JP2000281094A - Tube container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide excellent barring and protecting capacities and to ensure excellence in capability for filling and packaging by a method wherein a tubular trunk part is formed by heat sealing opposite faces of a laminated material composed of a surface resin layer, an intermediary layer and an internal resin layer, and a printed pattern layer is arranged over the surface of the surface resin layer of a laminate tube container having such tubular trunk part. SOLUTION: A laminated material A is formed by laminating at least a surface resin layer 1, an intermediary layer 2 and an internal resin layer 3 successively from the outside. Then, the laminated material A is rolled up, and the surface resin layer 1 being the outermost layer at one end and the internal resin layer 3 being the innermost layer at the other end are overlapped each other, and a tubular trunk part 12 is formed with a welding part arranged at the overlapped ends. After a head part 15 composed of a shoulder part 13 and a mouth part 14 forming a tube container is formed, following a normal method of producing, at the upside of an opening at one end of the tubular trunk part 12, a flexo-printed pattern layer 16 comprising letters, figures, symbols, designs and the like is formed on the surface of the tubular trunk part 12. Furthermore, a cap 17 for tightly closing the mouth part 14 of the head part 15 is attached, and the tube container R is completed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tube container, and more particularly, to a tube container having a beautiful printed pattern on its surface, and further having excellent barrier properties against oxygen gas, water vapor and the like, and excellent content resistance. The present invention relates to a tube container suitable for filling and packaging contents such as toothpaste, foods, cosmetics, pharmaceuticals and others.

[0002]

2. Description of the Related Art Tube containers such as a laminating tube container usually produce a laminated material by laminating at least a surface resin layer, an intermediate layer and an inner resin layer in this order. Using a laminated material, the surfaces of the surface resin layer and the inner surface resin layer at both ends are overlapped, and the opposing surfaces are heat-sealed to produce a cylindrical body, and thereafter, the cylindrical body is manufactured. A head portion consisting of a mouth portion, a shoulder portion, and the like is formed in one opening of the portion, and further, a cap is screwed into the head portion, and on the other hand, the content is filled from the other opening portion of the cylindrical body. Thereafter, the opening is hermetically sealed to form a bottom seal, and a packaged product comprising a tube container such as a laminating tube container is manufactured. By the way, in the tube container as described above, usually, a printed pattern layer for displaying predetermined items such as a product name, a manufacturer, a seller, a date of manufacture, etc. is formed together with a desired pattern. I have. Thus, the above-mentioned printed pattern layer is generally provided in advance on the back surface of a raw film such as a resin film forming a front resin layer constituting a tube container.
It is formed by a gravure printing method or the like, and thereafter, a laminated material is manufactured by laminating this and a material constituting the intermediate layer, the inner surface resin layer, and the like. -Tube containers such as tube containers are manufactured. Further, in a tube container such as the above-mentioned laminating tube container, as a material constituting the intermediate layer,
For example, to prevent the transmission of oxygen gas, water vapor, etc.,
A barrier substrate such as an aluminum foil or a resin film having a vapor-deposited inorganic oxide film is used.

[0003]

However, in the above-mentioned tube container, the back surface of a raw film such as a resin film forming a surface resin layer constituting the tube container is previously coated by a gravure printing method or the like. When forming a printed pattern layer, a printed pattern layer is formed on a raw film such as a resin film, and then laminated with a material constituting an intermediate layer, an inner resin layer, etc. Since a tube container is manufactured by forming a part or the like, when a defective product is manufactured, for example, at the time of lamination, at the time of forming a cylindrical body, or at the time of forming a head, a large amount of a raw film is produced. There is a problem that it is wasted. Further, when a printed picture layer is previously formed on the back surface of an original film such as a resin film forming a surface resin layer constituting the tube container, all the tube containers using the same are not consumed. There is also a problem that it is not possible to transfer to a tube container made of the next new form, new product and the like as long as it is possible. Further, in the above-mentioned tube container, when a resin film having a vapor-deposited inorganic oxide film is used as a material constituting the intermediate layer, the vapor-deposited inorganic oxide film is glassy. Cracks are easily generated in the deposited film of the inorganic oxide, for example, heating and pressurizing when manufacturing a laminated material, or a laminated material when manufacturing a cylindrical body constituting a laminating tube container. After heating and pressurizing when the surfaces of the surface resin layer and the inner resin layer at both ends are overlapped and heat-sealing the opposing surface, or after filling the contents from the other opening of the cylindrical body When the opening is hermetically sealed, cracks due to heat shrinkage are generated in the inorganic oxide vapor deposition film of the resin film having the inorganic oxide vapor deposition film due to heat and pressure, and the barrier property is significantly reduced. There is a problem. Furthermore, in a resin film having an inorganic oxide deposited film, usually, as the inorganic oxide deposited film, a silicon oxide deposited film is used, but this film itself is not colorless and transparent, Because it is slightly yellow, it is inferior in design when printed,
There is a problem that the merchantability is also lacking. For this reason,
As an alternative film, a vapor-deposited film of aluminum oxide is conceivable, but this is more excellent in transparency than a vapor-deposited film of silicon oxide, but has a gas barrier property, particularly, poor water vapor permeability, and in toothpaste. There is a problem that weight loss is large. Further, in the tube container as described above, when directly displayed at a store such as a standing tube or the like, a so-called low-weight stress crack occurs due to stacking at the time of transporting the packaged product. There is also a problem that the contents gradually leak from the bottom seal portion. Further, those using a barrier base material such as the above aluminum foil have a problem that the content is not visible due to lack of transparency, and further, the aluminum foil is a cause of environmental destruction, There is also a problem that the subsequent tube container lacks proper disposal treatment. Therefore, the present invention prevents waste of materials, and has a beautiful printed pattern on the surface, and furthermore, as a barrier substrate, a resin film or the like having a vapor-deposited film of an inorganic oxide is used. The inorganic oxide deposited film does not generate cracks due to the action of heat, does not generate low-load stress cracks, fully demonstrates its function as a barrier base material, protects contents, and fills An object of the present invention is to provide a tube container excellent in packaging suitability and the like.

[0004]

The inventor of the present invention has conducted intensive studies to solve the above-mentioned problems, and as a result, a flexographic printing method and a function having a barrier property, a fragrance retaining property, etc. in its structure. Attention is paid to a multilayer laminated heat seal material layer including a conductive resin layer. First, at least a surface resin layer, an intermediate layer, and an inner resin layer are sequentially laminated to produce a laminated material. In producing the laminated material, a laminated material is produced by using a multilayer laminated heat-sealing material layer including a functional resin layer having a barrier property, a scent-retaining property, etc., as an inner resin layer. Then, a tubular body is manufactured from the laminated material, and further, the tubular body is used, and a head including a mouth, a shoulder, and the like is formed in one opening thereof to form a tube. A container is manufactured, and thereafter, flexographic printing is performed on the surface of the tube container using a flexographic printing method. A desired printed pattern layer is formed, and then the packaged product is filled and packaged from the other opening of the tube container with contents such as toothpaste. It has a beautiful printed pattern layer on its surface, and furthermore, heat when manufacturing a laminated material or heat when manufacturing a container. It is possible to prevent cracks and the like from occurring in the silicon oxide thin film of the resin film having the silicon oxide thin film due to heat or the like during the heating, and also to prevent the transfer of offensive odor to the contents, and the like. In addition, it has sufficient resistance to low load stress cracks, does not show leakage of contents, etc., and has no phenomenon such as delamination, and has excellent fragrance retention and preservability of contents. , Toothpaste, food, cosmetics, pharmaceuticals, and other contents Useful Ju to filling and packaging - and completed the present invention have found that it is possible to produce a blanking container.

