JP2021020406A - Laminate and tube container - Google Patents

Abstract

To provide a laminate that protects a metal foil and has improved designability, and a tube container including such a laminate.SOLUTION: A laminate has a first sealant layer 12, a print substrate layer 13, a protective layer 19, an intermediate substrate layer 17, a metal foil 18, and a second sealant layer 15, which are laminated in the stated order, the protective layer 19 formed using a metal vapor deposition film. The metal vapor deposition film forming the protective layer 19 is an aluminum vapor deposition polyethylene terephthalate film.SELECTED DRAWING: Figure 7

Description

The present invention relates to a laminate that protects the metal foil that is the barrier layer and enhances the design, and a tube container that uses such a laminate.

Conventionally, as a laminate as a raw material for a tube container, a laminate structure having improved content resistance has been used (see, for example, Patent Document 1). The laminated material described in Patent Document 1 is composed of an intermediate support layer made of a biaxially stretched resin film, a barrier layer formed inside the intermediate support layer, and a thermoplastic resin layer located outside the intermediate support layer. By providing an outermost layer and an innermost layer made of a linear polyethylene resin, and an acid copolymer layer and a low-density polyethylene resin layer in this order from the barrier layer side between the innermost layer and the barrier layer, the structure is formed. The strength between layers is strengthened to improve the storage resistance of the contents.

Japanese Unexamined Patent Publication No. 7-195610

In the laminate constituting the tube container, a metal foil such as aluminum foil is preferably used as the barrier layer. However, in the conventional laminated body, when forming the tubular body to be the body portion or when forming the bottom seal portion on the body portion, the metal foil is cracked by the heat at the time of heat sealing, and the barrier property is lowered. There is a problem of doing. Further, since the body of the tube container is a laminated body, there is a problem that the metal foil, which is the barrier layer, has a matte appearance and the design is deteriorated.

Therefore, it is an object of the present invention to provide a laminate that protects a metal foil and enhances the design, and a tube container using such a laminate.

In order to solve the above problems, the present invention
The first sealant layer, the printing substrate layer, the protective layer, the metal foil, and the second sealant layer are laminated in this order.
The protective layer provides a laminate characterized by being formed using a metal-deposited film.

Moreover, the laminated body of this invention is
The metal foil is an aluminum foil.

Moreover, the laminated body of this invention is
The metal-deposited film is an aluminum-deposited polyethylene terephthalate film.

Moreover, the laminated body of this invention is
It is characterized in that at least one of the printing base material layer and the protective layer contains a plant-derived resin.

Moreover, the laminated body of this invention is
It is characterized in that at least one of the first sealant layer and the second sealant layer contains a plant-derived resin.

Moreover, the laminated body of this invention is
An intermediate base material layer is further provided between the protective layer and the metal foil.

In addition, the present invention
Provided is a tube container characterized in that the laminated body is used as a body portion.

According to the present invention, it is possible to provide a laminated body in which the metal foil is protected and the design is enhanced, and a tube container using such a laminated body.

It is a front view of the tube container with a cap attached. It is a partial cross-sectional view of a head molded body. It is sectional drawing of the cap attached to the tube container which concerns on one Embodiment of this invention. It is a figure which shows the tubular body part of the tube container which concerns on one Embodiment of this invention. It is a top view of the tube container which concerns on one Embodiment of this invention. It is a partial cross-sectional view of a tube container with a cap attached to a head molded body. It is sectional drawing of the laminated body of the body part of the tube container which concerns on one Embodiment of this invention. It is sectional drawing of the laminated body of the sealing seal used in the tube container which concerns on one Embodiment of this invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings.

However, the present invention is not limited to these concretely exemplified forms and various concretely described structures. In each figure, the size and ratio of the members may be changed or exaggerated for the sake of clarity. In addition, for the sake of readability, unnecessary parts for explanation and repeated codes may be omitted.

In the present specification, the "outer surface" and "inner surface" mean the "outer surface" and "inner surface" when the tube container 30 is manufactured using the laminated body 10. Further, "upper side" and "lower side" mean that when the tube container 30 has the mouth portion 36 and the cap 60 facing upward, the "upper side" means the mouth portion 36 side and the "lower side" means the mouth portion. Means the other side.

FIG. 1 is a front view of the tube container according to the present embodiment with the cap attached. As shown in FIG. 1, the tube container 30 according to the present embodiment is a head molded body produced by providing a body 31 and a synthetic resin to the body 31 by a method such as compression molding or injection molding. It is equipped with 37. The head molded body 37 further includes a shoulder portion 35, a mouth portion 36, and a neck portion 38. A sealing seal 20 is joined to the mouth 36 of the tube container 30, and a cap 60 is attached so as to cover the entire mouth 36, the neck 38 and a part of the shoulder 35.

The tube container 30 is connected to a neck portion 38 having a tubular body mouth portion 36 including an opening for discharge, a neck portion 38 which is connected to the mouth portion 36 and has a locking portion 45 whose outer circumference expands toward the lower side, and a neck portion 38. It has a head molded body 37 composed of a weight base tubular shoulder portion 35 which is provided and whose outer circumference expands toward the lower side. FIG. 2 is a partial cross-sectional view of the head molded body 37. In FIG. 2, the front surface of the head molded body 37 is shown in the right half, and the surface cut parallel to the front surface through the radial center thereof is shown in the left half. The hatched portion in the left half of FIG. 2 shows the substance of the head molded body 37, and the blank portion is hollow. The shoulder portion 35 is formed in the shape of a truncated cone, for example, which extends outward in the radial direction of the tube container 30 as the distance from the mouth portion 36 increases. For example, the shoulder 35 has an inclination of 30 degrees with respect to the horizontal. The shoulder portion 35 is continuously provided to the body portion 31 on the lower side.

