JPH10146924A - Laminated material, and laminate tube container using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To achieve excellent hygiene without adhesion or propagation of mildews, germs, or bacteria on the container surface even at a high temperature by providing an inorganic compound having an antibacterial property at least in the surface layer part of a surface resin layer. SOLUTION: A laminated material A comprises at least a surface resin layer 1, a middle layer 2 and an inner resin layer 3 successively laminated from the outer side. An inorganic compound 5 having an antibacterial property is contained at least in the surface layer of the surface resin layer 1. As the inorganic compound, a silver ion soluble glass for diluting silver ions at a constant rate can be used. With a Banbary type mixer, a silver ion containing dissolving glass, and another additive can be added optionally to the thermoplastic resin. By sufficiently mixing and kneading, a master batch can be produced. By mixing the master batch with a resin for forming the surface resin layer 1 and sufficiently kneading, followed by a film formation by a T die method or an inflation method, a film or a sheet containing the silver ion containing dissolving glass in a dispersed state can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated material and a laminating tube container using the same, and more particularly, for example, for filling and packaging contents such as toothpaste, food, cosmetics, pharmaceuticals and others. The present invention relates to a laminated material for forming a laminating tube container suitable for the above, and an extruded laminating tube container using the same.

[0002]

2. Description of the Related Art Conventionally, as a laminating tube container, a laminated material obtained by sequentially laminating at least a surface resin layer, an intermediate layer and an inner resin layer is usually used, and both ends of the laminated material are used. The surface of the surface resin layer and the surface of the inner resin layer are overlapped with each other, and the opposite surface is heat-sealed to produce a cylindrical body. Further, a mouth and a shoulder are formed at one opening of the cylindrical body. Form a part,
The cap is screwed onto this to manufacture a laminating tube container. Thus, the above-mentioned laminate tutu
Using a tube container, fill the contents such as toothpaste, cream, etc. from the other opening for the laminating tube, and then seal the opening with a bottom seal. A part is formed to manufacture a packaged product using a laminating tube container.

[0003]

However, a packaged product using the above-mentioned laminating tube container may be placed under high humidity at the time of use.
A packaged product in which the dough is polished, and a facial cleansing cream or the like is filled and packaged is generally placed in a washroom, a bathroom, or the like. By the way, such places are generally rich in moisture, moisture, etc.
Mold, bacteria, germs, etc. are liable to occur, and the molds, bacteria, germs, etc. thus generated are liable to adhere to the surface of the laminating tube container. If adhered to the surface, it will gradually propagate and there is a problem that the laminating tube container becomes extremely unsanitary. Moreover, on the surface of the laminating tube container,
When mold, bacteria, germs, etc. adhere and proliferate, the surface of the laminating tube container itself discolors, giving the user extreme discomfort, and in some cases, without using all the contents, There is also a problem that it is discarded and is extremely uneconomical. Therefore, the present invention provides an extremely hygienic and uncomfortable laminating tube container without mold, bacteria, germs and the like adhering to the surface of the container even under high humidity. The purpose is to do so.

[0004]

Means for Solving the Problems The present inventor has conducted intensive studies to solve the above problems, and as a result, focused on an inorganic compound having antibacterial properties, and at least focused on a surface resin layer, an intermediate layer, and an inner surface. In a laminated material obtained by sequentially laminating resin layers, a laminated material containing an antibacterial inorganic compound is produced on at least the surface layer of the surface resin layer, and then, using the laminated material, The surfaces of the surface resin layer and the inner surface resin layer at both ends are overlapped with each other, and the opposing surfaces are heat-sealed to produce a cylindrical body. Further, a mouth is formed at one opening of the cylindrical body. The laminating tube container is manufactured by forming a portion and a shoulder portion, and a cap is screwed into the portion, a toothpaste is formed from the other opening of the laminating tube container, and the cream is formed. Etc., and then the opening is hermetically sealed to form a bottom seal. Thus, when a packaged product using a laminating tube container was manufactured, there was no evidence that bacteria, various germs, etc. adhered and propagated on the surface of the container even under high humidity in a washroom, a bathroom, and the like. The present invention has been completed by finding that a laminating tube container having no hygiene and antibacterial properties which does not cause discomfort can be produced without generation of mold and the like.

