalyst, and a low pressure high density polyethylene resin (density = 0.95)
1, a melt index, MI = 1.0) as a main component, a white resin composition containing a white pigment (containing 8% by weight), and a multilayer inflation method to form a multilayer film. A multilayered opalescent polyethylene having a thickness of 140 μm including a transparent linear low-density polyethylene resin layer having a thickness of 30 μm, a milky low-density polyethylene resin layer having a thickness of 80 μm, and a transparent linear low-density polyethylene resin layer having a thickness of 30 μm. A film was produced, and one surface of the film was subjected to a corona discharge treatment to form a corona discharge treated surface. Next, a low-density polyethylene film having a thickness of 60 μm was extrusion-laminated on a corona-discharge treated surface of the multilayer milky polyethylene film produced above using a low-density polyethylene resin while melt-extruding it to 35 μm. . (4). Then, a two-component curable polyurethane-based laminating adhesive was used on the surface of the low-density polyethylene film laminated with the extruded laminate as described above, and this was applied by a gravure roll coating method. 0 g / m ² (dry state)
Then, an adhesive layer for laminating was formed. Next, the surface of the biaxially stretched polyethylene terephthalate film constituting the barrier film laminated in the above (2) is superimposed on the surface of the adhesive layer for laminating formed above, and then And dry laminating the two to form a laminating tube according to the present invention.
The packaging material constituting the container was manufactured. Further, on the surface of a transparent linear low-density polyethylene resin layer having a film thickness of 30 μm located on the outermost surface of the packaging material constituting the laminating tube container manufactured above, after corona discharge treatment, the corona treated surface is Using the ultraviolet-curable flexographic ink composition, a desired printed picture layer was formed by a flexographic printing method to produce a laminated material constituting the laminating tube container according to the present invention. (5). Next, using the laminated material constituting the laminated tube container manufactured above, first, the laminated material constituting the laminated tube container is punched to produce a blank plate, The blank plate was rolled up, and the back end of the overlapped end was set at 215 ° C. for 3 seconds at 3 Kg / cm.
Heat sealing was carried out under the heat welding conditions of ² to produce a cylindrical body serving as a body of a laminating tube container having a diameter of 35 mm and a height of 160 mm. Next, the above-prepared cylindrical body is mounted on a mandrel for molding a laminating tube container. Next, at one end of the cylindrical body, a frustoconical shoulder portion and a continuous narrow neck are connected in a conventional manner. The head consisting of the mouth and neck was molded by compression molding at a resin temperature of 245 ° C. using a high-density polyethylene composition obtained by adding 2.0% by weight of an opalescent pigment to 98.0 parts by weight of high-density polyethylene. Thus, a laminating tube container according to the present invention was manufactured. Next, a cap made of polypropylene resin is spirally wound around the mouth and neck of the cylindrical body having the above-mentioned head, and then, from the other opening of the cylindrical body, 150 g of kneaded wasabi is filled. The opening was heat-sealed to produce a packaged product comprising a tube container. The packaged product comprising the tube container manufactured as described 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 storage. Was something. . There was no particular problem even if the used tube container or the like was incinerated and disposed of.