The substantially cylindrical mouth portion 36 includes an annular top surface 46 at the upper end, an outer peripheral surface 47 extending from the radial outer side (outer edge) of the top surface 46 in the direction of the neck 38 and the shoulder 35 (axial direction), and a ceiling. It has an inner peripheral surface 48 extending in the axial direction from the inner edge of the surface 46. The top surface 46 is formed flat. The inner peripheral surface 48 of the mouth portion 36 defines an opening 49. The opening 49 serves as a discharge port for discharging the contents. The contents contained in the body portion 31 are discharged from the tube container 30 by passing through the opening 49.

The neck portion 38 is continuously provided between the mouth portion 36 and the shoulder portion 35, and has a locking portion 45 whose outer circumference expands from the mouth portion 36 toward the lower side. The locking portion 45 includes a portion whose outer circumference narrows as it goes downward from its maximum diameter portion. By providing the locking portion 45 having such a shape, the elastic leg piece 9A of the inner cylinder 9 of the cap 60 is locked.

In the present embodiment, the tube container 30 has a function of closing the opening 49 so that the contents are not discharged, and a sealing seal 20 having an easy-to-open property. Specifically, the sealing seal 20 is joined to the top surface 46 of the mouth portion 36. As shown in FIG. 2, the sealing seal 20 is attached to the top surface 46 so as to cover the opening 49. The top surface 46 and the sealing seal 20 may be joined in any manner. For example, the top surface 46 and the sealing seal 20 may be attached with an adhesive, or may be heat-sealed, thermocompression-bonded, or the like. The sealing seal 20 may be configured to break when a sharp object is pierced or a finger is pushed in. In such a case, the sealing seal 20 does not necessarily have to be easy to open.

The material of the sealing seal 20 may be selected according to the sealing property (barrier property) of the tube container 30, the bonding strength with the top surface 46, the piercing strength, the tearing strength, and the like. Therefore, a single layer body such as aluminum foil or biaxially stretched polypropylene (Oriented Polypropylene) or a laminated body thereof can be applied to the sealed seal 20.

Due to the structure as described above, the head molded body 37 has a gap between the outer cylinder 8 which is brought into contact with the shoulder portion 35 when pressed from the outside when the cap 60 is attached or detached, and the inside of the outer cylinder 8. It is detachable only by a cap 60 having an inner cylinder 9 for being arranged and fitted to the locking portion 45, and a linear motion in the vertical direction. That is, the head molded body 37 and the cap 60 are connected by so-called one-touch fitting. FIG. 3 is a cross-sectional view of the cap 60 used in the present embodiment as viewed from the front side. The cap 60 shown in FIG. 3 has the same shape as the cap used in the conventional one-touch fitting as shown in Japanese Patent Application Laid-Open No. 1-33483, and has a circular shape and a lower shape when viewed from the upper side (upper side). It is cylindrical when viewed from the side (bottom).

As shown in FIG. 3, the cap 60 used in the present embodiment is entirely molded of a flexible soft synthetic resin, and has a cylindrical outer cylinder 8 and an inner cylinder 9. The outer cylinder 8 has a lower end surface of the lower hem 8A formed on an inclined surface 8B, and the inner cylinder 9 has slits (not shown) formed at equal parts in the circumferential direction to form a plurality of elastic leg pieces 9A in a circle. They are arranged in a row. Further, an inward hook-shaped claw piece 7 is provided at the lower end of each elastic leg piece 9A, and the lower end surface of the hook-shaped claw piece 7 is an inclined surface 7A. Further, a cylindrical outer ring 2 is formed on the central upper surface of the inner cylinder 9.

The body portion 31 is a film-like laminate formed into a tubular shape. Then, one end of the body portion 31 extending in a tubular shape is joined to the shoulder portion 35. On the other hand, the other end of the body portion 31 is sealed by the bottom seal portion 39 in which the inner surfaces of the tubular body portion 31 are overlapped and joined (see FIG. 1). The bottom seal portion 39 may be joined after the body portion 31 is filled with the contents. The tube container 30, particularly the body portion 31, is configured to have flexibility (flexibility, squeeze property) capable of easily extruding a desired amount even if the contents have some viscosity. Good. The dimensions of the body portion 31 may be appropriately designed depending on the type of contents and the like, and for example, the diameter is 50 mm.

The tube container 30 having the above configuration is obtained through the following manufacturing process. First, as shown in FIG. 4, the laminated body 10 is used to superimpose a pair of bonded ends (hereinafter, may be referred to as both ends) 33A and 33B of the laminated body 10, and the overlapped portion thereof. A tubular body portion 31 is manufactured by heat-sealing and bonding the outer surface and the inner surface of the body portion 32 to form a body-pasting portion 32.

As a method for heat sealing, conventionally known methods such as bar seal, rotary roll seal, belt seal, impulse seal, high frequency seal, ultrasonic seal, and flame seal can be used.

Next, the tubular body 31 is mounted in a mold (not shown), and the head molded body is placed in one opening (upper side) 34A of the body 31 by, for example, compression molding or injection molding. 37 (shoulder 35, neck 38, mouth 36) is formed. In this way, the head molded body 37 (shoulder 35, neck 38, mouth 36) is integrally molded in one opening (upper side) 34A of the body 31, and the tube container 30 is manufactured.

On the other hand, the sealing seal 20 is obtained by punching the packaging material into a predetermined shape. The sealing portion 20A of the sealing seal 20 is applied to the top surface 46 of the mouth portion 36 of the tube container 30 and thermocompression bonded, and the sealing seal 20 is joined to the mouth portion 36. As a result, the opening 49 is covered with the sealing seal 20.

