JP2021160270A - Laminate and packaging container - Google Patents

Abstract

To provide a laminate favorably usable for producing a mono-material packaging container, with high adhesion to a vapor-deposited film, and capable of effectively preventing delamination when made into a packaging container.SOLUTION: A laminate at least includes a first sealant layer 11, a vapor-deposited film 12, a substrate 13 and a second sealant layer 14. The substrate 13 at least includes a polyethylene resin layer 16 and a surface resin layer 15. The polyethylene resin layer 16 of the substrate 13, the first sealant layer 11 and the second sealant layer 14 are composed of a polyethylene. The surface resin layer 15 of the substrate 13 includes a resin material with a melting point 150°C or higher. The vapor-deposited film 12 is disposed on the surface resin layer 15 of the substrate 13. A drawing process is applied to the substrate 13.SELECTED DRAWING: Figure 1

Description

The present invention relates to laminates and packaging containers.

Conventionally, a resin film made of a polyester resin such as polyethylene terephthalate (hereinafter, also referred to as a polyester film) is excellent in mechanical properties, chemical stability, heat resistance and transparency, and is inexpensive. It is used as a base material constituting the laminate used in.

Such a polyester film is usually laminated with a polyethylene film which is a sealant layer to form a laminate, and then molded into a packaging container.

The above-mentioned packaging container made of a laminate of different types of resin films, that is, a polyester film and a polyethylene film, is difficult to separate into each layer, and the packaging container recovered after use. Is not suitable for recycling and is not actively recycled.

Then, for the purpose of improving the recyclability of the packaging container, instead of the polyester film, a stretched polyethylene film (stretched polyethylene film) is applied to the base material, and packaging using a laminate composed of the same material is used. The production of containers (monomaterial packaging containers) is being considered.

Recently, the present inventors have tried to form a vapor-deposited film on the surface of the polyethylene film in order to compensate for the gas barrier property that has deteriorated due to the change of the polyester film to the polyethylene film. We have found a new problem that when a packaging container is manufactured using a polyethylene film on which a vapor-deposited film is formed due to insufficient properties, peeling (delamination) may occur between the polyethylene film and the vapor-deposited film.

Surprisingly, the present inventors provide a surface resin layer containing a resin material having a melting point of 150 ° C. or higher on the surface of the polyethylene film, so that the vapor-deposited film formed on the surface resin layer is formed. It has been found that the adhesion is improved, and the gas barrier property of the laminate is remarkably improved accordingly, and the above problem can be solved.

The present invention has been made based on such findings, and the problem to be solved is that it can be suitably used for producing a monomaterial packaging container, has high adhesion to a vapor-deposited film, and has a high adhesion to a packaging container. It is an object of the present invention to provide a laminated body capable of effectively preventing delamination in the case of such a case.

Another object to be solved by the present invention is to provide a packaging container made of the above-mentioned laminate.

The laminate of the present invention is a laminate including at least a first sealant layer, a vapor-deposited film, a base material, and a second sealant layer in this order.
The base material comprises at least a polyethylene resin layer and a surface resin layer.
The first sealant layer and the second sealant layer are made of polyethylene resin.
The surface resin layer of the base material contains a resin material having a melting point of 150 ° C. or higher.
The vapor-deposited film is provided on the surface resin layer of the base material, and is provided on the surface resin layer.
The base material is characterized in that it has been stretched.

In one embodiment, the surface resin layer of the base material contains a resin material having a melting point of 150 ° C. or higher and 265 ° C. or lower.

In one embodiment, the melting point difference between the polyethylene resin and the resin material having a melting point of 150 ° C. or higher contained in the surface resin layer is 20 to 80 ° C.

In one embodiment, the resin material of the surface resin layer is composed of a polymer having a polar group.

In one embodiment, the resin material of the surface resin layer is ethylene vinyl alcohol copolymer, polyvinyl alcohol, polyester, nylon 6, nylon 6,6, nylon 6-nylon 6,6 copolymer, MXD nylon and amorphous nylon. One or more resin materials selected from.