That is, the present invention relates to a laminated material comprising at least a surface resin layer, an intermediate layer and an inner resin layer sequentially laminated, wherein at least a surface layer of the surface resin layer contains an inorganic compound having antibacterial properties. And a laminating tube container using the same.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. First, the structure of the laminated material according to the present invention will be described with reference to the drawings.
FIG. 1 is a schematic sectional view showing an example of a layer configuration of a laminated material according to the present invention. First, as shown in FIG. 1, a laminated material A according to the present invention has a laminating tube container in which at least a surface resin layer 1, an intermediate layer 2, and an inner resin layer 3 are sequentially laminated from the outside. The laminated material for use 4 has a laminated structure characterized in that at least the surface layer of the surface resin layer 1 contains an inorganic compound 5 having antibacterial properties. More specifically, as shown in FIG. 2, a laminated material B according to the present invention is a laminate tube in which at least a surface resin layer 1, an intermediate layer 2, and an inner resin layer 3 are sequentially laminated from the outside. The laminated material 4 for forming a container has a laminated structure in which at least the surface layer of the surface resin layer 1 contains a silver ion-containing inorganic compound 5a that gradually elutes silver ions. Furthermore, as shown in FIG. 3, a laminated material C according to the present invention is a laminate tube container in which at least a surface resin layer 1, an intermediate layer 2, and an inner resin layer 3 are sequentially laminated from the outside. The laminated material for forming 4 has a laminated structure in which at least the surface layer of the surface resin layer 1 contains the silver ion-containing molten glass 5b.

[0007] In the present invention, the laminated material is not limited to the laminated material having the above structure.
Various forms of laminates can be used. Although not shown, as a laminated material according to the present invention, its purpose of use,
Depending on the contents to be filled, applications, etc., other materials can be further laminated, and the inorganic compound having antibacterial properties may be present at least in the surface layer of the surface resin layer. It may be contained in the entire resin layer, or may be further contained in an intermediate layer or a layer laminated with another material. However, in the present invention, it is desirable to provide a barrier layer on the content side so that the inorganic compound having antibacterial properties does not elute.

Next, in the present invention, an example of manufacturing a laminating tube container according to the present invention using the above-mentioned laminated material will be described. FIG. 4 shows the laminating 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 by using a laminated material A for forming a tube container. As shown in FIG. 4, first, using the laminated material A shown in FIG. 1 described above, first, the laminated material A is rolled, its edges are overlapped, and the overlapped end is welded to form a welded portion 6. Is formed to produce a cylindrical body 7, and the cylindrical body 7 is used as a cylindrical body constituting a laminating tube container. Next, in the present invention, a head such as a shoulder portion 8 and a mouth portion 9 constituting a laminating tube container is formed in a conventional manner above one opening of the cylindrical body portion 7. Further, a cap 10 to be hermetically sealed is attached to the mouth portion 9 to manufacture the laminating tube container R according to the present invention. Thus, the laminating tube container R manufactured as described above is filled with an appropriate amount of the contents 11 such as toothpaste and the like from the lower end of the other opening of the cylindrical body 7, and then filled. Thereafter, the opening is welded to form a bottom welded portion 12, and the contents 11 are filled and packaged in a laminating tube.
Can manufacture a packaged product consisting of a container. The above-mentioned examples are merely examples of the laminated material according to the present invention and a laminating tube container using the same, and the present invention is not limited thereto.