FIG. 5 is a top view of the tube container 30 before and after joining the sealing seal 20. FIG. 5A shows before joining the sealed seal 20, and FIG. 5B shows after joining the sealed seal 20. As shown in FIG. 5A, when viewed from the upper side (mouth 36 side), a top surface 46 corresponding to the thickness of the tubular mouth 36 is formed around the discharge opening 49, and the mouth A locking portion 45 is formed in which the outer circumference expands from the outer peripheral surface 47 of the portion 36 toward the lower side (backward direction in FIG. 5) of the tube container 30. Further, a shoulder portion 35 whose outer circumference expands toward the lower side of the tube container 30 (in the back direction in FIG. 5) is formed so as to connect the neck portion 38 provided with the locking portion 45 and the body portion 31.

The seal 20 is thermocompression-bonded to the top surface 46, which is the upper end of the mouth 36, so as to cover the opening 49 on the mouth 36 side shown in FIG. 5 (a). As shown in FIG. 5B, the sealing seal 20 has a sealing portion 20A defined by the outer peripheral surface 47 of the mouth portion 36, and a knob portion 20B protruding outward from the sealing portion 20A. The sealing portion 20A covers the opening 49 and is thermocompression bonded to the top surface 46 which is the upper end of the mouth portion 36. Therefore, the sealing portion 20A needs to be larger than the opening 49, and the outer circumference of the sealing portion 20A is preferably the same size as the outer circumference of the top surface 46. In the present embodiment, since the outer circumference of the top surface 46 is circular, the sealing portion 20A is also circular. The pinching portion 20B, which is a portion to be pinched by a finger when the sealing seal 20 is peeled off, has a rectangular shape, and is connected to the sealing portion 20A so that the longitudinal direction thereof is from the inside to the outside. As shown in FIG. 5B, when the sealing seal 20 is thermocompression bonded, the opening 49 and the top surface 46 are covered.

Then, the cap 60 is attached to the mouth portion 36 side of the tube container 30 to which the sealing seal 20 is joined. FIG. 6 is a partial cross-sectional view of the head molded body 37 with the cap 60 attached. In FIG. 6, as in FIG. 2, the front surface is shown in the right half, and the surface cut in parallel with the front surface through the radial center thereof is shown in the left half.

When the cap 60 as shown in FIG. 3 is attached to the mouth portion 36 of the head molded body 37 as shown in FIG. 2, the state as shown in FIG. 6 is obtained. Specifically, when the cap 60 is attached from the upper side of the tube container 30, the inner cylinder 9 of the cap 60 is first positioned so as to be located on the outer periphery of the mouth portion 36. Then, the cap 60 is moved downward from that state. Then, the elastic leg piece 9A is moved downward along the locking portion 45 that spreads outward as it goes downward, and the elastic leg piece 9A spreads outward. Then, when the hook-shaped claw piece 7 of the elastic leg piece 9A moves below the locking portion, the hook-shaped claw piece 7 moves inward, and as shown in FIG. 6, the cap 60 is attached to the tube container 30. It is installed.

As shown in FIG. 6, when the cap 60 is attached, the outer peripheral surface 47 of the mouth portion 36 is in a state of being in contact with and surrounded by the outer ring 2. At this time, the grip portion 20B of the sealing seal 20 is bent downward so as to be suppressed by the outer ring 2 so as to be in contact with the outer peripheral surface 47 of the mouth portion 36. However, since neither the inside of the outer ring 2 of the cap 60 nor the outer peripheral surface 47 has irregularities such as threads, the possibility that the grip portion 20B will be damaged is extremely low.

Next, for example, kneaded mustard, kneaded wasabi, and other contents are filled in an appropriate amount from the other opening (lower side) 34B of the tubular body 31 of the tube container 30. After that, the opening (lower side) 34B is welded to form the bottom seal portion 39, and a packaged product 30A including the tube container 30 filled and packaged with the contents is obtained.

The details of the head molded body 37 will be further described. The head molded body 37 can be molded so that the mouth portion 36, the neck portion 38, and the shoulder portion 35 have appropriate hardness, and the adhesiveness of the body portion 31 to the material is high, which affects the quality of the contents. A material that does not give hygiene even if it comes into contact with the contents is used. As such a material, a thermoplastic resin is used for the head molded body 37, and more specifically, high-density polyethylene is used.

Further, the head molded body 37 includes polyolefin resins such as low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, polypropylene (homopolypropylene, block-shaped polypropylene, random polypropylene), olefins, and vinyl-based monomers. Polyolefin-based resins such as acrylic monomers and copolymers with copolymerizable monomers such as unsaturated carboxylic acids and blend compositions thereof, and resins in which the above-mentioned resins are blended with high-density polyethylene are used. Is also good. Further, from the viewpoint of heat resistance and thermal adhesion to the body 31, it is preferable to use a resin in which high-density polyethylene is blended with linear low-density polyethylene for the head molded body 37. Further, a truncated cone-shaped cylinder as a barrier material may be laminated on the head molded body 37, particularly on the shoulder portion 35, in order to prevent the permeation of a gas such as oxygen. The shoulder portion 35 may contain a plant-derived resin.

The high-density polyethylene used for forming the shoulder portion 35 of the head molded body 37 may be derived from a fossil raw material, but in order to reduce the environmental load, a high-density polyethylene derived from biomass known as a carbon-neutral material is used. You may. Since the head and cap occupy a large proportion of the tube container, the amount of fossil raw material used in the tube container as a whole can be reduced by molding the head molded body 37 using high-density polyethylene derived from biomass. , The environmental load can be reduced. Further, the head molded body 37 of the tube container 30 is comparable to the head manufactured from the raw material obtained from the conventional fossil raw material in terms of physical properties such as mechanical properties, so that the conventional head is replaced. can do.