Embodiment 2 (1). A biaxially stretched nylon 6 film having a thickness of 15 μm was used, and was mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus. Then, a deposited film of silicon oxide having a thickness of 200 ° was formed. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1.2: 5.0: 2.5 (unit: sl)
m) Ultimate pressure; 5.0 × 10 ⁻⁵ mbar Film forming pressure; 7.0 × 10 ⁻² mbar Line speed; 300 m / min Power; 35 kW Next, a silicon oxide vapor deposition film having a thickness of 200 ° Immediately after the formation, on the surface of the deposited silicon oxide film, using a glow discharge plasma generator, power: 9 kW, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 (unit) : Slm) and a mixed gas pressure of 6
× 10 ^-2 mbar, oxygen /
An argon mixed gas plasma treatment was performed to form a plasma treatment surface in which the surface tension of the surface of the deposited silicon oxide film was improved by 54 dyne / cm or more, thereby producing a barrier film. (2). Next, a primer agent layer having a thickness of 0.4 g / m ² (dry state) was formed on the plasma-treated surface of the deposited silicon oxide film of the barrier film produced above in the same manner as in Example 1 above. Then, an adhesive layer for lamination having a thickness of 4.0 g / m ² (dry state) was formed on the entire surface including the primer agent layer. Next, the laminate formed above
A 12 μm-thick biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was overlaid on the adhesive layer surface with its corona-treated surface facing each other, and then both were laminated by dry lamination. Further, on the surface of the biaxially stretched polyethylene terephthalate film laminated as described above, a two-component curable urethane-based anchor coating agent was used.
An anchor coating agent layer is formed by coating with a coating method so as to have a film thickness of 0.4 g / m ² (dry state), and then the surface of the anchor coating agent layer is formed. Then, a low-density polyethylene film having a thickness of 80 μm was extruded and laminated using a low-density polyethylene while melt-extruding the film to a thickness of 35 μm. (3). On the other hand, a resin composition mainly composed of a linear low density polyethylene resin polymerized by a single-site catalyst, and a low pressure high density polyethylene resin (density = 0.95)
1, a melt index, MI = 1.0) as a main component, a white resin composition containing a white pigment (containing 8% by weight), and a multilayer inflation method to form a multilayer film. A multilayered opalescent polyethylene having a thickness of 140 μm including a transparent linear low-density polyethylene resin layer having a thickness of 30 μm, a milky low-density polyethylene resin layer having a thickness of 80 μm, and a transparent linear low-density polyethylene resin layer having a thickness of 30 μm. A film was produced, and one surface of the film was subjected to a corona discharge treatment to form a corona discharge treated surface. Next, a low-density polyethylene film having a thickness of 60 μm was extrusion-laminated on a corona-discharge treated surface of the multilayer milky polyethylene film produced above using a low-density polyethylene resin while melt-extruding it to 35 μm. . (4). Then, a two-component curable polyurethane-based laminating adhesive was used on the surface of the low-density polyethylene film laminated with the extruded laminate as described above, and this was applied by a gravure roll coating method. 0 g / m ² (dry state)
Then, an adhesive layer for laminating was formed. Next, the surface of the biaxially stretched polyethylene terephthalate film constituting the barrier film laminated in the above (2) is superimposed on the surface of the adhesive layer for laminating formed above, and then And dry laminating the two to form a laminating tube according to the present invention.
The packaging material constituting the container was manufactured. Further, on the surface of a transparent linear low-density polyethylene resin layer having a film thickness of 30 μm located on the outermost surface of the packaging material constituting the laminating tube container manufactured above, after corona discharge treatment, the corona treated surface is Using the ultraviolet-curable flexographic ink composition, a desired printed picture layer was formed by a flexographic printing method to produce a laminated material constituting the laminating tube container according to the present invention. (5). Next, using the laminated material constituting the laminating tube container produced above, first, the laminating tube was used.
A blank is manufactured by punching out a laminated material constituting a metal container, and then the blank is rolled, and the back end of the overlapped end is thermally welded at 215 ° C. for 3 seconds at 3 kg / cm ² . Heat seal under conditions, diameter 35mm, height 1
A cylindrical body serving as a body of a 60 mm laminating tube container was manufactured. Next, the above-prepared cylindrical body is mounted on a mandrel for forming a tube container, and then, at one end of the cylindrical body, a frustoconical shoulder portion and a continuous narrow neck opening are formed in a conventional manner. The head consisting of the neck is made of high-density polyethylene 9
A high-density polyethylene composition in which 2.0% by weight of an opalescent pigment is added to 8.0 parts by weight is molded at a resin temperature of 245 ° C. by a compression molding method.
The container was manufactured. Next, a cap made of polypropylene resin is spiraled around the mouth and neck of the cylindrical body having the above head,
Then, from the other opening of the cylindrical body, the toothpaste 150
g, and then the opening of the cylindrical body was heat-sealed to produce a packaged product consisting of a tube container. The packaged product comprising the tube container produced above has excellent barrier properties against oxygen gas, water vapor, etc.
It was excellent in strength and the like, withstanding distribution in the market, and excellent in storage and preservation. . There was no particular problem even if the used tube container or the like was incinerated and disposed of.