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, an outermost layer at both ends of the laminated material. The surface resin layer surface and the innermost resin layer surface, which is the innermost layer, are overlapped with each other, and the opposing surface is heat-sealed to form a cylindrical body. Further, a shoulder is provided at one opening of the cylindrical body. The present invention relates to a tube container characterized in that a printed picture layer by a flexographic printing method is provided on the surface resin layer surface of a laminating tube container provided with a head comprising a head and a mouth.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. First, the structure of a tube container according to the present invention will be described with reference to the drawings. FIGS. 1, 2 and 3 show a laminated material forming a tube container according to the present invention. FIG. 4 is a schematic sectional view showing an example, and FIG. 4 is a schematic half sectional view showing the structure of a tube container according to the present invention manufactured using the laminated material shown in FIG.

First, as shown in FIG. 1, a laminated material A for forming a tube container according to the present invention is, as shown in FIG.
At least the basic structure is such that the surface resin layer 1, the intermediate layer 2, and the inner resin layer 3 are sequentially laminated. More specifically, as shown in FIG. 2, at least the surface resin layer 1, the intermediate layer 2, and the inner resin layer 3 are sequentially laminated as shown in FIG. In addition, the inner resin layer 3 has at least a functional resin layer 4
And a two-layer laminated heat sink of the first heat-sealing resin layer 5.
Tosylate - can be used laminate A ₁ consisting of sealing material layer 6a. Further, in the present invention, as shown in FIG.
At least a surface resin layer 1, an intermediate layer 2, and an inner resin layer 3 are sequentially laminated, and the inner resin layer 3 is formed of at least a second heat-sealing resin layer 5.
a, functional resin layer 4, and the first heat - may be used a laminated material A ₂ consisting of sealing material layer 6b - tosylate - three-layer heat Le resin layer 5 - Toshi. Thus, the laminated materials exemplified above are only a few examples, and the present invention
The present invention is not limited to the laminate having the above-described configuration, and various forms of laminate can be used.
For example, although not shown, a layer made of another material can be provided between the respective layers depending on the use, the content to be filled, and the like, and the layers can be arbitrarily stacked in a stacking order. is there.

Next, in the present invention, one example of manufacturing a tube container according to the present invention using the laminated material forming the above-described tube container will be described. FIG. FIG. 2 is a schematic half sectional view showing a configuration of a tube container according to the present invention manufactured by using a laminated material A for forming the tube container shown in FIG. 1. In the present invention, as shown in FIG. 4, first, the laminated material A forming the tube container shown in FIG. The innermost resin layer surface, which is the innermost layer, is overlapped, and the overlapped end thereof is welded to form a welded portion 11 to produce a cylindrical body 12, thereby forming the tubular body 12 into a tube. It is to be the body constituting the container. Then, 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, on the surface of the cylindrical body 12, a flexographic printing composition layer 16 of characters, figures, symbols, pictures, etc. is formed by a flexographic printing method using a flexographic ink composition. Thus, in the present invention, as shown in FIG. 4, a sealing cap 17 is attached to the mouth 14 of the head 15 formed as described above to manufacture the tube container R according to the present invention. Things. In the tube container R manufactured as described above, for example, an appropriate amount of the contents 18 such as toothpaste is filled and packaged from the other opening of the cylindrical body 12, and then the opening is welded. Thus, the bottom welded portion 19 is formed, and the tube package Ra filled with the contents 18 can be manufactured. The above examples are merely examples of the tube container of the present invention, and the present invention is not limited thereto.

Next, in the present invention, the materials constituting the laminated material, tube container and the like as described above will be described.
First, in the present invention, as a material constituting the surface resin layer, and the inner surface resin layer, as described above, since the laminated material is rolled and the overlapped end thereof is welded to produce a cylindrical body, It is preferable to use a resin having a heat-sealing property that can be melted by heating and fused to each other. Particularly, as a material constituting the surface resin layer, a flexographic printing method is used. It is desirable to use a heat-sealable resin capable of forming a printed pattern layer by printing. Specifically, examples of the resin having heat sealability include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene, and ethylene-vinyl acetate. Copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methyl Penten polymer, polybutene polymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, acid-modified polyolefin resin obtained by acid-modifying a polyolefin resin such as polyethylene or polypropylene using an unsaturated carboxylic acid, Polyvinyl acetate resin, poly (meth) acrylic resin, It can be used vinyl chloride resin, other like resins. Thus, the resin having the heat sealing property is, for example,
It can be used in the form of a film or sheet or a coating film of a composition containing the resin. The thickness of the film or film or sheet is about 10 μm to 200 μm, preferably 15 μm.
m to 100 μm is desirable.

Further, in the present invention, an ethylene-α-olefin copolymer polymerized using a metallocene catalyst can be used as a material constituting the above-mentioned surface resin layer, inner surface resin layer and the like. . Examples of the ethylene-α-olefin copolymer polymerized using the above metallocene catalyst include, for example, a catalyst formed by a combination of a metallocene complex and an alumoxane such as a catalyst formed by a combination of zirconocene dichloride and methylalumoxane, that is, a metallocene catalyst. Ethylene-α-olefin copolymers obtained by polymerization can be used. The metallocene catalyst has a non-uniform active site and is called a multi-site catalyst, whereas the existing catalyst is called a single-site catalyst because the active site is uniform. Specifically, Mitsubishi Chemical Corporation's product name "Kernel",
Product name "Evolu" manufactured by Mitsui Petrochemical Industry Co., Ltd.
Exxon Chemical (USA)
Metallocene catalysts such as "EXACT" (trade name, manufactured by AL), "Affinity" (trade name), and "ENGAGE" (trade name), manufactured by DOW CHEMICAL, USA An ethylene-α-olefin copolymer polymerized by using the same can be used.