From the viewpoint of reducing the environmental load, it can be said that it is preferable to use only polyethylene derived from biomass, but in consideration of manufacturing cost and the like, a blend of polyethylene derived from fossil raw materials and polyethylene derived from biomass may be used. .. Here, the biomass-derived polyethylene is a monomer polymer containing ethylene derived from biomass. Since ethylene derived from biomass is used as the monomer as a raw material, the polyethylene polymerized is derived from biomass. The content of biomass-derived ethylene in the raw material monomer does not have to be 100% by mass, for example, preferably 10% by mass or more, more preferably 30% by mass or more.

The raw material monomer may contain ethylene derived from a fossil raw material, or may contain an α-olefin monomer such as butene, hexene, and octene. Even in such a case, the obtained polymer is called biomass polyethylene. When polyethylene derived from biomass is used, it may contain two or more kinds of polyolefins having different biomass degrees. When the polyethylene derived from the fossil raw material and the polyethylene derived from the biomass are blended, the mixing method is not particularly limited, and a dry blend or a melt blend may be used. When both are mixed, the mixing ratio of the fossil raw material-derived polyethylene and the biomass-derived polyethylene is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2 in terms of mass ratio.

For example, biomass-derived ethylene can be produced using biomass-derived ethanol as a raw material. In particular, it is preferable to use fermented ethanol derived from biomass obtained from plant raw materials. That is, it is preferable to use a plant-derived resin. The plant material is not particularly limited, and conventionally known plants can be used. For example, corn, sugar cane, beet, and manioc can be mentioned.

In the present invention, the fermented ethanol derived from biomass refers to ethanol purified by contacting a culture solution containing a carbon source obtained from a plant raw material with a microorganism that produces ethanol or a product derived from a crushed product thereof. Conventionally known methods such as distillation, membrane separation, and extraction can be applied to the purification of ethanol from the culture broth. For example, a method of adding benzene, cyclohexane or the like and azeotropically boiling the mixture, or removing water by membrane separation or the like can be mentioned.

The thickness of the head molded body 37 in which such a resin is used is preferably 0.5 mm or more and 2.0 mm or less. In the present embodiment, the head molded body 37 is manufactured by compression molding (compression molding). Therefore, in the head molded body 37 which is a compression molded product, it is possible to prevent dents, so-called sink marks, caused by shrinkage during molding from occurring even in a thick portion such as the top surface 46. Further, the waste of the material such as the gate portion can be reduced. The head molded body 37 may be manufactured by injection molding (injection molding).

Next, the laminated body 10 forming the tubular body portion 31 will be described with reference to FIG. 7. As shown in FIG. 7, the laminate 10 forming the body portion 31 of the tube container 30 includes a first sealant layer 12, a printing base material layer 13, and a protective layer 19 arranged in order from the outer surface to the inner surface. , An intermediate base material layer 17, a metal foil 18, and a second sealant layer 15.

An inner surface printing portion 13A containing a desired pattern is formed on the inner surface of the printing base material layer 13 by using printing ink. The inner surface printing portion 13A may be provided on the outer surface of the printing base material layer 13 by using printing ink.

Further, the first sealant layer 12 and the printing base material layer 13 are joined by an extrusion laminate. Further, the printing base material layer 13 and the protective layer 19 are joined by dry lamination. Further, the protective layer 19 and the intermediate base material layer 17 are joined by an extrusion laminate. Further, the intermediate base material layer 17 and the metal foil 18 are joined by extrusion lamination. Further, the metal foil 18 and the second sealant layer 15 are joined by an extrusion laminate. Between the layers of the metal foil 18 and the second sealant layer 15, an acid copolymer such as an ethylene-methacrylic acid copolymer (EMAA) is used and laminated by extrusion lamination.

When the two layers are bonded by dry laminating, the adhesive layer can be formed by applying an adhesive to the surface of the layer to be laminated and drying it. Examples of the adhesive include one-component or two-component curable or non-curable vinyl type, (meth) acrylic type, polyamide type, polyester type, polyether type, polyurethane type, epoxy type, rubber type, and others. Such solvent type, water-based type, or emulsion type adhesives can be used. As the two-component curable adhesive, a cured product of a polyol and an isocyanate compound can be used. As a coating method of the above-mentioned adhesive for lamination, for example, a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a fonten method, a transfer roll coating method, or other methods are used to form a laminate. It can be applied to the coated surface of the layer.

The thermoplastic resin used for the extruded laminate includes a polyethylene resin, a polypropylene resin, a cyclic polyolefin resin, or a copolymer resin containing these resins as a main component, a modified resin, or a mixture (including alloy). Can be used. Examples of the polyolefin resin include the above-mentioned polyethylene, polypropylene (PP), ethylene-α / olefin copolymer polymerized using a metallocene catalyst, ethylene / polypropylene random or block copolymer, and ethylene-vinyl acetate. Polymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene / ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA) ), Ethylene-maleic acid copolymer, ionomer resin, and in order to improve the adhesion between layers, the above-mentioned polyolefin-based resin is used as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid. An acid-modified polyolefin-based resin modified with an unsaturated carboxylic acid such as the above can be used. Further, as the polyolefin resin, an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, a resin obtained by graft-polymerizing or copolymerizing an ester monomer and the like can be used.

