JP2012144290A - Laminated material for toothpaste tube and tubular toothpaste container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated material for toothpaste tubes, which can be produced inexpensively by using a small number of base stocks.SOLUTION: The laminated material for toothpaste tubes includes an innermost layer, a gas barrier layer and an outermost layer from an inner layer toward an outer layer. Each of the innermost layer and the outermost layer includes a polypropylene film and the gas barrier layer includes a gas barrier polypropylene film or a polyethylene terephthalate film having a vapor-deposited film. The innermost layer and the gas barrier layer are stuck to each other and the gas barrier layer and the outermost layer are stuck to each other by a dry lamination method.

Description

  The present invention relates to a dentifrice tube laminate that can be manufactured at a low cost with the type of resin used, a dentifrice tube container and a dentifrice product made of the dentifrice laminate.

  Conventional toothpastes in tubes include abrasives such as calcium hydrogen phosphate, calcium carbonate, aluminum hydroxide; foaming agents such as lauroyl sarcosine soda, sodium lauryl sulfate, sucrose fatty acid ester; sorbitol, glycerin, propylene Moisturizing agents such as glycol; binders such as sodium alginate and carboxymethyl cellulose; in addition to medicinal ingredients such as fluoride and vitamin E, as flavoring agents, peppermint, spearmint, L-menthol, L-carvone, fruit flavors, It contains flower flavour, spice flavor, herb flavor, and wood flavor.

  Various types of toothpaste tube containers have been developed depending on the application and others, such as a layered material for toothpaste tubes that prevents the absorption of vitamin E contained as a medicinal component. In view of the fact that the residual amount of vitamin E is reduced when polyethylene is used for the innermost layer, the innermost layer and the outermost layer are made of at least one of polyacrylonitrile resin, ethylene-vinyl alcohol copolymer resin, polyester resin and homopolypropylene resin. It is composed of a thermoplastic resin (Patent Document 1). In particular, when homopolypropylene resin is used as the innermost layer, it is said that there is little weight loss during storage of vitamin E that can be expected to prevent alveolar pus leakage. In Example 1, a soft aluminum foil is dry laminated on a PET film, and a polyacrylonitrile resin film is further dry laminated on both sides thereof. In Example 2, a homopolypropylene film, a polyethylene film, a PET film, a metal-deposited PET film, an acid copolymer layer, an aluminum foil, an acid copolymer layer, a polyethylene film, and a homopolypropylene film are laminated in order from the innermost layer. In Example 2, a homopolypropylene film is used as the innermost layer, and the weight loss rate of vitamin E is within 10%.

  Also, a laminated tube container in which the outermost layer and the innermost layer are made of a thermoplastic resin, and a cylindrical tube body is constituted by a joining seal portion using a laminate sheet having an intermediate layer between the outermost layer and the innermost layer. A laminated tube container using at least one resin layer selected from polyacrylonitrile resin (PAN), ethylene-vinyl alcohol copolymer resin (EVOH) or cyclic polyolefin sulfone resin (TPO) as the innermost layer. There is also (patent document 2). The innermost layer described above functions as an active ingredient non-adsorbing layer for vitamin E, triclosan and the like, and can improve the stability of active ingredients such as vitamin E and triclosan. In the embodiment, aluminum foil is used as the intermediate layer.

  In addition, linear low density polyethylene is laminated on the vapor deposition surface of the vapor deposition film having a metal, metal oxide, or inorganic vapor deposition layer via an adhesive, and then the linear low density polyethylene is added to the other side of the vapor deposition film. There is also a restorative laminated tube container characterized in that a tube-shaped container is constructed by laminating a laminated film layer made of polyethylene / white ethylene / vinyl acetate copolymer / polyethylene on each side (patent) Reference 3). When an aluminum foil is used as the oxygen gas barrier layer, the load on the environment is large, so that the aluminum foil is not used and the resilience of the tube can be secured according to the above configuration.

  On the other hand, a toothpaste tube container is manufactured by forming a body part from a laminated material for toothpaste tubes and connecting a head part having a shoulder part and a mouth part to the body part, and a discontinuous part between the body part and the head part. If the bonding is not sufficient, the storage stability of the contents is lowered. The head connected to the toothpaste tube container is required to have gas barrier properties as well as moldability and adhesion to the cylindrical body, but polyolefin resins such as high-density polyethylene resins with high thermal stability, Since the oxygen gas barrier property is lacking and the rigidity is high, the head cannot be crushed by hand or the like, and the contents may remain. In addition, when compression molding the head composed of the shoulder and mouth, a cylindrically molded barrel member is attached to a mandrel, and a molding resin melted in a molding die formed on the upper surface of the mandrel is used. It is discharged in an annular shape and dropped, and the other molding die is pressed onto it and the shoulder and mouth are compression molded. At the same time, the opening end of the body member is thermally welded, but the molding resin is polyethylene. In this case, molding can be performed satisfactorily, but when polypropylene is used, the melt viscosity is low, so that the annular shape cannot be maintained, and stringing tends to occur. As a method of manufacturing a tube container by connecting such a body member, a shoulder portion, and a mouth portion, a method for manufacturing a tube container that is excellent in heat resistance, content preservation, and economy is disclosed. (Patent Document 4). Patent Document 4 is a tube container manufacturing method in which a shoulder portion and a mouth portion are formed by compression welding at the same time as resin molding at one opening end of a barrel member formed in a cylindrical shape, As a resin that forms at least the shoulder and mouth, a heat-resistant body formed in a cylindrical shape is used on a mandrel that is formed in a reverse funnel shape with a blended resin in which polyethylene is blended with polypropylene. When the member is mounted and the mixed resin is melt-extruded and supplied in an annular shape onto the mandrel molding die, an air blowing means is used as an auxiliary means to discharge the molten mixed resin discharged in an annular shape to the discharge unit. It is cut off from the mold and dropped onto the mandrel molding die, and then the other molding die is pressed onto it to perform compression molding of the shoulder and mouth, In addition, the mixed resin polyethylene is high density polyethylene, the content is 7 to 25% by weight, and the MFR of the mixed resin polypropylene is 5 or more. A method is disclosed. In addition, the tube container of patent document 4 has the heat resistance which can be retort-sterilized, and is excellent in the long-term storage property of the content.