Further, in the present invention, it is desirable to use a multilayer laminated heat seal material layer as a material constituting the inner resin layer. Specifically, as described above, at least the functional resin is used. Layer and a two-layered heat-sealing material layer of the first heat-sealing resin layer (see FIG. 2), or a second heat-sealing resin layer, a functional resin layer And a three-layered heat seal of the first heat sealable resin layer.
For example, a metal layer (see FIG. 3) can be used. Thus, in the present invention, as a material for forming the first or second heat-sealing resin layer constituting the multilayer laminated heat-sealing material layer according to the present invention, extrusion molding is used. Any material that can be melted by heat and can be fused to each other may be used. For example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene, ethylene -Vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene or Acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itako It is possible to use a resin composed of one or more resins such as an acid-modified polyolefin-based resin modified with an unsaturated carboxylic acid such as an acid, a polyvinyl acetate-based resin, a polyester-based resin, a polystyrene-based resin, and the like. it can. In the present invention, when the first and second heat-sealing resin layers are formed using the above-described resins, the same type of resin or a combination of different types of resins may be used. Specifically, for example, the first heat-sealing resin layer and the second heat-sealing resin layer may be formed using the same type of polyethylene resin. Further, the first heat-sealing resin layer and the second heat-sealing resin layer may be made of different kinds of polyethylene resin and ethylene-vinyl acetate copolymer, or polyethylene resin and ethylene resin. -It can also be formed using a methacrylic acid copolymer.

In the present invention, among the above resins, it is particularly preferable to use linear low-density polyethylene. The above-mentioned linear low-density polyethylene has the advantage of improving the impact resistance with less propagation of breakage due to having tackiness,
In addition, since the inner layer is in constant contact with the contents, it is also effective for preventing deterioration of environmental stress cracking resistance. In the present invention, the linear low-density polyethylene, other resins can be blended,
For example, by blending an ethylene-butene copolymer or the like, although the heat stability is slightly lower and the seal stability tends to deteriorate in a high-temperature environment, the tearing property is improved, which contributes to easy opening. There is an advantage. Further, in the present invention, as the linear low-density polyethylene as a resin having heat sealability as described above, specifically, an ethylene-α-olefin copolymer polymerized using a metallocene catalyst is used. Can be used. Examples of the ethylene-α-olefin copolymer polymerized using the above metallocene catalyst include, for example, a catalyst formed by a combination of a metallocene complex and an alumoxane such as a catalyst formed by a combination of zirconocene dichloride and methylalumoxane, that is, a metallocene catalyst. Ethylene obtained by polymerization using
α-Olefin copolymer can be used. The metallocene catalyst has a non-uniform active site and is called a multi-site catalyst, whereas the existing catalyst is called a single-site catalyst because the active site is uniform. Specifically, the product name “Car-
Nell ", trade name" Evolu "manufactured by Mitsui Petrochemical Industries, Ltd., Exxon Chemical, USA
EMICAL) EXACT
T) ", Dow Chemical, USA
AL) brand name "Affinity-(AFFINIT
Y), an ethylene-α-olefin copolymer polymerized using a metallocene catalyst such as “ENGAGE” can be used. In the present invention, when an ethylene-α-olefin copolymer polymerized by using the above-mentioned metallocene catalyst is used, an advantage that a low-temperature heat-sealing property can be obtained at the time of producing a bag is provided. Have

Next, in the present invention, as a material forming the functional resin layer constituting the multilayer laminated heat seal material layer according to the present invention, a barrier property against oxygen gas, water vapor and the like, and / or , Less adsorption of perfume components etc. contained in the contents to be packed and packed, rich in fragrance retention, etc.,
It is possible to use a resin which has a property of not causing taste, odor and the like, and which can be extruded. Specifically, for example, polyacrylic resin, polymethacrylic resin, polyacrylonitrile resin , Polymethacrylonitrile-based resin, polystyrene-based resin, polycarbonate-based resin, polyethylene terephthalate-based resin or a part of the ethylene component and / or terephthalate component thereof with other di- or more Resins copolymerized or modified with polyhydric alcohol components or dicarboxylic acid components, polyester resins such as polyethylene naphthalate resins, polyamide resins, saponified ethylene-vinyl acetate copolymers, polyvinyl alcohol Resin, polyvinyl chloride resin, polyvinylidene chloride resin, etc. Kill. 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 Saponified copolymer, polyamide resin,
It is desirable to use a polyacrylonitrile-based resin or a resin rich in fragrance retention, barrier properties, etc., made of a polyester-based resin or the like.

Next, in the present invention, a method for producing a multilayer laminated heat seal material layer according to the present invention using the above-mentioned materials will be described. A molding method for forming a resin into a multilayer film,
For example, a T-die method, an inflation method, a multilayer co-extrusion laminating method, or the like is employed. In particular,
Multi-layer T such as feed block method and multi-manifold method
The multilayer laminated heat seal material layer according to the present invention is manufactured by using a molding method such as a die casting molding method, a multilayer inflation molding method, and a multilayer co-extrusion lamination molding method. be able to. In the present invention,
For example, a first heat seal made of polyethylene resin
Resin layer / adhesive resin layer composed of acid-modified polyolefin resin / functional layer composed of saponified ethylene-vinyl acetate copolymer / adhesive resin layer composed of acid-modified polyolefin resin / polyethylene resin The second heat
A three-layered five-layer laminate such as a sealable resin layer, or a first heat-sealing resin layer made of a polyethylene resin /
Adhesive resin layer composed of acid-modified polyolefin resin / functional resin layer composed of saponified ethylene-vinyl acetate copolymer / adhesive resin layer composed of acid-modified polyolefin resin / ken of ethylene-vinyl acetate copolymer Resin layer composed of a compound / adhesive resin layer composed of an acid-modified polyolefin-based resin / second resin layer composed of a polyethylene-based resin
A three-layer, seven-layer laminate such as a sealing resin layer can be produced.

Further, in the present invention, a multi-layer T die-casting method such as a feed block method or a multi-manifold method, a multi-layer inflation molding method, and a multi-layer co-extrusion laminating method or the like. From the first heat-sealing resin layer composed of polyethylene resin / adhesive resin layer composed of acid-modified polyolefin resin / saponified ethylene-vinyl acetate copolymer, for example. Or a three-layered laminate of functional resin layers or a first heat-sealing resin layer made of a polyethylene resin / an adhesive resin layer made of an acid-modified polyolefin-based resin / a nylon resin. It is possible to produce a three-layered three-layered product such as a functional resin layer. Next, in the present invention, the thickness of each of the layers constituting the multilayer laminated heat seal material layer according to the present invention as described above may be, for example,
Alternatively, the thickness of the second heat-sealing resin layer is about 1 to 200 μm, preferably about 5 to 100 μm, and the thickness of the functional resin layer is about 1 to 100 μm.
m position, preferably 5 to 50 μm,
The adhesive resin layer between each of the first or second heat-sealing resin layer and the functional resin layer has a thickness of about 1 to 100 μm.
And preferably about 5 to 50 μm.

Next, in the present invention, the material constituting the intermediate layer has, for example, excellent properties in mechanical, physical, chemical, etc. as a basic material constituting the tube container. In particular, it is strong and tough,
In addition, a resin film or sheet 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. Thus, as the resin film or sheet, any one 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 10 μm to 50 μm.
The m-th position is desirable. In the present invention, the base film as described above is subjected to, for example, front printing or back printing by printing a desired printing pattern such as a character, a figure, a symbol, a picture, or a pattern by a normal printing method. It may be.