These materials can be used alone or in combination of two or more. As the cyclic polyolefin resin, for example, cyclic polyolefins such as ethylene-propylene copolymer, polymethylpentene, polybutene, and polynorbonene can be used. These resins can be used alone or in combination of two or more. As the polyethylene-based resin described above, a resin using the above-mentioned ethylene derived from biomass as a monomer unit can be used to further improve the degree of biomass.

When the adhesive resin layer is laminated by the extrusion laminating method, an anchor coat (AC) layer formed by applying an anchor coating agent and drying may be provided on the surface of the layer on the side to be laminated. Examples of the anchor coating agent include any resin having a heat resistant temperature of 135 ° C. or higher, for example, an anchor coating agent made of a vinyl-modified resin, an epoxy resin, a urethane resin, a polyester resin, a polyethyleneimine, or the like. An anchor coating agent which is a cured product of a polyacrylic or polymethacrylic resin (polyester) having two or more hydroxyl groups and an isocyanate compound as a curing agent can be preferably used. Further, a silane coupling agent may be used in combination with this as an additive, or nitric acid cotton may be used in combination to increase heat resistance.

The anchor coat layer after drying has a thickness of 0.1 μm or more and 1 μm or less, preferably 0.3 μm or more and 0.5 μm or less. The dried adhesive layer preferably has a thickness of 1 μm or more and 10 μm or less, more preferably 2 μm or more and 5 μm or less. The adhesive resin layer preferably has a thickness of 5 μm or more and 50 μm or less, and more preferably 10 μm or more and 30 μm or less.

Next, the material of each part constituting the laminated body 10 of the tubular body portion 31 will be described.

The first sealant layer 12 and the second sealant layer 15 may contain, for example, polyethylene (PE). Specifically, the first sealant layer 12 and the second sealant layer 15 may be prepared from the following materials.

The first sealant layer 12 and the second sealant layer 15 may be any as long as they can be melted by heat and fused to each other. For example, low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (high density polyethylene) ( HDPE), linear (linear) low density polyethylene (LLDPE), polypropylene (PP), ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, Polyethylene-based resins such as ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene or polypropylene can be used as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc. A resin made of one or more of acid-modified polyolefin-based resin modified with unsaturated carboxylic acid, polyvinyl acetate-based resin, polyester-based resin, polystyrene-based resin, and other resins can be used.

Further, as the printing base material layer 13, a polyethylene terephthalate (hereinafter, abbreviated as PET) layer can be used, and by printing on the PET layer 13, the PET layer 13 is provided with the inner surface printing portion 13A made of printing ink. Can be done. Further, the printed base material layer 13 is responsible for maintaining the rigidity of the tube container together with the intermediate base material layer 17.

Further, instead of using the PET layer as the printing substrate layer 13, a nylon layer may be used. When a nylon layer is used, the mechanical strength is often superior to that of the PET layer. In addition to PET and nylon, polyolefin resins such as polyethylene and polypropylene can also be used.

The protective layer 19 is a layer for protecting the metal foil 18 and enhancing the design of the appearance of the entire laminated body 10. In particular, when the metal foil 18 is an aluminum foil, the metal foil 18 is protected by preventing the metal foil 18 from cracking during heat sealing. The protective layer 19 cannot necessarily prevent the metal leaf 18 from cracking, but can protect it to a certain extent. As the protective layer 19, a metal-deposited film can be used. As the base film of the metal-deposited film, polyethylene terephthalate (PET), nylon or the like can be used as in the case of the printing substrate layer 13. As the metal to be deposited on the base film, various metals generally used for metal deposition such as copper and tin can be used, but aluminum is preferably used. In this embodiment, an aluminum-deposited polyethylene terephthalate film is used as the metal-deposited film of the protective layer 19. By using a metal-deposited film as the protective layer 19, a metallic appearance can be maintained when viewed from the outside through the first sealant layer 12 and the printing substrate layer 13. Further, by forming the protective layer 19 on the outer surface side of the metal foil 18, damage to the metal foil 18 can be suppressed. Since a metal foil such as an aluminum foil is a metal film, the film is hard and easily cracked by heat and pressure during heat sealing, and black streaks are easily visible in appearance. On the other hand, since the aluminum-deposited layer of aluminum-deposited PET is about 400 Å, the film is basically soft and follows the printed substrate layer 13 such as PET. Therefore, the protective layer 19 such as aluminum-deposited PET is a factor that is less likely to crack even if the same heat and pressure are applied.

As the intermediate base material layer 17, a polyolefin-based film such as polyethylene (PE) or polypropylene (PP) can be used. As the polyethylene (PE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear (linear) low density polyethylene (LLDPE) and the like can be used. The intermediate base material layer 17 has a function of further enhancing the content resistance and is responsible for maintaining the rigidity of the body portion 31 of the tube container. The same polyolefin-based film used as the first sealant layer 12 and the second sealant layer 15 may be used.

The ratio of the thickness of the intermediate base material layer 17 to the laminated body 10 is preferably 0.30 or more and 0.45 or less, and more preferably 0.35 or more and 0.40 or less. If the ratio of the thickness of the intermediate base material layer 17 to the laminate 10 is too small, the laminate 10 provided with the protective layer 19 and the metal foil 18 does not have sufficient elasticity and the elasticity of the body 31 is low. Therefore, if the ratio of the thickness of the intermediate base material layer 17 to the laminate 10 is too large, the flexibility is weakened, and the laminate 10 provided with the protective layer 19 and the metal foil 18 becomes difficult to handle.

As the metal foil 18, an appropriate metal leaf 18 is selected according to a required function such as water vapor and other gas barrier properties. As the metal foil, various metal foils having a barrier property such as copper and tin can be used, but it is preferable to use an aluminum foil.