Next, in the present invention, the materials constituting the laminated material, the laminating tube container and the like as described above will be described. First, in the present invention, as a material constituting the surface resin layer, as described above, the laminated material is rolled and the overlapped end thereof is welded to produce a cylindrical body, so that the inner resin layer is heated. It is preferable to use a resin film or sheet having heat sealability, which can be melted and fused to each other. Specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer Copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyolefin such as polyethylene or polypropylene Acrylic resin, methacrylic acid,
Acid-modified polyolefin resin, polyvinyl acetate resin, poly (meth) acrylic resin, polychlorinated acid modified with maleic acid, fumaric acid, itaconic acid, maleic anhydride and other unsaturated carboxylic acids A film or sheet of a resin such as a vinyl resin or the like can be used. Thus, the above-mentioned film or sheet can be used in a state of a coating film of a composition containing the resin. The thickness of the film, film or sheet is about 10 μm to 200 μm, preferably about 30 μm to 150 μm.

Next, in the present invention, the material constituting the intermediate layer is, for example, a material excellent in mechanical, physical, chemical, etc. as a basic material constituting a laminating tube container. In particular, a resin film or sheet having strength, toughness, and 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
About 50 μm 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.

Next, in the present invention, as a material constituting the inner resin layer, as described above, the laminated material is rolled and the overlapped end thereof is welded to produce a cylindrical body, so that the surface resin is formed. Layer or a heat-sealing resin film or sheet that can be melted and fused to each other by heating
It is preferred to use Specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, 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, methylpentene polymer, polybutene polymer -, Polyolefin resin such as polyethylene or polypropylene, acrylic acid, methacrylic acid,
Acid-modified polyolefin resin, polyvinyl acetate resin, poly (meth) acrylic resin, polychlorinated acid modified with maleic acid, fumaric acid, itaconic acid, maleic anhydride and other unsaturated carboxylic acids A film or sheet of a resin such as a vinyl resin or the like can be used. Further, in the present invention, for example, a catalyst obtained by combining a metallocene complex such as a catalyst obtained by combining zirconocene dichloride with methylalumoxane and alumoxane, that is, an ethylene-α-olefin copolymer obtained by polymerization using a metallocene catalyst is used. Polymers can be used. Specifically, the brand name “Kernel” manufactured by Mitsubishi Chemical Corporation, the brand name “Evolu” manufactured by Mitsui Petrochemical Industry Co., Ltd., Exxon Chemical (USA)
N Chemical Co., Ltd. product name "Exact (E
XACT) ", Dow Chemical, USA
MICAL) Affinity- (AFFI)
NITY), an ethylene-α-olefin copolymer polymerized using a metallocene catalyst such as trade name “ENGAGE”. Thus, the above-mentioned film or sheet can be used in a state of a coating film of a composition containing the resin. The thickness of the film or film or sheet is 10
The order of μm to 200 μm, preferably 30 μm to 150 μm is desirable.

In the present invention, the inorganic compound having antibacterial properties to be contained in at least the surface layer of the surface resin layer includes, for example, a silver ion-containing soluble glass capable of eluting silver ions at a constant rate. Can be used. This melting glass is used as an antibacterial agent, and is a general term for glass whose composition is adjusted in consideration of the physical and chemical properties of the glass so as to have a controlled melting rate. Is already known. In the present invention, in the silver ion-containing melting glass to which a silver compound is added, silver ions can be eluted at a predetermined constant rate over an arbitrary period of several hours to several years. Has antibacterial properties and exerts an antibacterial action against mold, various germs, bacteria and the like.

In the present invention, the silver ion-containing melting glass has a particle size of about 0.1 μm to 200 μm.
It is desirable to use one having a thickness of about 1 μm to 40 μm. In the above, if it is 0.1 μm or less, it is not preferable because the particles are too small and are buried in the surface resin layer, and if it is 200 μm or more,
It is extremely difficult to uniformly disperse the resin in the resin constituting the surface resin layer, which is not preferable. In the present invention, the amount of the silver ion-containing soluble glass contained in at least the surface portion of the surface resin layer is 0.0
It is preferably about 05% by weight to 15% by weight. In the above,
When the content is less than 0.005% by weight, the antibacterial effect of the eluted silver ions becomes insufficient, which is not preferable.
If the content is not less than% by weight, mixing and dispersion into the resin constituting the surface resin layer becomes difficult, which is not desirable.