JP-A-5-8352 JP-A-8-301212 Japanese Patent No. 3562931 Japanese Patent No. 4043912

  Toothpaste tube laminates have many required physical properties such as content protection and feeling of use, printed layers for product explanation, and resistance to content. As described above, dentifrices contain active substances such as flavoring agents and vitamins, but these components may be adsorbed on the innermost layer to reduce the remaining amount or change in flavoring. Adsorption of the active ingredient can be dealt with by increasing the addition amount of the specific component in advance by taking the adsorption amount into account, but it is not easy to prevent the change of the flavoring. On the other hand, in order to increase the residual ratio of volatile substances, there is a method of improving the gas barrier property, but it is preferable that the gas barrier property can be secured without using an aluminum foil from the viewpoint of disposal. The laminated materials for dentifrice tubes described in Patent Document 1 and Patent Document 2 are superior in that adsorption of vitamin E can be avoided, but an aluminum foil is used as a gas barrier layer. Therefore, it is desired to develop a dentifrice laminate for a dentifrice tube that can satisfy various required physical properties as a dentifrice laminate for a dentifrice tube and can be easily disposed of.

  Furthermore, if it is going to satisfy | fill various physical properties requested | required of the laminated material for dentifrice tubes, a layer structure will become complicated. For this reason, the number of layers increases, the manufacturing process is complicated, and the cost increases. For example, the laminated material for a dentifrice tube described in Patent Document 3 is obtained by laminating LLDPE on both surfaces of a vapor deposition film and laminating polyethylene / white ethylene / vinyl acetate copolymer / polyethylene on the other surface of the vapor deposition film. The film layers are laminated, and at least four kinds of film layers and an adhesive layer for dry lamination are required in addition to the vapor deposition film. Therefore, it is desired to develop a laminated material for a dentifrice tube that can be manufactured at a low cost with a simple structure by reducing the types of materials used.

  In addition, the toothpaste tube container needs to have a head portion having a shoulder portion and a mouth portion connected to a cylindrical trunk portion made of a laminated material for a toothpaste tube. In Patent Document 4, the head is connected to the cylindrical body by compression molding, but if the compatibility between the cylindrical body and the head is not compatible, the head and the cylindrical body are bonded. The strength may decrease.

In view of the above situation, it is desired to develop a toothpaste tube laminate and a toothpaste tube container that does not adsorb contents and does not change the flavoring from opening to end of use.
Furthermore, it is desired to develop a toothpaste tube container that is excellent in adhesiveness and gas barrier properties with the above-mentioned toothpaste tube laminate and that has a simplified material type.

  As a result of examining the dentifrice tube laminate in detail, the present inventors have used unstretched polypropylene films for the innermost layer and the outermost layer, and the gas barrier polypropylene film is used as the gas barrier layer between the innermost layer and the outermost layer. A tube body for toothpaste is prepared by connecting a head portion having a shoulder portion and a mouth portion formed of polypropylene resin to a cylindrical body portion laminated as follows, and a dentifrice is filled, and 40 ° C., 6 months When the sensory evaluation of the contents after storage was performed, it was found that the adhesive strength of the cylindrical body and the adhesive strength between the cylindrical body and the head were excellent and the sensory evaluation was extremely high.

  That is, the present invention comprises at least an innermost layer, a gas barrier layer and an outermost layer from the inner layer to the outer layer, wherein the innermost layer and the outermost layer are polypropylene films, and the gas barrier layer is a gas barrier polypropylene film or vapor-deposited polyethylene terephthalate. The present invention provides a laminated material for a dentifrice tube, which is a film, wherein the innermost layer and the gas barrier layer, and the gas barrier layer and the outermost layer are dry-laminated.

  The present invention is characterized in that an opaque layer is further laminated between the innermost layer and the gas barrier layer, and the innermost layer and the opaque layer, and the opaque layer and the gas barrier layer are bonded by dry lamination. A laminated material for a dentifrice tube is provided.

The present invention provides the above-mentioned laminated material for a dentifrice tube, wherein a printed layer is formed on at least one side of the gas barrier layer.
The present invention provides the above-mentioned laminated material for a dentifrice tube, wherein the gas barrier layer is white.

  In the present invention, a head portion made of polypropylene resin and having a shoulder portion and a mouth portion is continuously provided at one open end of a cylindrical body portion formed of the above-mentioned dentifrice tube laminate, and the head portion The present invention provides a toothpaste tube container having a cap attached thereto.

The present invention provides a dentifrice product obtained by filling a dentifrice into the above toothpaste tube container.
The present invention forms a cylindrical body from the above-mentioned laminated material for dentifrice tube, and injection-molds a head made of polypropylene resin at one open end of the cylindrical body and having a shoulder and a mouth. Alternatively, the present invention provides a method for producing a toothpaste tube container, characterized in that it is provided continuously by compression molding.

  According to the present invention, the layer configuration can be simplified by laminating a polypropylene film as the innermost layer and the outermost layer, and a gas barrier polypropylene or vapor-deposited polyethylene terephthalate film as the gas barrier layer. And it can be prepared at low cost. In addition, polypropylene is extremely excellent in the storage stability of the contents, and high sensory evaluation can be obtained over a long period of time.

  The laminated material for a dentifrice tube of the present invention is one in which the innermost layer, the gas barrier layer, and the outermost layer are each dry-laminated and bonded, and if a tandem laminated material manufacturing apparatus is used, the dentifrice is passed by passing the apparatus once. A laminated material for tubes can be easily produced.

  According to the present invention, by using a polypropylene resin for the head having a shoulder and a mouth, it is possible to simplify the material used and to manufacture a toothpaste tube container that can be easily disposed of at low cost. Can do.

  Furthermore, when a head portion having a shoulder portion and a mouth portion of a polypropylene resin is formed on the trunk portion made of the laminated material for a dentifrice tube of the present invention, the adhesive strength is excellent and the compression method can be used.