The above-mentioned resins as materials used for the first sealant layer 12, the printed base material layer 13, the protective layer 19, the intermediate base material layer 17, and the second sealant layer 15 are not only those derived from fossil raw materials but also those derived from biomass. May be used. For example, in addition to the above-mentioned biomass-derived polyethylene resin, biomass polyester using biomass-derived ethylene glycol as a diol component as described in JP2012-116802, polylactic acid resin, cellophane, starch, and cellulose. Etc. can be used. It is preferable to use a plant-derived resin as the biomass-derived resin.

Since the inner surface printing portion 13A provided on the inner surface of the printing base material layer 13 is printed on the printing base material layer 13 which is smooth and has excellent transparency, it is possible to perform printing excellent in cosmetics. ..

Next, a method of manufacturing the laminated body 10 of the tubular body portion 31 will be described with reference to FIG.

First, printing is applied to the inner surface of the printing base layer 13, and thus the inner surface printing portion 13A made of printing ink is provided on the inner surface of the printing base layer 13.

Next, the protective layer 19 is bonded to the inner surface of the printing substrate layer 13 with a dry laminate (DL).

Next, the intermediate base material layer 17 is joined to the inner surface of the protective layer 19 by extrusion lamination.

Next, the metal foil 18 is joined to the inner surface of the intermediate base material layer 17 by extrusion lamination.

Next, the second sealant layer 15 is joined to the inner surface of the metal foil 18 by extrusion lamination.

Next, the first sealant layer 12 is formed on the outer surface of the printing substrate layer 13 by extrusion lamination. As described above, the laminated body 10 of the body portion 31 is obtained. As long as the desired laminated body 10 can be obtained, the method is not limited to the above manufacturing method.

The laminated body 10 of the body portion 31 thus obtained is wound in a cylindrical shape, and both end portions 33A and 33B are overlapped as described above, and the outer surface and the inner surface of the laminated body 10 are formed on both end portions 33A and 33B. It is heat-sealed to form a body sticking portion 32, and a tubular body portion 31 is produced. In this case, the first sealant layer 12 provided on the outer surface side of the laminated body 10 and the second sealant layer 15 provided on the inner surface side are melted and joined to obtain a tubular body portion 31.

In the above, the body pasting portion 32 is formed by overlapping, but the end faces of both end portions 33A and 33B may be butted and joined. Further, the joint wire that has been joined together as described above may be protected by attaching a film to the inner surface or the outer surface of the tubular body portion 31. Further, the inner end portion 33B may be processed to protect the end face. For example, there are protection by attaching tape and processing (hemming processing) in which the end portion 33B is bent outward of the container.

Next, the opening (upper side) 34A of the tubular body 31 is inserted into a mold (not shown), and the tubular body 31 is formed into a tubular shape by using a method such as compression molding or injection molding. A shoulder portion 35 and a mouth portion 36 are formed in the opening (upper side) 34A of the body portion 31 of the tube container 30 (see FIGS. 1 and 4).

Next, after the sealing seal 20 is heat-sealed to the mouth 36 of the tube container 30 manufactured as described above, the cap 60 is attached, and a plurality of tube containers 30 to which the cap 60 is attached are put together. It is stored in a cardboard box. After that, the plurality of tube containers 30 to which the caps 60 are attached are conveyed for each cardboard box.

<Example 1>
A 12 μm-thick PET film was used as the printing substrate layer 13, a 12 μm-thick VM-PET film was used as the protective layer 19, a 130 μm-thick PE film was used as the intermediate substrate layer 17, and an aluminum foil having a thickness of 10 μm was used as the metal foil 18.

Specifically, first, the inner surface printing portion 13A was formed on the inner surface side of the polyethylene terephthalate (PET) film having a thickness of 12 μm to be the printing substrate layer 13.

Next, on the inner surface side where the inner surface printing portion 13A of the PET film which is the printing base material layer 13 was formed, a VM-PET film having a thickness of 12 μm to be the protective layer 19 was bonded by dry lamination using an adhesive. ..

Next, an anchor coat layer is formed on the inner surface side of the protective layer 19, and PE, which is a thermoplastic resin, is used as an adhesive layer with a thickness of 20 μm by extrusion lamination, and a PE film having a thickness of 130 μm to be an intermediate base material layer 17 is bonded. It was.

Next, an anchor coat layer is formed on the inner surface side of the intermediate base material layer 17, and an aluminum foil having a thickness of 10 μm to be a metal foil 18 is bonded to the metal foil 18 by using EMAA, which is a thermoplastic resin, as an adhesive layer having a thickness of 20 μm by extrusion lamination. It was.

Further, an ethylene-methacrylic acid copolymer (EMAA) resin film having a thickness of 35 μm is extruded and laminated on the inner surface side of the aluminum foil having a thickness of 10 μm to be the metal foil 18, and further, the ethylene-methacrylic acid copolymer resin surface is further laminated. On the other hand, a PE layer having a thickness of 50 μm to be the second sealant layer 15 was formed by extrusion laminating in two steps.

Next, an anchor coat layer is formed on the outer surface side of the printing substrate layer 13 on which the inner surface printing portion 13A is not formed, and a PE layer having a thickness of 60 μm to be the first sealant layer 12 is formed by extrusion lamination in two steps. did.

As a result, the laminate 10 having a composition of PE35 μm / PE25 μm / AC / PET12 μm / printing layer (ink) / DL / VM-PET12 μm / AC / PE20 μm / PE130 μm / AC / EMAA20 μm / ALM foil 10 μm / EMAA35 μm / PE25 μm / PE25 μm Obtained.