Next, in the present invention, a method of dispersing and containing a silver ion-containing soluble glass on at least the surface of the surface resin layer will be described.
The following method can be adopted. First, using a Banbury-type mixer, a roller-type mixer, or the like, the above-mentioned silver ion-containing soluble glass, etc.
The required additives and the like are arbitrarily added, thoroughly mixed and kneaded to produce a master batch, and then the master batch is mixed with the resin constituting the surface resin layer and thoroughly kneaded. Thereafter, a film is formed by using a conventionally known T-die method or inflation method, and a film or sheet containing a silver ion-containing soluble glass is produced.
A silver ion-containing soluble glass can be dispersed and contained in at least the surface portion of the surface resin layer. In the above,
In particular, when a co-extruded film or sheet is produced by a co-extrusion method using a T-die method or an inflation method, silver is applied only to one of the co-extruded film or sheet. A film or a sheet containing the ion-containing soluble glass can be produced, whereby the silver ion-containing soluble glass can be contained and dispersed on the surface constituting the surface resin layer. The other coextruded film or sheet can be a film or sheet having functions such as strength and barrier properties.

Next, in the present invention, as a material constituting the above-mentioned intermediate layer, for example, a substrate having various barrier properties can be used. As the base material, a material having a property of blocking light such as sunlight or a property of not transmitting water vapor, water, gas, or the like can be used. A composite base material or the like obtained by combining the above base materials may be used. Specifically, for example, an aluminum foil having a light-shielding property, a barrier property against oxygen or water vapor or the like, a resin film having a vapor-deposited film thereof, an inorganic oxide such as silicon oxide or aluminum oxide having a barrier property against oxygen or water vapor or the like. Film of a resin having a vapor-deposited film of a substance, water vapor, low-density polyethylene having a barrier property against water, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene copolymer and other resins. Films or sheets, resins such as polyvinylidene chloride, polyvinyl alcohol, saponified ethylene-vinyl acetate copolymer, etc., which have a barrier property against gas such as oxygen; Is formed into a film by adding and kneading other desired additives. Film or sheet of various colored resins having a light-- can be used bets like. These materials can be used alone or in combination of two or more. The thickness of the above-mentioned film or sheet is arbitrary, but is usually preferably about 5 μm to 300 μm, more preferably about 10 μm to 100 μm. Further, in the above description, an aluminum foil having a thickness of about 5 μm to 30 μm, and an aluminum or inorganic oxide deposited film having a thickness of about 100 to 3000 mm can be used. Examples of the resin film supporting the above-mentioned vapor-deposited film include a polyester film, a polyamide film, a polyolefin film, a polyvinyl chloride film, a polycarbonate film, a polyvinylidene chloride film, a polyvinyl alcohol film, and an ethylene-acetic acid film. Saponified vinyl copolymer films and the like can be used.

Further, in the above, as the inorganic oxide constituting the above-mentioned inorganic oxide vapor-deposited film layer, for example, silicon oxide (SiO _x ), aluminum oxide, indium oxide, tin oxide, zirconium oxide or the like is used. can do. Furthermore, in the present invention, the inorganic oxide may be a mixture of silicon monoxide and silicon dioxide, or a mixture of silicon oxide and aluminum oxide. In the present invention, as a method of forming the inorganic oxide thin film layer, the thin film layer is formed by forming a vapor deposition film by a vacuum vapor deposition method such as an ion beam method or an electron beam method, or a sputtering method. be able to. In the above description, the thickness of the inorganic oxide thin film layer is usually preferably about 500 to 2000 degrees in order to obtain sufficient barrier properties. In the above, when the thickness of the inorganic oxide thin film layer is 500 ° or less, it is difficult to expect the effect, and when it exceeds 2000 °, cracks and the like are liable to occur in the inorganic oxide thin film layer. In addition, there is a risk that the barrier property is reduced due to the warpage, and the material cost is increased.