It is a fragmentary sectional view of the tube container for toothpaste of this invention. FIG. 2 is a diagram showing an example of a preferred embodiment of the layer structure of the dentifrice tube laminate of the present invention, in which at least the innermost layer (10), the gas barrier layer (20), and the outermost layer (30) are in order from the innermost layer. These are laminated by a dry laminate adhesive layer (40). In addition, the gas barrier resin layer or vapor deposition layer which comprises a gas barrier layer (20) is shown with code | symbol 20 '. FIG. 2 shows a mode in which the gas barrier resin layer or the vapor deposition layer (20 ′) is laminated on the innermost layer side of the gas barrier layer (20), but the present invention is not limited to this. FIG. 3 is a view showing an example of a preferred embodiment of the layer structure of the dentifrice tube laminate of the present invention. In addition, an opaque layer (50) is further passed through the dry laminate adhesive layer (40) on the laminate shown in FIG. FIG. FIG. 4 is a diagram showing an example of a preferred embodiment of the layer configuration of the dentifrice tube laminate of the present invention, showing an embodiment in which a printed layer (60) is formed on the gas barrier layer (20) of the laminate of FIG. . FIG. 5 is a diagram showing an example of a preferred embodiment of the layer configuration of the dentifrice tube laminate of the present invention, showing an embodiment in which a shielding gas barrier layer (25) having a shielding effect is used as the gas barrier layer (20). . FIG. 6 is a partial cross-sectional view in which the toothpaste tube container of the present invention with the cap (C) attached to the head (B) is filled with the contents and the open end of the cylindrical body (A) is end-sealed. It is.

  The first of the present invention consists of at least an innermost layer, a gas barrier layer and an outermost layer from the inner layer to the outer layer, wherein the innermost layer and the outermost layer are polypropylene films, and the gas barrier layer is a gas barrier polypropylene film or vapor deposition It is a polyethylene terephthalate film, wherein the innermost layer and the gas barrier layer, and the gas barrier layer and the outermost layer are dry-laminated and bonded to each other.

  In the second aspect of the present invention, a head portion having a shoulder portion and a mouth portion is continuously provided at one opening end of a cylindrical body portion formed of the dentifrice tube laminate, and made of polypropylene resin. And a toothpaste tube container having a cap attached to the head.

Furthermore, a third aspect of the present invention is a toothpaste product obtained by filling a toothpaste into the toothpaste tube container. Hereinafter, the present invention will be described in detail.
(1) Configuration of Toothpaste Tube Container A partial cross-sectional view of the toothpaste tube container of the present invention is shown in FIG. The toothpaste tube container of the present invention comprises a cylindrical body part (A) and a head part (B) connected to the cylindrical body part (A).

  The said cylindrical trunk | drum (A) shape | molds the laminated material for dentifrice tubes of this invention in a cylinder shape, and is manufactured. There is no particular limitation on the method of forming the cylindrical body part (A), and it may be a lap joint in which the one side part and the other side part of the laminated material for dentifrice tube are welded together. A butt joint in which innermost layers at the end portions of the material are heat-sealed may be used. In addition, in FIG. 1, the aspect of the overlap joining in which the overlap part (A10) of the 1st side part and other side part of the laminated material for dentifrice tubes was shown is shown. FIG. 1B is a cross-sectional view taken along line X-X ′ in FIG.

  The head part (B) includes a shoulder part (B10) and a mouth part (B20) connected to the shoulder part (B10). In the toothpaste tube container, a cap (not shown) is attached to the mouth (B20). In FIG. 1A, a spiral for attaching the cap is formed on the outer periphery of the mouth portion (B20). However, the attachment of the cap is not limited to the spiral. You can choose.

  The head (B) is formed by molding a polypropylene resin, and can be formed by a compression molding method or an injection molding method. A cylindrical body (A) is prepared with a dentifrice tube laminate, a head (B) consisting of a shoulder and a mouth is connected to the open end, and a cap is attached to the mouth. The toothpaste tube container of the invention can be manufactured.

  If the contents are filled from the open end of the cylindrical body portion (A) of the toothpaste tube container, and the open end is thermally welded to form an end seal portion, the toothpaste tube container filled and packaged with the contents is used. Can be produced.

  The cylindrical body (A) constituting the toothpaste tube container of the present invention can be formed by either butt joining or lap joining because the innermost layer and the outermost layer are composed of a polypropylene layer. it can. Moreover, if the head (B) is a polypropylene resin, the adhesive strength between the cylindrical body (A) and the head (B) is high. In particular, if the gas barrier layer constituting the laminated material for a dentifrice tube is prepared from a gas barrier polypropylene, an all-polypropylene toothpaste tube container having a simplified layer structure is obtained.

(2) Dentifrice Tube Laminate As shown in FIG. 2, the dentifrice tube laminate used in the present invention has at least an innermost layer (10), a gas barrier layer (20) and an outermost layer (from the inner layer to the outer layer). 30), the innermost layer (10) and the outermost layer (30) are polypropylene films, the gas barrier layer (20) is a gas barrier polypropylene film or a vapor-deposited polyethylene terephthalate film, and the innermost layer (10). And a gas barrier layer (20), and a gas barrier layer (10) and an outermost layer (30) are dry laminated and bonded (40).

  As shown in FIG. 3, an opaque layer (50) may be further laminated between the innermost layer (10) and the gas barrier layer (20). As shown in FIG. 4, the gas barrier layer (20 ) May have a printing layer (60) formed on at least one side thereof. Moreover, as shown in FIG. 5, the film which comprises the said gas barrier layer is the shielding white gas barrier layer (25) which is white which has shielding property, and has shielding property and gas barrier property.

The present invention is characterized in that a gas barrier polypropylene film or a vapor-deposited polyethylene terephthalate film is used as the gas barrier layer (20), and each layer is laminated with a dry laminate adhesive. Conventionally, for example, as disclosed in Japanese Patent Application Laid-Open No. 2007-144688, there is a laminated material in which an innermost layer and an outermost layer are prepared from polypropylene, and it is used for a retort pack that requires ensuring heat resistance. However, in fields that do not require heat treatment such as dentifrice, there is little need to use polypropylene for the outermost layer or innermost layer. However, an unstretched polypropylene film having a thickness of 100 μm is used as the innermost layer (10) and the outermost layer (30), and the oxygen permeability is 15 (cc / m ² · d) as the gas barrier layer (20) in order to simplify the layer structure.・ When a tube container for toothpaste was manufactured by laminating gas barrier polypropylene film of MPa) by dry lamination adhesion, extremely excellent evaluation results were obtained in a sensory evaluation for 6 months at 40 ° C. filled with a dentifrice. It was. In the sensory evaluation of dentifrices, it is thought that the change in the ratio of each of the plurality of flavoring agents affects the results of sensory evaluation, but the dentifrice tube laminate of the present invention has an excellent balance between these. It can be considered that the film has a wonderful effect that cannot be assumed as a polypropylene film.