<Example 2>
PE 35 μm / PE 25 μm / AC / bio PET 12 μm / printing layer (ink) / DL / VM-PET 12 μm / AC / PE 20 μm in the same manner as in Example 1 except that a bio-PET film having a thickness of 12 μm was used as the printing substrate layer 13. A laminate 10 having a composition of / PE 130 μm / AC / EMAA 20 μm / ALM foil 10 μm / EMAA 35 μm / PE 25 μm / PE 25 μm was obtained. As the bio-PET film of the printing substrate layer 13, "DE024" manufactured by Toyobo Co., Ltd. was used.

<Example 3>
PE35 μm / PE25 μm / AC / PET12 μm / printing layer (ink) / DL / thin-filmed bio-PET 12 μm / AC / PE20 μm / PE130 μm A laminated body 10 having a composition of / AC / EMAA 20 μm / ALM foil 10 μm / EMAA 35 μm / PE 25 μm / PE 25 μm was obtained. As the vapor-deposited bio-PET film of the protective layer 19, "IB-PET-PBIR" manufactured by DNP Technopack Co., Ltd. was used.

<Example 4>
PE 35 μm / PE 25 μm / AC / PET 12 μm / printing layer (ink) / DL / VM-PET 12 μm / AC / PE 20 μm / in the same manner as in Example 1 except that a bio-PE film having a thickness of 130 μm was used as the intermediate base material layer 17. A laminate 10 having a composition of bio-PE 130 μm / AC / EMAA 20 μm / ALM foil 10 μm / EMAA 35 μm / PE 25 μm / PE 25 μm was obtained. As the bio-PE film of the intermediate base material layer 17, "BDP-401" manufactured by Dai Nippon Printing Co., Ltd. was used.

The ratio of the thickness of the intermediate base material layer 17 to the laminated body 10 is the same in all of Examples 1 to 4, and is 0.372. In any of Examples 1 to 4, the thickness of the intermediate base material layer 17 is 130 μm, and the thickness of the entire laminate 10 is 349 μm.

<Comparison example>
A PET film having a thickness of 12 μm was used as the printing base material layer, a PE film having a thickness of 130 μm was used as the intermediate base material layer, and an aluminum foil having a thickness of 10 μm was used as the barrier layer. Compared with the first embodiment, the major difference is that the protective layer 19 is not provided. The first sealant layer, the printing base material layer, the intermediate base material layer, the barrier layer, and the second sealant layer are the same as in Example 1.

As a result, a laminate having a composition of PE35 μm / PE25 μm / AC / PET12 μm / printing layer (ink) / DL / PE130 μm / AC / EMAA20 μm / ALM foil 10 μm / EMAA35 μm / PE25 μm / PE25 μm was obtained.

<Evaluation>
A total of five laminates of Examples 1 to 4 and Comparative Examples were evaluated. Two evaluation indexes were used: the appearance of cracks and wrinkles after heat sealing, and the metallic appearance. The evaluation results are shown in Table 1.

As for the appearance state of cracks and wrinkles after the heat seal, the appearance state of the cracks and wrinkles was visually observed after the heat seal for forming the bottom seal portion 39 of the body portion 31. As a result of visual observation, the evaluation was made on a scale of 〇, Δ, and × under the following conditions.
・ No cracks or wrinkles can be confirmed 〇 ・ Wrinkles can be confirmed △
・ Check for cracks ×

The glossiness (metallic appearance) was measured with a gloss meter "Gloss Checker IG-320" manufactured by HORIBA, Ltd.

Specifically, the measurement was performed in accordance with JIS standard (Z8741). The glossiness was measured by a light receiver that incidents light on the sample surface at a defined incident angle θ from a light source and reflects the light reflected at a reflection angle θ ′ in the specular reflection direction. In the JIS standard (Z8741), a black mirror-finished glass plate having a refractive index of 1.567 is used as a reference, and the specular reflectance at a defined incident angle θ is defined as a specular glossiness of 100. The conditions of the optical system used for the measurement are as follows.

<Optical system>
Incident angle 60 ° -Reception angle 60 °
Measurement area: 12 x 6 mm ellipse Light source: LED (wavelength 880 nm)
Operating temperature range: 0-40 ° C

As shown in Table 1, regarding the appearance state of cracks and wrinkles, neither cracks nor wrinkles could be confirmed in the laminated bodies of Examples 1 to 4, but the laminated bodies of Comparative Examples had no cracks or wrinkles. , Cracks were confirmed (x). The case where neither cracks nor wrinkles can be confirmed includes the case where the aluminum foil itself is not necessarily cracked, but the aluminum foil is not cracked or wrinkled because it is passed through the aluminum vapor deposition film which is the protective layer. This is because the aluminum-deposited film has a higher followability to PET of the printing substrate layer than the aluminum foil, and thus cracks are less likely to occur. In addition, the glossiness (metallic appearance) was about twice as high as that of the laminated bodies of Comparative Examples in all of the laminated bodies of Examples 1 to 4.

From the evaluation results shown in Table 1, the first sealant layer 12, the printing base material layer 13, the protective layer 19, the intermediate base material layer 17, the metal foil 18, and the second sealant layer 15 are laminated in this order, and the protective layer is formed. As shown in 19, it was found that the laminated body using the metal-deposited film was superior in all of the appearance state of cracks and wrinkles and the glossiness (metallic appearance) as compared with the other laminated bodies.

As described above, by using a laminate having a good appearance of cracks and wrinkles and a high glossiness (metallic appearance) as the body 31 of the tube container 30, the barrier function is fully exhibited and the high metallicity is achieved. I was able to enhance the design by the tone.