Next, in the present invention, as the material constituting the intermediate layer, for example, various paper base materials constituting the paper layer can be used. The paper base material is provided with shapeability, bending resistance, rigidity, etc., for example, strong size bleached or unbleached paper base material, or pure white roll paper, kraft paper, paperboard, A paper substrate such as a processed paper or the like can be used. In the above, as the paper base material constituting the paper layer, it is desirable to use a base material having a basis weight of about 80 to 600 g / m ² , preferably a base weight of about 100 to 450 g / m ² . Needless to say, in the present invention, a paper base constituting the paper layer and various resin films or sheets as the base films mentioned above can be used in combination.

Further, in the present invention, as a material constituting the intermediate layer, for example, a material having a barrier property against oxygen gas and water vapor, a material having a light shielding property against sunlight and the like,
Alternatively, a material having a scent-retaining property or the like for the contents can be used. Specifically, as the barrier material, for example, a resin film or a sheet having a deposited thin film of an inorganic oxide such as silicon oxide and aluminum oxide is used.
Can be used. For example, a physical vapor deposition method (Physical V method) such as a vacuum evaporation method, a sputtering method, an ion plating method, a cluster ion beam method, and the like.
apor Deposition method, PVD method), or 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.
A resin film or sheet in which a vapor-deposited thin film of an inorganic oxide such as silicon oxide or aluminum oxide is formed on a resin film using a vapor deposition method, a CVD method, or the like can be used. More specifically, in the above-mentioned PVD method, for example, a roll-up type vapor deposition machine is used, and a film of a resin discharged from an unwinding roll is placed in a vapor deposition chamber in a vacuum chamber. Here, the evaporation source heated in the crucible is evaporated, and if necessary, a mask is put on the resin film on the cooled coating drum while spouting oxygen or the like from the oxygen outlet. A film of an inorganic oxide such as aluminum oxide or silicon oxide is formed through the film, and then a film of the resin on which the vapor-deposited thin film has been formed is taken up on a take-up roll, thereby depositing the inorganic oxide according to the present invention. A resin film having a thin film can be manufactured. On the other hand, in the above-mentioned CVD method, a resin film unwound from an unwinding roll arranged in a vapor deposition chamber has a film surface.
Cooling inside the deposition chamber, on the electrode drum peripheral surface,
It is possible to introduce a mixed gas comprising an organic silicon compound, an oxygen gas, and an inert gas as a monomer gas supplied from a vaporization material volatilization supply device, and produce a resin film in which a vapor-deposited thin film of silicon oxide is formed by plasma. it can. Thus, in the present invention, in a resin film having a vapor-deposited thin film of an inorganic oxide such as aluminum oxide and silicon oxide as described above, oxygen gas or water vapor or the like is prevented from permeating, and It functions as a barrier substrate.

In the above, the thickness of the deposited inorganic oxide thin film is usually 5 to obtain a sufficient barrier property.
It is preferably about 0 ° to 3000 °, and particularly preferably about 100 ° to 2000 ° in the present invention. More specifically, in the above-mentioned PVD method, the thickness of the deposited thin film of aluminum oxide is 200 to 1000 °.
, Preferably about 300 ° to 500 °, and in the above CVD method, the thickness of the deposited silicon oxide thin film is about 50 ° to 500 °, preferably about 10 °.
0 ° to 300 ° is desirable. In the above description, if the thickness of the deposited inorganic oxide thin film exceeds 2,000 mm, cracks and the like are likely to be formed in the deposited inorganic oxide thin film, and there is a risk that the barrier property is reduced by warpage. At the same time, it is not preferable because the material cost is high.
It is not preferable because it is difficult to perform the function. Examples of the resin film supporting the vapor-deposited thin film of the inorganic oxide include a polyester film, a polyamide film, a polyolefin film, a polyvinyl chloride film, a polycarbonate film, a polyvinylidene chloride film, and a polyvinyl alcohol film.
Film, a saponified ethylene-vinyl acetate copolymer film, and others. The surface of the resin film described above can be coated in advance with, for example, a deposition primer or the like in order to enhance the adhesion of the deposited film, and other necessary pretreatment can be optionally performed. is there. In the present invention, an organic silicon compound or a derivative thereof can be used as a deposition material by the above-mentioned CVD method.

In the present invention, examples of the barrier material or the material having a scent-retaining property include polyvinylidene chloride resin, polyester resin, polyamide resin, ethylene-vinyl acetate copolymer ( Ethylene-vinyl alcohol having an ethylene content of 25 to 50 mol%, obtained by completely saponifying (79 to 92 wt% of vinyl acetate).
A film or sheet of a resin having a high gas barrier property such as a copolymer, polyvinyl alcohol, polyacrylonitrile, or the like, or a coating film can be used.

Furthermore, in the present invention, as the barrier material, a so-called inorganic / organic hybrid film made of a sol-gel film can be used. Specifically, for example, a general formula, M (0R) _n ( _where , M represents a metal element, and specific examples thereof include Si, Al, Sr,
Ba, Pb, Ti, Zr, La, Na and the like;
Is a compound having 1 carbon atom such as methyl, ethyl, propyl, butyl, etc.
Represents up to 8 alkyl groups. )), One or more metal alkoxides are used.
A water-soluble resin such as polyvinyl alcohol or a saponified ethylene-vinyl acetate copolymer, or a hydrophilic resin is added, and the mixture is further kneaded with a solvent such as water or alcohol, and then coated. A liquid is formed, and the compounds coexisting in it cause a hydrolysis reaction and a polycondensation reaction, or, in the course of this reaction or after completion of the reaction, add an organic substance or a catalyst to increase the molecular weight. Thus, a sol-like coating solution can be obtained. Thus, the above-mentioned sol-like coating solution is in-line or on the aluminum oxide deposited film.
Coating off-line, then coating the coating layer with 7
By heating in a temperature range of about 0 to 200 ° C., an amorphous ceramic transparent thin film can be produced, and this can be used as an inorganic / organic hybrid film formed by a sol-gel film.

In the above, the organic substance to be added to the reaction system is, for example, a low to high polymer having a functional group having high chemical reactivity, such as alcohol, aldehyde, carboxylic acid, amide, amine, isocyanate and the like. Things can be used. In the above, as the catalyst,
Organic acids, organic bases, inorganic acids, inorganic bases, metal oxides and the like can be used. The inorganic / organic hybrid film formed by the sol-gel film is provided on the surface of the inorganic oxide vapor-deposited thin film of the resin film having the above-mentioned inorganic oxide vapor-deposited thin film. It acts as a barrier substrate against gases, water vapor, etc., and acts in synergy with the barrier properties of a resin film having a vapor-deposited thin film of an inorganic oxide, thereby acting as an extremely advanced barrier substrate. In the above, as a coating method, for example, gravure coating, roll coating, reverse coating, knife coating, or the like can be used. The thickness of the inorganic / organic hybrid film formed by the above-mentioned sol-gel film may be about 1000 to 50 μm. In the present invention,
In forming the sol-gel film, for example, a curing agent such as an isocyanate compound may be used.