[0018] Usually, the laminate tube container is subjected to severe physical and chemical conditions, so that the laminated material constituting the laminate tube container has strict packaging suitability. Various requirements such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealing property, quality maintenance, workability, hygiene, etc. are required. Is, in addition to the above materials,
Any other material that satisfies 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 (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, polyaceta Any of known resin films or sheets such as cellulose resin, polyurethane resin, nitrocellulose, etc. can be used. 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 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, a method of manufacturing the laminated material according to the present invention by using the above-mentioned materials in the present invention will be described. As the method, a normal packaging material is laminated. Methods, for example, wet lamination method, dry lamination method, solventless dry lamination method, T-die extrusion molding method, T-die coextrusion molding method, extrusion lamination method, coextrusion lamination method, inflation -Inflation method, multilayer inflation method, etc. Thus, in the present invention, when the above lamination is performed, if necessary, a pretreatment such as a corona treatment or an ozone treatment can be performed on the film.
(An urethane), polyethyleneimine, polybutadiene, organic titanium-based anchor coating agents,
Or polyurethane, polyacrylic, polyester, epoxy, polyvinyl acetate, cellulose,
Known anchors such as laminating adhesives and the like
Agents, adhesives and the like can be used.

In the above-described method for producing a laminated material, the extruded resin constituting the adhesive resin layer at the time of extruding and laminating is, for example, polyethylene,
Ethylene-α-olefin copolymer, polypropylene,
Polybutene, polyisobutene, polyisobutylene, polybutadiene, polyisoprene, ethylene-methacrylic acid copolymer, or copolymer of ethylene and unsaturated carboxylic acid such as ethylene-acrylic acid copolymer, or acid-modified polyolefin resin, ethylene -Ethyl acrylate copolymer, ionomer resin, ethylene-vinyl acetate copolymer, etc. can be used. Further, in the present invention, as the adhesive constituting the adhesive layer when dry laminating, specifically, a two-component curable urethane-based adhesive or a polyester urethane-based adhesive used in dry laminates and the like Polyether urethane adhesives, acrylic adhesives, polyester adhesives, polyamide adhesives, polyvinyl acetate adhesives, ethoxy adhesives, rubber adhesives, and the like 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, the laminated material produced as described above is used, and firstly, it is rolled, the overlapped end thereof is welded, and the extruded laminating tube container is manufactured. Then, above, for example, injection molding of high-density polyethylene or the like, and molding and welding by other molding methods to form a head such as a shoulder and a mouth, and then a cap is attached to the mouth. The extrusion laminating tube container according to the present invention is manufactured. Thus, in the present invention,
From the opening at the lower end of the extruded laminating tube container manufactured as described above, the contents to be filled and packed are filled, and then the opening is heat-sealed to form a bottom welded portion. Can manufacture packaged products. In the above, the contents to be filled and packaged include, for example, toothpaste, cosmetics, paste, paste, paste wasabi, cream,
Examples include paints, ointments, pharmaceuticals, and others. In the above, in addition to the above-described high-density polyethylene, ethylene-α-olefin polymerized using the above-described metallocene catalyst is used as a material for forming the shoulder, head, etc. of the laminating tube container. Copolymers and the like can also be used.

[0023]