Next, the layer structure of the sealing seal 20 will be described with reference to FIG. As shown in FIG. 8, the sealing seal 20 is a laminate having a first base material layer 21, a second base material layer 22, and a sealant layer 23 arranged in order from the upper side to the lower side.

An inner surface printing portion 21A containing a desired pattern is formed on the lower side of the first base material layer 21 by using printing ink.

Further, the first base material layer 21 and the second base material layer 22 are joined by a dry laminate. Further, the second base material layer 22 and the sealant layer 23 are joined by a dry laminate.

Next, the material of each part constituting the sealing seal 20 will be described.

The sealant layer 23 may contain, for example, polyethylene (PE). Specifically, the sealant layer 23 may be made of the following materials.

The sealant layer 23 may be any as long as it can be melted by heat and fused to the mouth 36 of the tube container 30, for example, low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene. (HDPE), linear (linear) low density polyethylene (LLDPE), polypropylene (PP), ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer , Ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene or polypropylene, and other polyolefin resins such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc. A resin made of one or more of acid-modified polyolefin-based resin modified with unsaturated carboxylic acid, polyvinyl acetate-based resin, polyester-based resin, polystyrene-based resin, and other resins can be used.

Further, as the first base material layer 21 and the second base material layer 22, a polyethylene terephthalate (PET) layer can be used. When the PET layer is used as the first base material layer 21, the inner surface printing portion 21A made of printing ink can be provided on the PET layer by printing on the PET layer.

Further, instead of using the PET layer as the first base material layer 21, a nylon layer may be used, or a PET layer having a metal vapor deposition film on at least one surface and having gas barrier properties may be used, or at least. A nylon layer having a metal vapor deposition film on one surface and having a gas barrier property may be used.

Further, a PET layer having a silica vapor deposition film on at least one surface and having a gas barrier property may be used, or a nylon layer having a silica vapor deposition film on at least one surface and having a gas barrier property may be used. ..

Further, a PET layer having an aluminum oxide vapor deposition film on at least one surface and having a gas barrier property may be used, or a nylon layer having an aluminum oxide vapor deposition film on at least one surface and having a gas barrier property may be used. May be good.

Further, instead of using the PET layer as the second base material layer 22, a nylon layer may be used.

When a nylon layer is used, the mechanical strength is often superior to that of the PET layer. Further, the film provided with various thin-film deposition films has a better gas barrier property than the film as a base material.

As a preferable example of the sealing seal 20, a PET layer having a metal vapor deposition film on the upper side as the first base material layer 21 and having gas barrier properties, a PET layer as the second base material layer 22, and polyethylene (PE) as the sealant layer 23. , VMPET 12 μm / ink / adhesive / PET 25 μm / adhesive / PE 30 μm.

Although the preferred embodiment of the present invention has been described above, the present invention is not limited to the above embodiment, and various modifications are possible. For example, in the above embodiment, the sealing seal 20 is joined to the mouth 36 so as to seal the tube container 30, but the sealing seal 20 does not necessarily have to be provided.

Further, in the above embodiment, in order to increase the elasticity of the body portion 31, the laminated body 10 is configured to include the intermediate base material layer 17 between the protective layer 19 and the metal foil 18, but the intermediate base material layer 17 is not necessarily provided. There is no need to prepare.

Further, in the above embodiment, as the cap, a type that is connected by so-called one-touch fitting, in which the cap is attached to and detached from the container only by a linear motion in the vertical direction, is used, but on the outer peripheral surface of the mouth portion. Other types such as a screw type having a thread groove on the inner surface of the cap may be used so as to provide a thread and screw the thread.

2 ... Outer ring 7 ... Hook-shaped claw piece 7A ... Inclined surface 8 ... Outer cylinder 8A ... Lower hem 8B ... Inclined surface 9 ... Inner cylinder 9A ... Elastic Leg piece 10 ... Laminated body (of the body 31 of the tube container 30) 12 ... First sealant layer 13 ... Printing base material layer 15 ... Second sealant layer 17 ... Intermediate base material layer 18 ... Metal leaf 19 ... Protective layer 20 ... Sealing seal 20A ... Sealing part 20B ... Picking part 21 ... First base material layer 22 ... Second base material layer 23.・ ・ Sealant layer 30 ・ ・ ・ Tube container 31 ・ ・ ・ Body 32 ・ ・ ・ Body pasting 33A ・ ・ ・ Bonding end 33B ・ ・ ・ Outside when body is pasted Bonded end 34A ・ ・ ・ Opening (upper side)
34B ・ ・ ・ Opening (lower side)
35 ... Shoulder 36 ... Mouth 37 ... Head molded body 38 ... Neck 39 ... Bottom seal 45 ... Locking part 46 ... Top surface 47 ... Outer circumference Surface 48 ・ ・ ・ Inner peripheral surface 49 ・ ・ ・ Opening 60 ・ ・ ・ Cap

Claims (7)

The first sealant layer, the printing substrate layer, the protective layer, the metal foil, and the second sealant layer are laminated in this order.
The protective layer is a laminate characterized in that it is formed by using a metal vapor deposition film. The laminate according to claim 1, wherein the metal foil is an aluminum foil. The laminate according to claim 1 or 2, wherein the metal-deposited film is an aluminum-deposited polyethylene terephthalate film. The laminate according to any one of claims 1 to 3, wherein at least one of the printing base material layer and the protective layer contains a plant-derived resin. The laminate according to any one of claims 1 to 4, wherein at least one of the first sealant layer and the second sealant layer contains a plant-derived resin. The laminate according to any one of claims 1 to 5, wherein an intermediate base material layer is further provided between the protective layer and the metal foil. A tube container characterized in that the laminate according to any one of claims 1 to 6 is used as a body portion.

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