Example 3 In Example 1, instead of laminating an 80 μm-thick low-density polyethylene film on the surface of the biaxially stretched polyethylene terephthalate film by extrusion lamination, first, a single-site catalyst was used. Using a resin composition containing a polymerized linear low-density polyethylene resin as a main component and a resin composition containing a high-pressure method low-density polyethylene resin as a main component, forming a multilayer film by a multilayer inflation method, and forming a film. A multi-layered polyethylene film having a thickness of 100 μm comprising two layers, a linear low-density polyethylene resin layer having a thickness of 70 μm and a high-pressure low-density polyethylene resin layer having a thickness of 30 μm, was manufactured.
m, and used in place of the low-density polyethylene film, and otherwise used in exactly the same manner as in Example 1 above, to form a laminate material and a laminate tube constituting the same laminate tube as in Example 1 above. -Produced container and packaging products.

EXPERIMENTAL EXAMPLE The lamine according to the present invention produced in Examples 1 to 3 described above.
For the laminated material constituting the tube container, the oxygen permeability, the water vapor permeability, the suitability for hand massage, and the aging test were measured. (1). Measurement of Oxygen Permeability This is a condition under the condition of a temperature of 23 ° C. and a humidity of 90% RH in the United States,
The measurement was carried out using a measuring instrument (model name, OXTRAN) manufactured by MOCON. (2). Measurement of water vapor transmission rate This is the condition under the condition of temperature 40 ° C and humidity 90% RH,
The measurement was carried out using a measuring instrument (model name, PERMATRAN) manufactured by MOCON. (3). Measurement of hand massage suitability This was evaluated by measuring the oxygen permeability and the water vapor permeability in the same manner as described above for the laminated material after 1000 and 5000 times of hand massage. (4). Measurement of aging test This is as follows. A tube container (45φ) is filled with contents of vinegar: oil = 1: 1, left at 40 ° C. 90% RH for 3 months, and the contents are taken out. The oxygen permeability and the water vapor permeability were measured and evaluated in the same manner as described above. The above measurement results are shown in Table 1 below.

[0052] In Table 1 above, 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. 100% RH].

As is clear from the measurement results shown in Table 1 above, the packaging material for a tube container according to the present invention has excellent oxygen barrier properties and water vapor barrier properties, as well as suitability for hand massage and aging. It is also excellent in testing etc.
As a laminating tube container for filling and packaging various contents, it was able to withstand sufficient use.

[0054]

As apparent from the above description, the present invention
At least the surface resin layer, the intermediate layer, and the inner resin layer
Is a laminated material having a configuration in which
The outermost and innermost layers of the surface resin layer, which are the outermost layers at both ends of the laminated material
The surface of the inner resin layer, which is
The joint is heat-sealed to form a cylindrical body, and
A head consisting of a shoulder and a mouth is set in one opening of the
The above-mentioned surface resin
As a layer, for example, the density is 0.935 g / cm ^Three~
0.960 g / cm^ThreePolyethylene resin consisting of
Multilayer including milky polyethylene resin layer composed using
Uses a resin layer, and as an intermediate layer, chemical vapor deposition
Using a barrier layer containing a deposited inorganic oxide film
In addition, as the inner resin layer, for example, a polyethylene resin layer
To produce a laminated material in which these are sequentially laminated.
And then, on the surface of the laminate, for example, a flexo mark
Desired print pattern by flexographic printing using printing method etc.
After forming a layer, a cylindrical body is manufactured from the laminated material.
And, further, using the cylindrical body, in one opening thereof,
Forming the head consisting of the mouth, shoulder, etc.
A tube container, and then the other opening of the tube container
From the part, for example, filling and packaging contents such as toothpaste
Manufacture packaging products to prevent waste of materials used
One has a beautiful printed pattern layer on its surface,
During the manufacture of the laminating tube container, the contents are
When manufacturing packaging products for filling or packaging
Has sufficient strength, waist, etc. to withstand storage and sales
It also has sufficient resistance to low load stress cracks.
The contents have no leakage, etc.
Etc., and further impedes the transmission of oxygen gas, water vapor, etc.
Excellent barrier properties to stop, fragrance retention of filled and packed contents,
Excellent preservability, etc., and when disposed of after use
Without the generation of harmful substances,
Extremely environmentally friendly, for example, toothpaste, food,
Useful for filling and packaging of contents such as cosmetics, pharmaceuticals, etc.
Laminate tube container can be manufactured
Is Umono.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of a laminated material constituting a laminating tube container according to the present invention.