  Moreover, as disclosed in JP-A-5-8352 and JP-A-8-30312, the polypropylene film has an extremely low adsorption rate for vitamin E, triclosan, and the like. In the present invention, the type of material can be simplified by using the same type of gas barrier polypropylene film as the polypropylene used for the outermost layer and the innermost layer, and the manufacturing process can be simplified by laminating each layer, It is possible to obtain a toothpaste tube container excellent in storage stability and sensory evaluation of contents. The same sensory evaluation results were obtained when a vapor-deposited polyethylene terephthalate film was used as the gas barrier layer. This has never been known before. In order to secure a high gas barrier property, there is a method of laminating a film having a higher oxygen permeability, but it is expensive, and when a high gas barrier film is used, the sensory test is not always excellent. The present invention is extremely excellent in that it is inexpensive and can produce a high-quality laminated material for a dentifrice tube that can actually provide a high sensory evaluation.

(I) Polypropylene film The polypropylene film used as the outermost layer (30) and the innermost layer (10) constituting the laminated material for a dentifrice tube of the present invention is an unstretched polypropylene film. There is no particular limitation as long as it functions as a heat seal layer. Accordingly, examples of the polypropylene include atactic polypropylene and syndiotactic polypropylene, and may be homopolypropylene, random copolymer polypropylene, or block copolymer polypropylene. Since both the outermost layer and the innermost layer are made of polypropylene film, the cylindrical body can be manufactured by various welding methods, and the selection range of the manufacturing process can be set widely.

  On the other hand, in order to function as a heat seal layer, the thermal bonding temperature is preferably 120 to 280 ° C. Moreover, in order to ensure the high adhesive strength of a cylindrical trunk | drum, it is preferable that breaking strength (MPa) is MD / TD = 40 or more / 30 or more. Accordingly, the comonomer copolymerized with propylene includes ethylene, butene, hexene, 4-methylpentene, octene, and the like, which can be appropriately selected and used within the range of the above characteristics.

  The thickness of the polypropylene film is 100 to 200 μm, more preferably 100 to 150 μm for both the outermost layer and the innermost layer. However, the innermost layer and the outermost layer may be polypropylene films of the same type and the same thickness or different polypropylene films. If it is the said range, it is because high adhesive strength can be ensured in formation of a cylindrical trunk | drum, and continuous connection with a cylindrical trunk | drum and a head, and the high preservability of the content can be ensured.

(Ii) Gas barrier polypropylene film Examples of the gas barrier polypropylene film used as the gas barrier layer (20) in the present invention include a film obtained by coating a polypropylene film with a gas barrier resin layer. In FIG. 2, the gas barrier resin layer laminated on the gas barrier layer (20) is indicated by reference numeral 20 ′.

  Examples of the gas barrier resin layer include a polyvinyl alcohol resin, a polyvinylidene chloride resin, an ethylene-vinyl alcohol copolymer (EVOH), and the like. The resin coating method can be appropriately selected from blade coaters, bar coaters, air knife coaters, slit die coaters, curtain coaters, gravure coaters, roll coaters, gate roll coaters, spray coaters, and known methods. The gas barrier resin can be applied to the polypropylene film so as to have the oxygen permeability, and used as a gas barrier propylene film.

  As the polypropylene film constituting the gas barrier polypropylene film, a biaxially stretched polypropylene film can be suitably used. The thickness is 10 to 100 μm, preferably 10 to 50 μm, more preferably 10 to 30 μm.

The gas barrier polypropylene film has an oxygen permeability (cc / m ² · d · MPa) of 70 or less, more preferably 50 or less. This is because, within this range, the sensory test when the dentifrice is filled is excellent.

Commercial products can also be used. For example, polyvinyl alcohol coat A-OP of Tosero Co., Ltd. can be illustrated.
(Iii) Vapor-deposited polyethylene terephthalate film As the vapor-deposited polyethylene terephthalate film used as a gas barrier layer in the present invention, for example, a biaxially stretched polyethylene terephthalate film in which a thin film layer such as an inorganic oxide or an oxide of an amphoteric metal is formed. There is.

  As the polyethylene terephthalate film constituting the vapor-deposited polyethylene terephthalate film, a biaxially stretched polyethylene terephthalate film can be suitably used. The thickness is 10 to 100 μm, preferably 10 to 50 μm, more preferably 10 to 30 μm.

  The above film is provided with a vapor deposition film containing a compound of one or more elements selected from inorganic elements, oxygen, and hydrogen and carbon or simple carbon, and an oxide of the inorganic element. Examples of the inorganic oxide constituting the deposited film include silicon oxide, tin oxide, zinc oxide, indium oxide, titanium oxide, aluminum oxide, and magnesium oxide. That is, the inorganic element is silicon, tin, zinc, indium, titanium, aluminum, magnesium, and the like, among which silicon is most preferable.

  Examples of the method for forming the vapor deposition film on the surface of the resin film include physical vapor deposition and chemical vapor deposition. As the physical vapor deposition method, the evaporation source is heated by resistance heating, high-frequency induction heating, electron beam heating, etc. under high vacuum to evaporate and sublimate, thereby depositing a vapor deposition film such as the above inorganic oxide on the film. Can be formed. As the evaporation source, the same oxide as described above can be used. When vapor deposition is performed using such an evaporation source, in order to make up for the lack of free oxygen, a method of introducing oxygen from the outside and activating the oxygen with plasma or the like to oxidize the evaporated particles may be used. it can.

  Such a physical vapor deposition method may be used, but if a chemical vapor deposition method as described below is used, the vapor deposition film is formed following the flexibility of the film, so that a flexible film can be obtained, and pinholes and cracks can be obtained. Occurrence is prevented, which is more preferable. For example, when the inorganic oxide constituting the deposited film is silicon oxide, the organosilicon compound forming the deposited film layer is 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinylmethyldisiloxane. Siloxane, methyltrimethoxysilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, phenyltrimethoxysilane, methyltrimethoxy It can be selected from silane, methyltriethoxysilane, octamethylcyclotetrasiloxane, and the like, and preferably 1,1,3,3-tetramethyldisiloxane and hexamethyldisiloxane.

  A vacuum chamber of a plasma chemical vapor deposition apparatus in which a film for adhering a vapor deposition film is prepared by vaporizing the organosilicon compound, which is a liquid, and mixing oxygen and an inert gas such as helium or argon. -Blowing in, silicon is turned into plasma by high frequency or electromagnetic waves, and a deposited film having a thickness of about 60 to 500 mm is formed while being oxidized by oxygen. The deposited film thus formed contains a compound of one or more elements of silicon, oxygen, and hydrogen with carbon or a simple substance of carbon, and an oxide of silicon. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a simple substance of carbon is in the form of graphite, diamond, or fullerene, further includes an organic silicon compound as a raw material or a derivative thereof. There is a case. Specific examples include hydrocarbons having an alkyl group such as a methyl group, hydrosilica having a silyl group and a silylene group, and derivatives having a hydroxyl group such as silanol. The type and amount of the compound contained in the gas barrier layer can be controlled by changing the composition of the source gas and the deposition conditions.