Further, in the present invention, the material constituting the intermediate layer may be, for example, a light-shielding material having a property of blocking light such as sunlight, or a property of impermeable to water vapor or water. A water-resistant material may be used, which may be a single substrate or a composite substrate obtained by combining two or more types of substrates. Specifically, for example, water-resistant materials having barrier properties such as water vapor and water include, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, and ethylene-propylene. A resin film or sheet of a polymer or the like can be used, and as a light-shielding material, for example, a coloring agent such as a pigment is added to a resin, and further, a desired additive such as other is added and kneaded. Various colored resin films or sheets having a light-shielding property formed into a film can be used. These materials can be used alone or in combination of two or more. The above film or sheet
Although the thickness of the gate is arbitrary, it is usually preferably about 5 μm to 300 μm, more preferably about 10 μm to 100 μm.

In general, a laminated tube container is subjected to severe physical and chemical conditions. Therefore, the laminated material constituting such a container is required to have strict packaging suitability and to be deformed. Prevention strength, drop impact strength, anti-pinho
Properties, heat resistance, sealing, quality maintenance, workability, hygiene,
Various other conditions are required. For this reason, in the present invention, in addition to the above-described materials, other materials satisfying the above-described various conditions can be arbitrarily used. Specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate Copolymer, ethylene-
Acrylic or methacrylic acid copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acryl Resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate Resin, polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, fluorine resin, diene resin, polyacetal resin, polyurethane resin, nitrocellulose
And any other known resin film or sheet. In addition, for example, a film such as cellophane, synthetic paper, or the like can be used. In the present invention, the above-mentioned film or sheet can be used in any of unstretched and uniaxially or biaxially stretched. The thickness is arbitrary, but can be selected from a range of several μm to about 300 μm. Further, in the present invention, as the film or sheet, extrusion film formation,
Any film such as an inflation film or a coating film may be used.

Next, in the present invention, a method for producing a laminated material for forming the tube container according to the present invention using the above-mentioned materials will be described. Lamination methods used when manufacturing packaging materials, such as wet lamination methods, dry lamination methods, solventless dry lamination methods, extrusion lamination methods, T-die coextrusion molding methods, Extrusion lamination method, inflation
It can be carried out by any method such as a method of application and others.
Thus, in the present invention, when performing the above lamination, if necessary, a pretreatment such as a corona treatment or an ozone treatment can be applied to the film. (Urethane-based), polyethyleneimine-based, polybutadiene-based, organic titanium-based anchor co-
Polyurethane, polyacrylic, polyester, epoxy, polyvinyl acetate,
Known anchor coating agents, adhesives and the like, such as cellulose and other laminating adhesives, can be used arbitrarily.

By the way, in the above-mentioned method for producing a laminated material, as the extruded resin constituting the adhesive resin layer at the time of extruding and laminating, for example, polyethylene,
Ethylene-α-olefin copolymer, polypropylene,
Copolymers of ethylene and unsaturated carboxylic acids such as polybutene, polyisobutene, polyisobutylene, polybutadiene, polyisoprene, ethylene-methacrylic acid copolymer, or ethylene-acrylic acid copolymer, or acid-modified polyolefins obtained by modifying them A series resin, an ethylene-ethyl acrylate copolymer, an ionomer resin, an ethylene-vinyl acetate copolymer, and the like can be used. Further, in the present invention, as the adhesive constituting the adhesive layer at the time of dry lamination, specifically,
Two-component curable urethane adhesives, polyester urethane adhesives, polyether urethane adhesives, acrylic adhesives, polyester adhesives, polyamide adhesives, polyvinyl acetate adhesives used in dry laminates, etc. An adhesive, an ethoxy-based adhesive, a rubber-based adhesive, or the like can be used.

Next, in the present invention, when manufacturing the tube container according to the present invention, for example, as a method of heat sealing when manufacturing the cylindrical body, for example, a base seal is used. It can be carried out by a known method such as a roll seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal, a flame seal and the like.

Next, in the present invention, a laminated material for forming the tube container manufactured as described above is used. First, the laminated material is rolled, and its overlapping end is welded to form a cylindrical tube for forming an extruded tube. A body is manufactured, and then, for example, an injection molding method, a compression molding method of high-density polyethylene or the like above the cylindrical body,
Forming and welding by other molding methods to form a head consisting of a shoulder and a mouth, and then, on the surface of the cylindrical body,
Using flexographic ink, using flexographic printing method,
The tube container according to the present invention can be manufactured by printing and forming a flexographic printing pattern layer composed of characters, figures, symbols, patterns, and the like, and then attaching a cap to the mouth constituting the head. Thus, in the present invention, the contents to be filled and packed are filled through the opening at the lower end of the tube container manufactured as described above, and then the opening is heat-sealed to form a bottom welded portion. Thus, a tube package can be manufactured. In the above, as the contents to be filled and packed,
For example, toothpaste, cosmetics, glue, paste, paste wasabi, cream, paint, ointment, medicine, etc. can be mentioned. In the above, in addition to the high-density polyethylene as described above, ethylene-α polymerized using the above-described metallocene catalyst is used as a material for forming the head portion of the tube container including the shoulder and the mouth. -An olefin copolymer or the like can be used. In the above, the flexographic printing can be performed on the surface of the plain laminated material instead of on the surface of the plain cylindrical portion as described above.

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 desired characters, figures, symbols, patterns, etc. Is formed by printing the printed pattern layer. In addition, as the above-mentioned flexo ink, an evaporation-drying ink mainly containing an alcohol-based 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 the flexographic printing method, it is possible to manufacture a laminated material in a plain state, and further, to manufacture a tubular part in a plain state. Thus, the plain laminated material or the tubular part is produced. Since the desired print pattern layer can be formed by directly printing on the surface, even if printing failures occur, if only a small amount of laminated material or several tubular parts are defective, This is advantageous in that the generation of defective products can be suppressed as much as possible. That is, usually, a desired printing pattern 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 to produce a laminated material with a printing pattern,
Next, the same cylindrical part is manufactured from the laminated material, but if a defective print is found in the laminated material, or the same cylindrical part, all the semi-finished products are defective. However, the present invention has an advantage that such a problem can be solved.