EXAMPLES Next, the present invention will be described more specifically with reference to examples. Example 1 After melting 80 parts by weight of low density polyethylene (manufactured by Mitsui Petrochemical Co., Ltd., trade name: Mirason 16), melting glass containing silver ions (trade name, ion pure WA11i, manufactured by Ishizuka Glass Co., Ltd.) 20 parts by weight were added and mixed well so that the silver ion-containing glass content was 20%.
A wt% master batch was produced. Next, a mixture of 15 parts by weight of the above-prepared master batch and 85 parts by weight of linear low-density polyethylene (trade name, manufactured by Mitsui Petrochemical Industries, Ltd., Ultzex 3021F) was used as a first layer. Using a linear low-density polyethylene (manufactured by Idemitsu Petrochemical Co., Ltd., trade name, Mooretec 0238N) as the two layers, a multilayer film having a heat seal property with a thickness of 40 μm was produced by a multilayer inflation method. . In the above multilayer film, the first layer was a linear low-density polyethylene layer having a thickness of 10 μm and having antibacterial properties, and the second layer was a linear low-density polyethylene layer having a thickness of 30 μm. Next, a biaxially stretched polyethylene terephthalate film having a thickness of 25 μm having a desired printed pattern and a thickness of 70 μm.
A 20 μm thick polyethylene film was extruded with a low density polyethylene to a thickness of 20 μm and bonded by a sand lamination method. Further, a 10 μm thick aluminum foil was coated on the surface of the milky polyethylene film with an ethylene-methacrylic acid copolymer. The polymer was extruded to a thickness of 25 μm and bonded together by a sand lamination method to produce an intermediate laminated material. Next, the multilayer film produced above was used as a surface resin layer, and the first layer having a thickness of 10
The linear low-density polyethylene layer having an antibacterial property of μm is the outermost surface, and the biaxially stretched polyethylene terephthalate of the intermediate laminated material produced above is provided on the second layer of the linear low-density polyethylene layer having a thickness of 30 μm. With the two film-curable urethane-based adhesives facing each other, dry laminating is performed, and a 50-μm-thick low-density polyethylene film is coated on the aluminum foil surface of the intermediate laminated material with ethylene-methacrylic. Using an acid copolymer, it was extruded to a thickness of 40 μm and bonded by a sand lamination method to produce a laminate according to the present invention having the following layer constitution.
Antibacterial linear low-density polyethylene layer having a thickness of 10 μm, linear low-density polyethylene layer having a thickness of 30 μm / adhesive layer / biaxially stretched polyethylene terephthalate having a thickness of 25 μm
Film / printed pattern layer / low-density polyethylene layer having a thickness of 20 μm / milk-white polyethylene film having a thickness of 70 μm /
Ethylene-methacrylic acid copolymer layer having a thickness of 25 μm / aluminum foil having a thickness of 10 μm / ethylene-methacrylic acid copolymer layer having a thickness of 40 μm / low-density polyethylene film having a thickness of 50 μm

Example 2 In the same manner as in Example 1 described above, a 25 μm-thick biaxially oriented polyethylene terephthalate film having a desired printed pattern and a 70 μm-thick opalescent polyethylene film were mixed with a low-density polyethylene. And extruded to a thickness of 20 μm and stuck by a sand lamination method. Furthermore, an aluminum foil having a thickness of 10 μm was extruded on the opalescent polyethylene film surface to a thickness of 25 μm using an ethylene-methacrylic acid copolymer. An intermediate laminated material was manufactured by laminating by a sand luminescence method. On the other hand, after melting 80 parts by weight of low-density polyethylene (manufactured by Mitsui Petrochemical Industry Co., Ltd., trade name, Mirason 16), a silver ion-containing melting glass (trade name, ion pure WA11i, manufactured by Ishizuka Glass Co., Ltd.) 20 Add parts by weight, mix well,
Kneading produced a masterbatch having a silver ion-containing fusing glass content of 20% by weight. Next, 15 parts by weight of the master batch produced above was mixed with linear low-density polyethylene (trade name, Mirason 1 manufactured by Mitsui Petrochemical Industries, Ltd.).
1) A mixture obtained by mixing with 85 parts by weight was used as a first layer, and a second layer was formed using a linear low-density polyethylene (trade name, Mirason 11, manufactured by Mitsui Petrochemical Industries, Ltd.) by a multilayer extrusion method. The first layer constitutes the outermost layer,
The second layer was coextruded so as to face the biaxially stretched polyethylene terephthalate film surface of the intermediate laminate produced above to form a heat-sealing multilayer film having a thickness of 60 μm. In the above multilayer film, the first layer was a linear low-density polyethylene layer having a thickness of 10 μm and having antibacterial properties, and the second layer was a linear low-density polyethylene layer having a thickness of 50 μm. Next, after laminating the multilayer film and the intermediate laminated material as described above, a 50-μm-thick low-density polyethylene film is further formed on the aluminum foil surface of the intermediate laminated material using an ethylene-methacrylic acid copolymer. Extruded to 40 μm
The laminated material according to the present invention having the following layer constitution was manufactured by laminating the laminated materials according to the present invention. Antimicrobial linear low-density polyethylene layer having a thickness of 10 μm, linear low-density polyethylene layer having a thickness of 50 μm / biaxially stretched polyethylene terephthalate film having a thickness of 25 μm / printing pattern layer / thickness of 20 μm
m low density polyethylene layer / 70 μm thick milky white polyethylene film / 25 μm thick ethylene-methacrylic acid copolymer layer / 10 μm thick aluminum foil / 4 thickness
0 μm ethylene-methacrylic acid copolymer layer / thickness 50
μm low density polyethylene film