  In this vapor-deposited film, the content of one or more elements of silicon, oxygen, and hydrogen described above and carbon or simple carbon and an oxide compound of silicon is 0.1 to 40 wt%, particularly 5 to 20 wt%. % Is preferred. If this content is less than 0.1 wt%, the impact resistance and spreadability of the gas barrier layer will be insufficient, cracks may occur due to bending and the like, and high gas barrier properties cannot be maintained. On the contrary, if it exceeds 40 wt%, the gas barrier property is lowered, which is not preferable. In addition, the concentration of the compound composed of one or more elements among the above-mentioned carbon, hydrogen, silicon and oxygen contained in the deposited film is high on the surface of the deposited film and decreases from the surface toward the interface with the base film. When formed in such a manner, the impact resistance is improved on the surface where cracks are most likely to occur, and the adhesion between the base film and the deposited film becomes strong, which is preferable.

Moreover, as a film having this deposited film, a film having a total light transmittance of 75% or more, an oxygen transmission rate of 10 cc / m ² · day · atm or less, and a water vapor transmission rate of 10 g / m ² · day · atm or less is desirable. The film properties of the silicon oxide vapor deposition film will be described as an example. The silicon oxide vapor deposition film is composed of a mixture of SiO, Si ₃ O 4, Si ₂ O ₃ , SiO _2, etc. , SiOx (x = 1 to 2), and its properties are glassy. In addition, as a thin film layer of an inorganic oxide, the case of using silicon oxide is preferable because it is very little colored and good barrier performance is obtained.

  In this invention, a commercial item can also be used as a vapor deposition polyethylene terephthalate film. For example, a product name “Tech Barrier” manufactured by Mitsubishi Chemical Corporation can be preferably used.

(Iv) Opaque layer In the present invention, an opaque layer is preferably laminated between the gas barrier layer and the innermost layer. In the present invention, the opaque layer means an opaque layer capable of shielding the contents from the appearance of the toothpaste tube container. The laminated material for a dentifrice tube of the present invention does not use an aluminum foil as a gas barrier layer, and therefore, the outermost layer, the innermost layer, and the gas barrier layer can all be composed of a transparent film. Therefore, it is preferable to laminate an opaque layer to shield the contents from the outside.

  Such an opaque layer is only required to shield the contents, but is preferably made of a polyolefin-based resin in order to simplify the type of material used. For example, there are a milky white resin film in which titanium oxide is kneaded with a polyolefin resin, a pearl resin film in which a pearl pigment is kneaded.

The thickness of the opaque layer is not particularly limited as long as the above object can be achieved. Generally, it is 10-100 micrometers, Preferably it is 10-50 micrometers.
In addition, without forming an opaque layer separately, a shielding function is added by kneading titanium oxide or pearl pigment to polypropylene or polyethylene terephthalate constituting the gas barrier layer, and the gas barrier layer and the opaque layer are used in combination. It may be a reactive gas barrier layer.

(V) Printing layer A printing layer can be formed in any layer which comprises the laminated material for dentifrice tubes. More preferably, a printing layer is formed on one side of the gas barrier layer. Preferably, a printing layer is formed on the innermost layer side. Since the print layer and the innermost layer are adjacent to each other via the dry lamination adhesive layer, the print on the print layer can be clearly laid out.

  The print layer is preferably formed after performing a surface treatment on the print layer forming side of the gas barrier layer in advance. Such surface treatments include corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc., and other pretreatments, etc. is there. In addition, a primer coating agent, an undercoat agent, an anchor coating agent or the like can be optionally applied in advance to form a surface treatment.

  The printing layer is composed of one or more ordinary ink vehicles as the main component, and if necessary, a plasticizer, a stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a curing agent, and a crosslinking agent. Add one or more additives such as additives, lubricants, antistatic agents, fillers, etc., add colorants such as dyes and pigments, and use solvents, diluents, etc. An ink composition obtained by kneading to prepare an ink composition can be used. As such an ink vehicle, known ones such as sesame oil, drill oil, soybean oil, hydrocarbon oil, rosin, rosin ester, rosin modified resin, shellac, alkyd resin, phenolic resin, maleic resin, Natural resin, hydrocarbon resin, polyvinyl chloride resin, polyacetic acid resin, polystyrene resin, polyvinyl butyral resin, acrylic or methacrylic resin, polyamide resin, polyester resin, polyurethane resin, epoxy resin, urea resin , Melamine resin, amino alkyd resin, nitrocellulose, ethyl cellulose, chlorinated rubber, cyclized rubber, etc. can be used alone or in combination.

The printing method may be a printing method such as relief printing, screen printing, transfer printing, flexographic printing, or the like in addition to gravure printing.
(Vi) Dry Laminate Adhesive Layer In the present invention, the outermost layer and the gas barrier layer, and the gas barrier layer and the innermost layer are dry laminated. When the opaque layer is laminated, the gas barrier layer and the opaque layer, and the opaque layer and the innermost layer are dry laminated. At that time, a primer layer is formed in advance by applying a primer to each layer, and then a base material such as a heat seal layer is laminated on the surface of the primer layer via a laminating adhesive using a dry lamination laminating method. it can.

  Dry laminate adhesion is often used when preparing a laminated material constituting a retort container, and there are few examples of dry lamination adhesion of all layers constituting a dentifrice tube laminated material. However, in the present invention, the above-mentioned innermost layer, gas barrier layer, and outermost layer were each dry-laminated and bonded to each other, so that an excellent dentifrice sensory test result could be obtained.

  Examples of the laminating adhesive used in the present invention include polyvinyl acetate adhesives, homopolymers such as ethyl acrylate, butyl, and 2-ethylhexyl ester, and co-polymers thereof with methyl methacrylate, acrylonitrile, styrene, and the like. Polyacrylate adhesives composed of polymers, cyanoacrylate adhesives, ethylene copolymer adhesives composed of copolymers of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, and methacrylic acid Cellulose adhesive, polyester adhesive, polyamide adhesive, polyimide adhesive, amino resin adhesive made of urea resin or melamine resin, phenol resin adhesive, epoxy adhesive, polyurethane adhesive , Reactive (meth) acrylic acid adhesive, chloropre Rubber, nitrile rubber, styrene - made of butadiene rubber inorganic adhesive, silicone adhesive, an alkali metal silicate, and the like low-melting glass inorganic adhesive, there are other adhesives.