[0030]

EXAMPLES Next, the present invention will be described more specifically with reference to examples. Example 1 (1). A linear low-density polyethylene film polymerized with a single-site catalyst having a thickness of 80 μm and having one surface subjected to corona discharge treatment was prepared. (2). On the other hand, a thickness of 80 with a corona discharge treatment on one side
μm milky low-density polyethylene film with a corona discharge treated surface and a thickness of 12
The biaxially stretched polyethylene terephthalate film having a thickness of μm was opposed to the silicon oxide vapor-deposited thin film surface, and both were dry-laminated using a two-component curable urethane-based adhesive and laminated. (3). Furthermore, a high pressure method low density polyethylene (density = 0.
918, melt index, MI = 7.0) and acid anhydride graft polymerized low density polyethylene (adhesive resin, density = 0.91, melt index, MI = 6.2)
And a saponified ethylene-vinyl acetate copolymer (ethylene content 38 mol%, density = 1.17, melt index, MI = 8.0) using a multilayer inflation method. Multilayer film forming was carried out to produce three types and five layers of a multilayer laminated heat seal material layer having the following layer constitution. Low-density polyethylene layer having a thickness of 5 μm / anhydride graft polymerization having a thickness of 5 μm Low-density polyethylene layer / saponified layer of ethylene-vinyl acetate copolymer having a thickness of 5 μm / acid anhydride graft polymerization having a thickness of 5 μm Polyethylene layer / low-density polyethylene layer having a thickness of 5 μm (4). Next, a two-part curable urethane-based adhesive is coated on the corona discharge treated surface of the film (1), and then the low-density polyethylene is used to form a film having a thickness of 20 μm.
While being melt-extruded, the surfaces of the milky white low-density polyethylene film laminated in the above (2) were opposed to each other, and both were extruded and laminated. (5). Next, a two-part curable urethane-based adhesive is applied to the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm having the deposited silicon oxide thin film laminated in (4) above. After coating the agent, the low-density polyethylene was melt-extruded to a thickness of 20 μm, and one of the low-density polyethylene layers of the multilayer laminated heat seal material layer (3) was opposed to the other. The two were extruded and laminated to produce a laminated material. (6). Next, using the laminated material manufactured above,
The laminated material is punched to produce a blank plate, and the back bonded portion is heat-sealed at 215 ° C. for 3 seconds under heat welding conditions of 3 kg / cm ² so that the inner surface is on the inner surface side. hand,
A cylindrical body serving as a body of a tube container having a diameter of 35 mm and a height of 160 mm was manufactured. Next, the cylindrical body manufactured as described above 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 narrow neck opening continuous therewith are formed in a conventional manner. The head consisting of the neck was mixed with 98.0 parts by weight of high-density polyethylene and 2.0% by weight of milky pigment.
Using the added high-density polyethylene composition, molding was performed by a compression molding method at a resin temperature of 245 ° C. Further, after the head is formed as described above, a desired printing pattern layer is formed on the surface of the cylindrical body by a flexographic printing method using an ultraviolet curable flexographic ink composition, and the tube according to the present invention is formed. A container was manufactured. Next, on the mouth and neck of the cylindrical body having the above head,
The cap was spirally wound, and the other opening of the cylinder was filled with 150 g of commercially available toothpaste, and the opening of the cylinder was heat-sealed to produce a tube container package. .

Embodiment 2 In the above-mentioned embodiment 1, the multi-layer laminated heat sheet (3) is used.
A tube container according to the present invention was used in the same manner as in Example 1 except that a multilayer laminated heat-sealing agent layer shown in the following (1) was used instead of the metal material layer. ,and,
A tube container package was manufactured. (1). High-pressure low-density polyethylene (density = 0.91
8, melt index, MI = 7.0) and acid anhydride graft polymerized low density polyethylene (adhesive resin, density =
0.90, melt index, MI = 4.4) and polymeta-xylene diadipamide resin (aromatic nylon resin, manufactured by Mitsubishi Gas Chemical Industry Co., Ltd., trade name, MX-N
y, melting point, Tm = 240 ° C., melt index, MI
= 7.0, relative viscosity, 2.1), and co-extrusion molding by a multi-layer co-extrusion laminating method to form a multilayer laminated heat seal having the following layer constitution. A material layer was manufactured. Low-density polyethylene layer having a thickness of 5 μm / anhydride-grafted low-density polyethylene layer having a thickness of 5 μm / polymethaxylenediadipamide resin layer having a thickness of 5 μm /
5 μm thick acid anhydride graft polymerized low density polyethylene layer / 5 μm thick low density polyethylene layer

Embodiment 3 In the above-described embodiment 1, the multi-layer laminated heat sheet (3) is used.
A tube container according to the present invention was used in the same manner as in Example 1 except that a multilayer laminated heat-sealing agent layer shown in the following (1) was used instead of the metal material layer. ,and,
A tube container package was manufactured. (1). High pressure low density polyethylene (density = 0.92,
Melt index, MI = 0.6) and acid anhydride graft polymerized linear low density polyethylene (adhesive resin, density = 0.92, melt index, MI = 3.5),
Saponified ethylene-vinyl acetate copolymer (ethylene content 38 mol%, density = 1.17, melt index,
MI = 1.6) and a metallocene-based α-olefin copolymer polyethylene (density = 0.92, melt index, MI = 2.0) using four types of resins, and a multilayer inflation method. Film forming was carried out to produce a multilayer laminated heat seal material layer of four types and five layers having the following layer constitutions. 20 μm thick low density polyethylene layer /
10 μm-thick acid anhydride graft-polymerized low density polyethylene layer / 10 μm-thick saponified layer of ethylene-vinyl acetate copolymer / 10 μm-thick acid anhydride graft-polymerized low-density polyethylene layer / 30 μm-thick metallocene system α-olefin copolymer polyethylene layer

Embodiment 4 In the above-mentioned embodiment 1, the multi-layer laminated heat sheet (3) is used.
A tube container according to the present invention was used in the same manner as in Example 1 except that a multilayer laminated heat-sealing agent layer shown in the following (1) was used instead of the metal material layer. ,and,
A tube container package was manufactured. (1). Metallocene α-olefin copolymer polyethylene (density = 0.92, melt index, MI =
4.0) and acid anhydride graft polymerized low density polyethylene (adhesive resin, density = 0.90, melt index,
MI = 4.4) and polymeta-xylene diadipamide resin (aromatic nylon resin, manufactured by Mitsubishi Gas Chemical Industry Co., Ltd., trade name, MX-Ny, melting point, Tm = 240 ° C., melt index, MI = 7. Using the three types of resins (0, relative viscosity, 2.1), a multi-layered heat seal material layer having the following layer constitution was produced by a multilayer T-die casting method. Metallocene α-olefin copolymer polyethylene layer having a thickness of 30 μm / thickness of 10
μm acid anhydride graft-polymerized low-density polyethylene layer / 10 μm-thick polymethaxylene diadipamide resin layer / 10 μm-thick acid anhydride-grafted low-density polyethylene layer / 30 μm-thick metallocene α-olefin copolymer Combined polyethylene layer

Fifth Embodiment In the first embodiment, the multi-layer laminated heat sheet (3) is used.
A tube container according to the present invention was used in the same manner as in Example 1 except that a multilayer laminated heat-sealing agent layer shown in the following (1) was used instead of the metal material layer. ,and,
A tube container package was manufactured. (1). Saponified ethylene-vinyl acetate copolymer (ethylene content 38 mol%, density = 1.17, melt index, MI = 8.0) and acid anhydride graft polymerized low density polyethylene (adhesive resin, density = 0) .91, melt index, MI = 6.2) and metallocene α-olefin copolymer polyethylene (density = 0.92, melt index, MI = 9.0). Multi-layer film forming was performed by a die-casting method to produce three types of three-layered multi-layered heat seal material layers having the following layer constitutions. 10 μm thick ethylene
Saponified layer of vinyl acetate copolymer / Acid anhydride graft-polymerized low-density polyethylene layer of 10 μm thickness / 30 μm thickness
Metallocene α-olefin copolymer polyethylene layer