COMPARATIVE EXAMPLE 1 A linear low-density polyethylene (manufactured by Mitsui Petrochemical Co., Ltd., trade name: Ultex X 3021F) was used as a first layer, and a linear low-density polyethylene (manufactured by Idemitsu Petrochemical Co., Ltd.) was used as a second layer. Using a trade name, Moretec 0238N), a multilayer film having a heat seal property with a thickness of 40 μm was produced by a multilayer inflation method. In the above multilayer film, the first layer is a linear low-density polyethylene layer having a thickness of 10 μm, and the second layer has a thickness of 30 μm.
Was a linear low-density polyethylene layer. Using the multilayer film produced above, a laminated material having the following layer constitution was produced in the same manner as in Example 1 above. Thickness 1
0 μm linear low density polyethylene layer, 30 μm thick linear low density polyethylene layer / adhesive layer / 25 μm thick 2
Axial stretched polyethylene terephthalate film / printed pattern layer / low density polyethylene layer with a thickness of 20 μm / thickness 70 μm
m / milk-white polyethylene film / 25 μm-thick ethylene-methacrylic acid copolymer layer / 10 μm-thick aluminum foil / 40 μm-thick ethylene-methacrylic acid copolymer layer / 50 μm-thick low-density polyethylene film

Comparative Example 2 The intermediate laminated material used in Example 2 was used.
On the surface of the axially stretched polyethylene terephthalate film, a linear low-density polyethylene (trade name, Mirason 11 manufactured by Mitsui Petrochemical Industry Co., Ltd.) is used as a first layer, and a linear low-density polyethylene (Mitsui Petrochemical Industry) is used as a second layer. The first layer constitutes the outermost surface layer and the second layer is a biaxially stretched polyethylene terephthalate of the above-mentioned intermediate laminated material by a multilayer extrusion method using a product name, Mirason 11) manufactured by Co., Ltd. A multi-layer film having a heat seal property of 60 μm in thickness was laminated by co-extrusion so as to face the film surface. In the above multilayer film, the first layer is
A linear low density polyethylene layer having a thickness of 10 μm;
The layer was a 50 μm thick linear low density polyethylene layer. Hereinafter, in the same manner as in Example 2 described above, a laminated material having the following layer configuration was manufactured. Linear low-density polyethylene layer having a thickness of 10 μm and linear low-density polyethylene layer having a thickness of 50 μm / biaxially stretched polyethylene terephthalate having a thickness of 25 μm
Film / printed pattern layer / low-density polyethylene layer having a thickness of 20 μm / milk-white polyethylene film having a thickness of 70 μm /
Ethylene-methacrylic acid copolymer layer having a thickness of 25 μm / aluminum foil having a thickness of 10 μm / ethylene-methacrylic acid copolymer layer having a thickness of 40 μm / low-density polyethylene film having a thickness of 50 μm