  More preferably, for example, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, or aliphatic polyisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, etc. Mainly used are polyether polyurethane resins, polyester polyurethane resins, and polyacrylate polyurethane resins obtained by reacting polyfunctional isocyanates with polyether polyols, polyester polyols, polyacrylate polyols, and other hydroxyl group-containing compounds. Ingredients. According to these, a thin film rich in flexibility and flexibility can be formed, its tensile elongation is improved, it acts as a film having flexibility, flexibility, etc. on the polypropylene film and gas barrier layer, and laminate Processing suitability such as processing and printing can be improved.

  The composition system of these adhesives may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the property may be any of a film, a sheet, a powder, a solid, and the like. Furthermore, the reaction mechanism may be any of a chemical reaction type, a solvent volatilization type, a heat welding type, a hot pressure type, and the like.

Although there is no limitation in the usage-amount of the adhesive agent for lamination, Generally, it is 0.1-10 g / m < ² > (dry state). The laminating adhesive can be applied by roll coating, gravure coating, kiss coating or other coating methods or printing methods.

(Vii) Layer structure of laminated material A preferred embodiment of the laminated material for a dentifrice tube of the present invention is shown in FIG. In FIG. 2, at least the innermost layer (10), the gas barrier layer (20), and the outermost layer (30) are laminated in order from the innermost layer via the dry laminate adhesive layer (40). In addition, the gas barrier resin layer or vapor deposition layer which comprises a gas barrier layer (20) is shown with code | symbol 20 '.

  Further, in FIG. 3, an opaque layer (50) is further laminated on the laminate shown in FIG. 2, and the innermost layer (10) and the opaque layer (50), and the opaque layer (50) and the gas barrier layer (20), Shows a layer structure of a laminated material for a dentifrice tube that is laminated via a dry laminate adhesive layer (40).

FIG. 4 shows a mode in which a printed layer (60) is formed on the gas barrier layer (20) in the laminated material shown in FIG.
FIG. 5 shows a mode in which a shielding gas barrier layer (25) having a shielding effect is used as the gas barrier layer (20). In FIG. 5, a printed layer may be further formed. In addition, although FIGS. 2-5 shows the aspect by which a gas barrier resin layer or vapor deposition layer (20 ') is laminated | stacked on the innermost layer side of a gas barrier layer (20), this invention is not limited to this. Absent.

  In the present invention, when a gas barrier polypropylene is used as the gas barrier layer (20), it becomes an all-polypropylene dentifrice tube laminate. Since the innermost layer (10) and the outermost layer (30) are made of polypropylene, it is easy to produce a cylindrical body portion, and since polypropylene has high adhesive strength, the storage stability of the contents is excellent.

  An example of a conventional layer structure is, as shown in a comparative example described later, a polyethylene film having a thickness of 80 μm / a polyethylene molten resin layer having a thickness of 25 μm / a PET film having a thickness of 12 μm / a printing layer / a polyethylene having a thickness of 25 μm. Melted resin layer / 100 μm thick milk white polyethylene film / dry laminated adhesive layer / 12 μm thick silica vapor deposited PET film / 25 μm thick ethylene methacrylate resin layer / 80 μm thick polyethylene film. A polyethylene film is used for the innermost layer and the outermost layer, a silica-deposited PET film is used as the gas barrier layer, and all are laminated by melt adhesion using a polyethylene resin or an ethylene methacrylate resin, except for lamination of the opaque layer and the gas barrier layer. Since a heat treatment such as retort is unnecessary, adjacent films are laminated via a molten resin layer, but the layer structure is complicated and the laminating process is not easy. For this reason, cheap manufacture was also difficult. ADVANTAGE OF THE INVENTION According to this invention, the laminated material for dentifrice tubes can be provided cheaply and simply by only three layers, an innermost layer, an outermost layer, and a gas barrier layer.

In addition, the laminated material for dentifrice tubes prepared by the above is 200-500 micrometers in thickness, More preferably, it is 200-350 micrometers.
(Viii) Method for Producing Dentifrice Tube Laminate The dentifrice tube laminate of the present invention is produced by dry-laminating each layer. For example, in the layer configuration shown in FIG. 2, the gas barrier layer (20), the innermost layer (10), and the outermost layer (30) are introduced into a tandem laminating apparatus, and the respective layers are dry laminated. Thereby, the laminated material for dentifrice tubes which consists of a laminated body of 3 layers can be manufactured only by letting each said film pass through a tandem-type lamination apparatus once.

  When the print layer (60) is formed on the gas barrier layer (20), the print layer is previously formed on the gas barrier layer, and then the gas barrier layer, the innermost layer, and the outermost layer are introduced into the tandem laminating apparatus. Then, each layer is dry laminated. Thereby, the laminated material for dentifrice tubes which consists of a laminated body of 3 layers can be manufactured only by letting each said film pass through a tandem-type lamination apparatus once.

  Further, when the opaque layer is laminated, if the gas barrier layer and the opaque layer are previously dry-laminated and bonded, the respective films are passed through a tandem laminating apparatus in the same manner as described above and the dentifrice comprising a four-layer laminate. A laminated material for a tube can be manufactured.

(5) Head In the present invention, a head having a shoulder and a mouth is connected to the cylindrical body made of the above-mentioned laminated material for a dentifrice tube. If the said head has a shoulder part and a mouth part, there will be no limitation in the structure in particular. Moreover, there is no restriction | limiting in particular also in a shaping | molding method, It can shape | mold by compression molding or injection molding.

  For example, when molding with a polypropylene resin alone, an injection molding method is suitable. According to the injection molding method, since the head can be molded with a single polypropylene resin, all toothpaste tube containers can be prepared with polypropylene.

  On the other hand, the head can also be formed by compression molding using a polypropylene resin. Polypropylene resin is a resin composed mainly of polypropylene and blended with other components.

  Examples of such polypropylene resins include resins containing 50 to 93% by mass of polypropylene, 7 to 50% by mass of high-density polyethylene resin, and 0 to 25% by mass of linear low-density polyethylene resin. .