Embodiment 6 (1). Corona discharge-treated surface of a milky white low-density polyethylene film having a thickness of 80 µm with a corona discharge treatment on one side, and silicon oxide vapor deposition of a 12 µm-thick biaxially stretched polyethylene terephthalate film having a thin film of silicon oxide deposited on one side The thin film surface was opposed, and both were dry-laminated using a two-component curable urethane-based adhesive and laminated. (2). On the other hand, a thickness of 80 μm with corona discharge treatment on one side
After coating a two-component curable urethane-based adhesive on the corona-discharge treated surface of a linear low-density polyethylene film polymerized by a single-site catalyst, the low-density polyethylene is used to melt it to a thickness of 20 μm. While extruding, the surfaces of the milky white low-density polyethylene film laminated in the above (1) were opposed to each other, and both were extruded and laminated. (3). Furthermore, a high pressure method low density polyethylene (density = 0.
918, melt index, MI = 7.0) and acid anhydride graft polymerized low density polyethylene (adhesive resin, density = 0.91, melt index, MI = 6.2)
And a saponified ethylene-vinyl acetate copolymer (ethylene content 38 mol%, density = 1.17, melt index, MI = 8.0) using a multilayer inflation method. Multilayer film forming was carried out to produce three types and five layers of a multilayer laminated heat seal material layer having the following layer constitution. Low-density polyethylene layer having a thickness of 5 μm / anhydride graft polymerization having a thickness of 5 μm Low-density polyethylene layer / saponified layer of ethylene-vinyl acetate copolymer having a thickness of 5 μm / acid anhydride graft polymerization having a thickness of 5 μm Polyethylene layer / low-density polyethylene layer having a thickness of 5 μm (4). Next, a two-component curable urethane-based adhesive is applied to the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm and having the deposited silicon oxide thin film laminated in (2) above. After coating the agent, the low-density polyethylene was melt-extruded to a thickness of 20 μm, and one low-density polyethylene layer of the multilayer laminated heat-sealing material layer of (3) was opposed to the other. And both were extruded and laminated. (5). Next, the thickness of 80 μm laminated in (4) above
After corona discharge treatment on the surface of the linear low-density polyethylene film polymerized by the single-site catalyst, a corona discharge-treated surface is coated with a UV-curable flexographic ink composition to form a desired print pattern layer by flexographic printing. Once formed, a laminate was produced. (6). Next, using the laminated material manufactured above,
The laminated material is punched to produce a blank plate, and the back bonded portion is heat-sealed at 215 ° C. for 3 seconds under heat welding conditions of 3 kg / cm ² so that the inner surface is on the inner surface side. hand,
A cylindrical body serving as a body of a tube container having a diameter of 35 mm and a height of 160 mm was manufactured. Next, the cylindrical body manufactured as described above 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 narrow neck opening continuous therewith are formed in a conventional manner. The head consisting of the neck was mixed with 98.0 parts by weight of high-density polyethylene and 2.0% by weight of milky pigment.
Using the added high-density polyethylene composition, molding was performed by a compression molding method at a resin temperature of 245 ° C. Furthermore, after the head is molded above, a cap is spiraled around the mouth and neck of the cylinder having the above-described head, and then, from the other opening of the cylinder,
150 g of commercially available toothpaste was filled, and then the opening of the cylindrical body was heat-sealed to produce a tube container package.

Embodiment 7 In the above-described embodiment 6, the multi-layer laminated heat sheet (3) is used.
A tube container according to the present invention was used in the same manner as in Example 1 except that a multilayer laminated heat-sealing agent layer shown in the following (1) was used instead of the metal material layer. ,and,
A tube container package was manufactured. (1). High-pressure low-density polyethylene (density = 0.91
8, melt index, MI = 7.0) and acid anhydride graft polymerized low density polyethylene (adhesive resin, density =
0.90, melt index, MI = 4.4) and polymeta-xylene diadipamide resin (aromatic nylon resin, manufactured by Mitsubishi Gas Chemical Industry Co., Ltd., trade name, MX-N
y, melting point, Tm = 240 ° C., melt index, MI
= 7.0, relative viscosity, 2.1), and co-extrusion molding by a multi-layer co-extrusion laminating method to form a multilayer laminated heat seal having the following layer constitution. A material layer was manufactured. Low-density polyethylene layer having a thickness of 5 μm / anhydride-grafted low-density polyethylene layer having a thickness of 5 μm / polymethaxylenediadipamide resin layer having a thickness of 5 μm /
5 μm thick acid anhydride graft polymerized low density polyethylene layer / 5 μm thick low density polyethylene layer

Embodiment 8 In the above-mentioned embodiment 1, the multi-layer laminated heat sheet (3) is used.
A tube material and a tube material according to the present invention are used in the same manner as in Example 1 except that the laminated material shown in the following (1) is used instead of the metal material layer. A package was manufactured. (1). 150 μm thick milky white polyethylene film, 20 μm thick aluminum foil, and 60 μm thick
m, using a linear low-density polyethylene film, and further using an ethylene-methacrylic acid copolymer as a melt-extruded resin, by an extrusion lamination method,
The layers were sequentially laminated to produce a laminated material having the following layer configuration. 150 μm thick milky white polyethylene film / 30 μm thick ethylene-methacrylic acid copolymer layer / 20 μm thick aluminum foil / 40 μm thick ethylene-methacrylic acid copolymer layer / 60 μm thick linear low density polyethylene film

Comparative Example 1 (1). A gravure printing method using a gravure ink containing a polyurethane resin as the main component of the vehicle on the corona discharge treated surface of a linear low-density polyethylene film polymerized with a single-site catalyst having a thickness of 80 μm and corona discharge treated on one side. The desired printed picture layer was printed. (2). On the other hand, a thickness of 80 with a corona discharge treatment on one side
μm milky low-density polyethylene film with a corona discharge treated surface and a thickness of 12
The biaxially stretched polyethylene terephthalate film having a thickness of μm was opposed to the silicon oxide vapor-deposited thin film surface, and both were dry-laminated using a two-component curable urethane-based adhesive and laminated. (3). Next, after coating the two-component curable urethane-based adhesive on the printed pattern layer surface of the film of the above (1),
Using low-density polyethylene, the milky white low-density polyethylene film laminated in (2) above was melt-extruded to a thickness of 20 μm, and the two surfaces were extruded and laminated. (4). Next, a two-component curable urethane-based adhesive is applied to the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm and having the deposited silicon oxide thin film laminated in (3) above. After coating the agent, using an ethylene-methacrylic acid copolymer, this was melt-extruded to a thickness of 20 μm, and the corona-discharge treated surface of a 80 μm-thick linear low-density polyethylene film having one surface subjected to a corona discharge treatment was opposed. Then, both were extruded and laminated to produce a laminated material.