FIG. 2 is a schematic cross-sectional view showing an example of a layer structure of a laminated material constituting a laminating tube container according to the present invention.

FIG. 3 is a schematic cross-sectional view showing an example of the layer structure of the laminated material constituting the laminate tube container according to the present invention.

FIG. 4 is a schematic cross-sectional view showing an example of the layer structure of a laminated material constituting the laminating tube container according to the present invention.

FIG. 5 is a schematic half sectional view showing the configuration of the laminate tube container according to the present invention manufactured using the laminated material constituting the laminate tube container according to the present invention shown in FIG. 1; .

FIG. 6 is a schematic configuration diagram illustrating an example of a low-temperature plasma chemical vapor deposition apparatus.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Surface resin layer 2 Intermediate layer 3 Inner resin layer 4 Milky-white polyethylene resin layer fat layer 4a Milky-white polyethylene resin layer fat layer 5 Multilayer resin layer 5a Multilayer resin layer 6 Barrier layer 7 Polyethylene resin layer 7a Low-density polyethylene resin layer 7b linear low-density polyethylene resin layer 8 transparent polyethylene resin layer 11 welded portion 12 the cylindrical body 13 the shoulder portion 14 necked portion 15 head 16 cap 17 contents 18 bottom welded part A laminate A ₁ to A ₃ laminate R Laminate tube container Ra Packaging product

Continued on the front page F-term (reference) 3E065 AA01 BA15 BA16 BA17 BA18 BA30 BA40 BB03 CA09 DA04 DB01 DC01 DD05 EA04 FA05 FA15 GA01 GA02 GA10 HA01 4F100 AA01B AA17B AA20B AK01A AK04A AK04C AK04B13 AK13 BAK AK04 AK06 CB02 EH66B EJ38B GB17 JA11D JD01B JD02B JL10D JN01A JN01E YY00D 4K030 AA06 AA14 AA16 BA24 BA27 BA29 BA44 CA07 CA12 DA02 FA01 GA14 HA02 LA01 LA24

Claims (6)

[Claims] 1. A laminated material having a structure in which at least a surface resin layer, an intermediate layer, and an inner resin layer are sequentially laminated, and further, a surface of a surface resin layer which is an outermost layer at both ends of the laminated material. And the surface of the innermost resin layer which is the innermost layer,
A heat-sealing portion of the opposed overlapped portion forms a tubular body, and a laminating tube provided with a head including a shoulder and a mouth at one opening of the tubular body. -In the container
The above-mentioned surface resin layer is composed of a multilayer resin layer including a milky polyethylene-based resin layer, and the intermediate layer is composed of a barrier layer including a vapor-deposited film of an inorganic oxide formed by a chemical vapor deposition method. Characterized by comprising a polyethylene resin layer. 2. The laminating tube container according to claim 1, wherein the intermediate layer comprises a barrier layer including a deposited film of silicon oxide formed by plasma enhanced chemical vapor deposition. 3. The intermediate layer is mainly composed of silicon oxide formed by a plasma-enhanced chemical vapor deposition method. 3. A laminate according to claim 1, comprising a barrier layer including a highly flexible vapor-deposited film containing at least one kind by a chemical bond or the like.
Tube container. 4. The surface resin layer according to claim 1, wherein the surface resin layer comprises a laminate in which a transparent polyethylene resin layer, a milky polyethylene resin layer, and a transparent polyethylene resin layer are sequentially laminated. The laminating tube container described in 1. 5. The polyethylene resin constituting the milky polyethylene resin layer has a density of 0.935 g / cm ^{3 to} 0.5 g / cm ³ .
5. The laminating tube container according to claim 1, comprising 960 g / cm ³ . 6. The inner surface resin layer comprises a low-density polyethylene resin layer, a linear low-density polyethylene resin layer, or two layers of a linear low-density polyethylene resin layer and a low-density polyethylene resin layer. The laminating tube container according to claim 1.