The compression molding method can be sequentially performed, for example, in accordance with the method disclosed in Japanese Patent No. 4043912.
(7) Manufacturing method of toothpaste tube container The toothpaste tube container of the present invention is formed by continuously connecting the head to a cylindrical body portion made of the above-mentioned laminated material for toothpaste tubes. The said cylindrical trunk | drum can be formed on the 1 side edge part of the laminated material for dentifrice tubes, and the other side edge part is piled up to 1.0-3.0 mm, More preferably, it is 1.0-2.0 mm. . However, butt-bonding may be used in which both ends of the dentifrice tube laminate are bonded to each other in a palm-like manner, and further, a tape may be attached to the inner surfaces of both ends of the end portion of the dentifrice tube laminate.

  The said cylindrical trunk | drum can be formed by heat-seal | fusing the edge part of the laminated material for dentifrice tubes. As a heat sealing method for forming the cylindrical body portion, a known method such as a bar seal, a rotary roll seal, a belt seal, or a high frequency seal can be used.

Next, a head portion composed of a shoulder portion and a mouth portion is connected to the cylindrical body portion, whereby a toothpaste tube container can be manufactured.
The upper end of the cylindrical barrel is attached to a mandrel that is formed into a reverse funnel shape on the upper part, and the resin is melt-extruded into a ring and supplied onto the mandrel mold. Then, the mandrel is dropped onto the molding die, and then the other molding die is pressed thereon to perform compression molding of the shoulder portion and the mouth portion. Thereby, the tube container for toothpaste excellent in the adhesive strength of a head and a cylinder trunk | drum body part can be manufactured.

  Next, if a cap is attached to the mouth, a predetermined amount of dentifrice is filled from the open end of the cylindrical body, and the open end is thermally welded to form an end seal portion. A container can be obtained. FIG. 6 shows a partial cross-sectional view in which the toothpaste tube container with the cap (C) attached to the mouth part (B20) is filled with the contents and the open end of the cylindrical body part is end-sealed.

EXAMPLES Next, although an Example is given and this invention is demonstrated concretely, these Examples do not restrict | limit this invention at all.
(1) Example 1
Gravure printing was performed on the coating surface of a 20 μm gas barrier coating oriented polypropylene film (oxygen permeability 15 cc / m ² · d · MPa) to form a printed layer.

  Next, a 100 μm unstretched polypropylene film was laminated using a urethane-based two-component curable adhesive. Further, a non-printed surface of the stretched polypropylene film was laminated with a 100 μm unstretched polypropylene film using a urethane-based two-component curable adhesive to prepare a three-layer laminate film.

(2) Example 2
Gravure printing was performed on the coating surface of a 20 μm gas barrier coating oriented polypropylene film (oxygen permeability 15 cc / m ² · d · MPa) to form a printed layer.

  Next, a 30 μm milk-white stretched polypropylene film was laminated using a urethane-based two-component curable adhesive. Also, a 100 μm unstretched polypropylene film was laminated on the milky white stretched polypropylene film using a urethane two-component curable adhesive. Further, an unstretched polypropylene film of 100 μm was laminated on the non-printing surface of the gas barrier OPP of the previous laminated film using a urethane two-component curable adhesive to produce a four-layer laminated film.

(3) Example 3
A printing layer was formed by gravure printing on the vapor-deposited surface of a gas barrier PET film (oxygen permeability 1 cc / m ² · d · MPa) provided with a silica vapor-deposited layer on one side of a 12 μm PET film.

  Next, a 30 μm milk-white stretched polypropylene film was laminated using a urethane-based two-component curable adhesive. Also, a 100 μm unstretched polypropylene film was laminated on the milky white stretched polypropylene film using a urethane two-component curable adhesive. Further, an unstretched polypropylene film of 100 μm was laminated on the non-printing surface of the gas barrier PET film of the previous laminated film using a urethane-based two-component curable adhesive to produce a four-layer laminated film.

(4) Example 4
The laminated film prepared in Example 1 is cut to a width of 120 mm, and both sides thereof are overlapped with a width of 1.8 mm, welded at a temperature of 250 ° C. by heat sealing, and a cylindrical body is produced and cut to a length of 150 mm. did.

  A head portion composed of a shoulder portion and a mouth portion of a lami tube was molded at one open end of the cylindrical body portion by an injection molding method using polypropylene resin, and a toothpaste tube container was manufactured.

(5) Example 5
The laminated film prepared in Example 2 was cut to a width of 120 mm, and both sides thereof were overlapped with a width of 1.8 mm, welded at a temperature of 250 ° C. by heat sealing, a cylindrical body was produced, and cut to a length of 150 mm. .

  At one open end of the cylindrical body, a polypropylene resin, a linear low density polyethylene resin, and a high density polyethylene resin are mixed in a ratio of 50:20:30, and the shoulder portion of the lami tube is mixed with a compression molding method. The head part which consists of a mouth part was shape | molded, and the tube container for toothpaste was manufactured.

(6) Example 6
The laminated film prepared in Example 3 was cut to a width of 120 mm, both sides thereof were overlapped with a width of 1.8 mm, welded at a temperature of 250 ° C. by heat sealing, a cylindrical body was produced, and cut to a length of 150 mm. .

  Polypropylene resin, linear low-density polyethylene resin, and high-density polyethylene resin are mixed at a ratio of 50:10:40 at one open end of the cylindrical body, and the shoulder portion of the lami tube is mixed by a compression molding method. The head part which consists of a mouth part was shape | molded, and the tube container for toothpaste was manufactured.

(7) Comparative Example 1
100 μm milk white PEF and 12 μm silica-deposited PET were laminated with a urethane-based two-component curable adhesive.

  Next, after applying a urethane two-component curable anchor coating agent to the silica-deposited PET surface, 25 μm of ethylene methacrylate was extruded to laminate 80 μm of PEF. Then, 25 μm of polyethylene is extruded onto the milky white PEF surface of the previous laminate raw material, laminated on the printing surface of 12 μm PET film provided with a printing layer by gravure printing, and further 25 μm of polyethylene is extruded onto the non-printing surface of the PET film 80 μm PEF was laminated to produce a laminate.

(8) Comparative Example 2
The laminated material manufactured in Comparative Example 1 was cut to a width of 120 mm, both sides thereof were overlapped with a width of 1.8 mm, and welded by heat sealing to produce a cylindrical body portion, which was cut to a length of 150 mm. A head portion composed of a shoulder portion and a mouth portion of a lami tube was formed on one open end of the cylindrical body portion by a compression molding method using a high-density polyethylene resin, and a toothpaste tube container was manufactured.