Experimental Example Each of the tube packages of Examples 1 to 8 and Comparative Example 1 manufactured above was placed in a thermo-hygrostat at 37 ° C./45% RH.
Stored for months. Then, the following evaluations 1 to 3 were performed. [Evaluation 1] First, the oxygen permeability and water vapor permeability of the laminated materials forming the tube containers of Examples 1 to 8 produced in the above and Comparative Example 1 were measured under the following conditions. The results are shown in Table 1 below. Oxygen permeability is
Under the condition of 23 ° C./90% RH, US Mocon (MOCO
N) was measured using an oxygen permeability measuring instrument [model name, OXTRAN], and the water vapor permeability was measured at 40 ° C./90% RH under the condition of Mocon (M.
The measurement was carried out using a water vapor permeability measuring instrument (model name, PERMATRAN) manufactured by OCON Corporation. [Evaluation 2] Next, the oxygen permeability and the water vapor permeability of each of the tube containers of Examples 1 to 8 and Comparative Example 1 produced above were measured under the following conditions. It is shown in Table 2 below. Oxygen permeability is 23 ° C / 90%
Under the condition of RH, an oxygen permeability analyzer [model name, OXTRAN] manufactured by MOCON, USA
The water vapor transmission rate was measured by putting 10 g of calcium chloride through the opening of the tube container and then heating the opening with a heat sink. To produce a tube container,
The container is stored in a constant temperature / humidity chamber at 40 ° C / 90% RH.
The water vapor transmission rate was measured from the weight increase. [Evaluation 3] Further, for each of the tube containers of Examples 1 to 8 and Comparative Example 1 produced above, the laminate strength and sensory evaluation of the fragrance retention were measured under the following conditions. The results are shown in Table 3 below. Laminate strength is
The peeling speed was 50 mm /
It was measured in min. The sensory evaluation of the fragrance retention was evaluated by a taste test using a panel.

[0040]

[0041]

[0042] In Table 3 above, the percentage of the residual strength of the laminating strength is shown in%.
Is the ratio of the laminate strength after storage to the laminate strength before filling the contents.
Indicates that the scent of the contents has hardly changed, and x indicates that the scent of the contents has been significantly reduced.

As is evident from the above results, the laminated material forming the tube container according to the present invention and the tube container using the same all show good results and sufficiently endure practical use. Was something.

[0044]

As is apparent from the above description, the present invention relates to a flexographic printing method and a multi-layer laminated heat sheet including a functional resin layer having a barrier property and a scent-retaining property in its structure. -Focusing on the metal layer, first, at least, the surface resin layer, the intermediate layer, and the inner surface resin layer is sequentially laminated to produce a laminated material, and when producing the laminated material, particularly, As the inner resin layer, a laminated material is manufactured using a multilayer laminated heat seal material layer including a functional resin layer having a barrier property, a fragrance retaining property, and the like, and then a cylindrical body is formed from the laminated material. And using the tubular body to form a head having a mouth, a shoulder, and the like at one opening thereof to produce a tube container. On the surface of the container, form a desired print pattern layer by flexographic printing using a flexographic printing method, and then The Ju - from the other opening of the probe containers, for example, to produce a packaged product contents, such as toothpaste filling and packaging, whereby to prevent the waste of materials used, and,
It has a beautiful printed picture layer on its surface, and furthermore, the heat when manufacturing the laminated material, the heat when manufacturing the container, and the heat when filling the contents and heat sealing the opening. It is possible to prevent the occurrence of cracks and the like in the silicon oxide thin film of the resin film having the silicon oxide thin film, etc., to prevent the transfer of offensive odor to the contents, etc. It has sufficient resistance to cracks, no leakage of its contents, etc., and no phenomenon such as delamination,
It is excellent in fragrance retention and preservability of the contents, and can produce a tube container useful for filling and packaging contents such as toothpaste, foods, cosmetics, pharmaceuticals, etc. .

[Brief description of the drawings]

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

FIG. 2 is a schematic sectional view showing an example of a layer configuration of a laminated material forming a tube container according to the present invention.

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

FIG. 4 is a schematic half sectional view showing a configuration of a tube container according to the present invention manufactured using the laminated material shown in FIG. 1;

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Surface resin layer 2 Intermediate layer 3 Inner resin layer 4 Functional resin layer 5 1st heat-sealing resin layer 5a 2nd heat-sealing resin layer 6a Two-layer laminated heat-sealing material layer 6b 3-layer laminated heat - tosylate - sealing material layer 11 welded portion 12 the cylindrical body 13 the shoulder portion 14 necked portion 15 head 16 print pattern layer 17 cap 18 contents 19 bottom welded part A laminate A ₁ laminate A ₂ laminates R lamination - Tochu - Bed vessel Ra Chu - Bed package

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Chizuruko Oshina 1-1-1 Ichigaya-Kaga-cho, Shinjuku-ku, Tokyo F-term in Dai Nippon Printing Co., Ltd. (reference) 3E065 BA02 BA12 BA16 BA28 BA35 BA40 BB03 CA09 DC01 DD05 EA04 GA01 GA02 4F100 AA20 AK01A AK01C AK01E AK06 AK42 AK51G AK63 AK69 AL07 AR00D AT00B BA04 BA05 BA07 BA10C BA10D BA13 CB02 DA02 EC03 EH23 EH66 EJ55 GB17 GB23 GB66 HB31D JD00E JK14L

Claims (6)

[Claims] 1. A laminated material having a configuration in which at least a surface resin layer, an intermediate layer, and an inner resin layer are sequentially laminated, and further comprising a surface resin layer surface which is an outermost layer at both ends of the laminated material. The inner resin layer surface, which is the innermost layer, is overlapped, and the opposing surface is heat-sealed to form a cylindrical body.
A printing pattern layer by a flexographic printing method is provided on a surface resin layer surface of a laminating tube container provided with a head portion including a shoulder portion and a mouth portion at one opening of the cylindrical body portion. Tube container. 2. The tube container according to claim 1, wherein the inner resin layer comprises a multi-layer laminated heat seal material layer. 3. The multi-layer heat seal material layer comprises at least a functional resin layer and a two-layer heat seal material layer of a first heat seal resin layer. 3. The tube container according to claim 2, wherein: 4. The multi-layered heat-sealing material layer comprises at least three of a second heat-sealing resin layer, a functional resin layer, and a first heat-sealing resin layer. Layer stacking heather
3. The tube container according to claim 2, wherein the tube container comprises a metal material layer. 5. A multilayer heat seal material layer comprising: a multilayer inflation molding film, a multilayer T die cast molding film,
4. The tube container according to claim 2, wherein the tube container is formed by multilayer co-extrusion lamination molding. 6. The tube container according to claim 3, wherein the functional resin layer comprises a resin layer having a barrier property and / or a scent-retaining property.