Experimental Examples Using the laminated materials manufactured in Examples 1 and 2 and Comparative Examples 1 and 2, first, each laminated material was punched to produce a blank plate. Rolled and heat-melted the polymerized portion at the end, diameter 35mm, height 150m
Thus, a cylindrical body serving as a body constituting a laminating tube container of m 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 placed on the head
Using high-density polyethylene to which weight% was added, molding was performed by a compression molding method at a resin temperature of 245 ° C. Next, a cap is spirally wound on the mouth and neck of the cylinder having the above-mentioned head, and then the cylinder is removed from the mandrel. Thereafter, 135 g of a commercially available toothpaste is filled through the other opening of the cylinder. Then, the opening of the cylindrical body was sealed by heat welding. next,
Bacillus subtilis spores and Escherichia coli were sprayed and adhered to the surface of each tube package produced above at a rate of 10 ³ cells per E. coli and stored at 20 ° C. and 70% for 3 days. Thereafter, the number of bacteria was measured. The results are shown in Table 1 below.

[0028]

[Table 1]

As is clear from the above results, Example 1
It was confirmed that the number of adhered bacteria was extinct in the samples of Nos. 2 to 2 as compared with those of Comparative Examples 1 and 2.

[0030]

As apparent from the above description, the present invention focuses on inorganic compounds having antibacterial properties,
In a laminated material obtained by sequentially laminating a surface resin layer, an intermediate layer, and an inner resin layer, at least a surface layer of the surface resin layer, to produce a laminated material containing an inorganic compound having antibacterial properties, Using a laminated material, the surfaces of the surface resin layer and the inner resin layer at both ends of the laminated material are overlapped, and the opposite surface is heat-sealed to produce a cylindrical body. A mouth and a shoulder are formed in one opening of the body, and a cap is screwed into the mouth to produce a laminating tube container.
From the other opening of the laminating tube container, the contents such as toothpaste and cream are filled and then the opening is hermetically sealed to form a bottom seal portion. A packaged product using a laminating tube container is manufactured, and even under high humidity in a washroom, a bathroom, etc., there is no trace of bacteria, germs, etc. adhering to the surface of the container, and there is no trace of mold. No such occurrence is observed, and it is possible to manufacture an extremely hygienic laminating tube container having an antibacterial property which does not cause discomfort.

[Brief description of the drawings]

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

FIG. 2 is a schematic cross-sectional view illustrating an example of a layer configuration of a laminated material according to the present invention.

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

FIG. 4 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.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Surface resin layer 2 Intermediate layer 3 Inner surface resin layer 4 Laminate tube container forming laminated material 5 Inorganic compound which has antibacterial property 5a Silver ion containing inorganic compound 5b Silver ion containing soluble glass 6 Welding part 7 Cylindrical trunk part Reference Signs List 8 shoulder 9 mouth 10 cap 11 contents 12 bottom welded part A laminated material B laminated material C laminated material R Laminate tube container

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI B65D 35/08 B65D 35/08

Claims (6)

[Claims] 1. A laminated material comprising a surface resin layer, an intermediate layer, and an inner resin layer sequentially laminated, wherein at least a surface layer of the surface resin layer contains an inorganic compound having antibacterial properties. A laminated material characterized by the following. 2. The laminate according to claim 1, wherein the inorganic compound having antibacterial properties is a silver ion-containing inorganic compound that gradually elutes silver ions. 3. The laminated material according to claim 2, wherein the silver ion-containing inorganic compound is a silver ion-containing molten glass. 4. A laminate in which at least a surface resin layer, an intermediate layer, and an inner resin layer are sequentially laminated, wherein at least a surface layer of the surface resin layer contains an inorganic compound having antibacterial properties. The outermost layer and the innermost layer at both ends of the laminated material are overlapped with each other, and the opposing surfaces are heat-sealed.
A laminating tube container comprising a sealed tubular body, and a head comprising a shoulder and a mouth provided at one opening of the tubular body. 5. The laminating tube container according to claim 4, wherein the inorganic compound having antibacterial properties is a silver ion-containing inorganic compound that gradually elutes silver ions. 6. The laminating tube container according to claim 5, wherein the silver ion-containing inorganic compound is silver ion-containing molten glass.