(9) Evaluation of adhesive strength (i) Body portion The laminated films produced in Examples 1 to 3 and Comparative Example 1 were cut to a width of 120 mm, and both sides thereof were overlapped with a width of 1.8 mm and welded by heat sealing. A cylindrical body was prepared and cut to a length of 150 mm. A 15 mm wide cut was made at a right angle to the welded portion of the cylindrical body having a width of 1.8 mm. The 15 mm wide portion into which the cut was made was fixed to a chuck of a tensile tester, and the speed was 300 mm / sec. The strength at the time of pulling and breaking was measured. The results are shown in Table 1. As shown in Table 1, the laminates produced in Examples 1 to 3 had higher adhesive strength than the laminate produced in Comparative Example 1.

（ｉｉ）頭部
実施例４〜６、比較例２で製造した歯磨き用チューブ容器と頭部と筒状胴部との溶着部に直角に１５ｍｍ幅の切込みを入れた。前記切り込みをいれた１５ｍｍ幅の部分を引っ張り試験機のチャックに固定し、スピード３００ｍｍ／ｓｅｃ．で引っ張り、破断する際の強度を測定した。結果を表２に示す。表２に示すように、実施例４〜６で製造した歯磨き用チューブ容器は、比較例２で製造した歯磨き用チューブ容器に比べ、接着強度が高かった。

(Ii) Head A 15 mm-wide cut was made at right angles to the welded portion of the toothpaste tube container manufactured in Examples 4 to 6 and Comparative Example 2, the head, and the cylindrical body. The 15 mm wide portion into which the cut was made was fixed to a chuck of a tensile tester, and the speed was 300 mm / sec. The strength at the time of pulling and breaking was measured. The results are shown in Table 2. As shown in Table 2, the toothpaste tube containers produced in Examples 4 to 6 had higher adhesive strength than the toothpaste tube container produced in Comparative Example 2.

（１０）有効成分の残存試験
実施例４〜６および比較例２の歯磨き用チューブ容器にイソプロピルメチルフェノールを有効成分とする歯磨剤を充填し、４０℃、６ヶ月保存した。イソプロピルメチルフェノールの規定値に対する残存率を測定した。実施例４では９８．２％、比較例２では９４．５％であった。実施例５、実施例６についても実施例４と同等の残存率であった。表３に結果を示す。残存率は、◎：残存率９５〜１０５％、○：残存率９０〜９５％及び１０５〜１１０％、×：残存率９０％未満及び１１０を超える残存率（％）で表記した。

(10) Remaining test of active ingredients Dentifrices containing isopropylmethylphenol as active ingredients were filled in the toothpaste tube containers of Examples 4 to 6 and Comparative Example 2, and stored at 40 ° C for 6 months. The residual ratio with respect to the specified value of isopropylmethylphenol was measured. In Example 4, it was 98.2%, and in Comparative example 2, it was 94.5%. The remaining rates of Example 5 and Example 6 were the same as those of Example 4. Table 3 shows the results. The residual ratios are indicated by ◎: residual ratio 95 to 105%, ○: residual ratio 90 to 95% and 105 to 110%, x: residual ratio less than 90% and higher than 110 (%).

（１１）官能試験
実施例４〜６および比較例２の歯磨き用チューブ容器にイソプロピルメチルフェノールを有効成分とする歯磨剤を充填し、４０℃、６ヶ月保存した後の香味安定性を評価し、官能試験とした。表４に結果を示す。香味安定性は、◎：非常に良好、○：良好、×：劣化が認められる、で表記した。いずれの場合も良好な結果であったが、実施例４、実施例５は実施例６、比較例２より更に良い結果であった。

(11) Sensory test The dentifrice containing isopropylmethylphenol as an active ingredient was filled in the toothpaste tube containers of Examples 4 to 6 and Comparative Example 2, and the flavor stability after storage at 40 ° C. for 6 months was evaluated. A sensory test was performed. Table 4 shows the results. The flavor stability was expressed as ◎: very good, ○: good, ×: deterioration was observed. In all cases, good results were obtained, but Example 4 and Example 5 showed better results than Example 6 and Comparative Example 2.

  ADVANTAGE OF THE INVENTION According to this invention, the container for toothpaste tubes which consists of the laminated material for dentifrice tubes which is excellent in sensory evaluation by the simple layer structure, and the said laminated material for dentifrice tubes can be manufactured. Since the layer structure is simple, the production process is simple, and it can be produced at low cost, which is useful.

10 ... innermost layer,
20 ... gas barrier layer,
20 '... gas barrier resin layer or vapor deposition layer constituting the gas barrier layer (20),
25 ... shielding gas barrier layer,
30: outermost layer,
40 ... Dry laminate adhesive layer,
50 ... opaque layer,
60 ... Printing layer A ... Cylindrical body,
B ... head,
C ... Cap

Claims (7)

From the inner layer to the outer layer, it consists of at least the innermost layer, the gas barrier layer and the outermost layer,
The innermost layer and the outermost layer are polypropylene films,
The laminated material for a dentifrice tube, wherein the gas barrier layer is a gas barrier polypropylene film or a vapor-deposited polyethylene terephthalate film, and the innermost layer and the gas barrier layer, and the gas barrier layer and the outermost layer are bonded by dry lamination. An opaque layer is further laminated between the innermost layer and the gas barrier layer,
The dentifrice tube laminate according to claim 1, wherein the innermost layer and the opaque layer, and the opaque layer and the gas barrier layer are bonded by dry lamination.   The dentifrice tube laminate according to claim 1 or 2, wherein a printed layer is formed on at least one side of the gas barrier layer.   The denture tube laminate according to any one of claims 1 to 3, wherein the gas barrier layer is white.   The head part which consists of polypropylene resin and has a shoulder part and a mouth part at one opening end of the cylindrical trunk | drum formed with the laminated material for dentifrice tubes in any one of Claims 1-4 is connected. And a toothpaste tube container having a cap attached to the head.   A dentifrice product obtained by filling a toothpaste tube container according to claim 5 with a dentifrice. A cylindrical body is formed with the laminated material for a dentifrice tube according to any one of claims 1 to 4,
A method for producing a toothpaste tube container, characterized in that, at one open end of the cylindrical body, a head made of a polypropylene resin and having a shoulder and a mouth is continuously provided by compression molding.

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