In one embodiment, the polyethylene resin layer of the base material has a multilayer structure.

In one embodiment, the polyethylene resin layer of the base material includes at least one layer containing a compatibilizer.

In one embodiment, the substrate is a co-press film.

In one embodiment, a barrier coat layer is further provided between the first sealant layer and the vapor-deposited film.

In one embodiment, the laminate is used in a packaging container.

In one embodiment, the content of the polyethylene resin in the entire laminate is 95% by mass or more.

The packaging container of the present invention is characterized by being made of the above-mentioned laminate.

In one embodiment, the packaging container is a laminated tube.

According to the present invention, it can be suitably used for producing a monomaterial packaging container, the adhesion between layers with a vapor-deposited film can be remarkably improved, and a preferable gas barrier property can be achieved. Can be provided,
Further, according to the present invention, it is possible to provide a packaging container made of a laminated body.

It is a schematic cross-sectional view which shows one Embodiment of the laminated body of this invention. It is the schematic sectional drawing which shows one Embodiment of a thin-film deposition apparatus. It is the schematic sectional drawing which shows one Embodiment of a thin-film deposition apparatus. It is a front view which shows the laminated tube which is one Embodiment of the packaging container of this invention. FIG. 4 is a cross-sectional view taken along the line aa of FIG.

(Laminated body)
As shown in FIG. 1, the laminate 10 of the present invention includes at least a first sealant layer and 11, a vapor-deposited film 12, a base material 13, and a second sealant layer 14.
The polyethylene resin layer, the first sealant layer, and the second sealant layer of the base material included in the laminate are made of the same resin, that is, polyethylene resin, and the laminate having such a configuration is mono. It can be suitably used as a laminate for producing a material packaging container.
Further, the laminate of the present invention has a remarkably improved adhesion between the base material and the vapor-deposited film, and has an extremely high gas barrier property.

The base material 13 includes at least a surface resin layer 15 and a polyethylene resin layer 16. The base material 13 can be provided with an adhesive resin layer between the surface resin layer 15 and the polyethylene resin layer 16 (not shown).

In one embodiment, the laminate 10 includes a melt extruded resin layer or an adhesive layer 17 between the first sealant layer 11 and the vapor deposition film 12, and between the base material 13 and the second sealant layer 14. be able to.

The content of the polyethylene resin with respect to the total amount of solids contained in the laminate is preferably 95% by mass or more. This makes it possible to obtain a laminate that can be suitably used for producing a monomaterial packaging container.

Hereinafter, each layer included in the laminated body 10 will be described.

(Base material)
The base material includes at least a polyethylene resin layer and a surface resin layer. Further, in one embodiment, the base material includes an adhesive resin layer between the polyethylene resin layer and the surface resin layer.

The ratio of the thickness of the surface resin layer to the total thickness of the base material is preferably 2% or more and 20% or less, and more preferably 4% or more and 15% or less.
By setting the ratio of the thickness of the surface resin layer to the total thickness of the base material to 2% or more, the adhesion of the vapor-deposited film can be further improved, and the gas barrier property can be further improved.
Further, by setting the ratio of the thickness of the surface resin layer to the total thickness of the base material to 20% or less, a laminate that can be suitably used for manufacturing a monomaterial packaging container can be obtained. Further, the film-forming property and processability of the base material can be further improved.

(Polyethylene resin layer)
The polyethylene resin layer is made of polyethylene resin.
As the polyethylene resin, high-density polyethylene resin (HDPE), medium-density polyethylene resin (MDPE), low-density polyethylene resin (LDPE), linear low-density polyethylene resin (LLDPE) and ultra-low-density polyethylene resin (VLDPE) are used. can do.
Further, as the polyethylene resin, a copolymer of ethylene and other monomers can also be used.
Further, as the polyethylene resin, a polyethylene resin derived from biomass or a polyethylene resin mechanically recycled or chemically recycled can also be used.

Here, as the high-density polyethylene resin, a polyethylene resin having a density of 0.945 g / cm ³ or more can be used, and as a medium-density polyethylene resin, a density of 0.925 g / cm ³ or more is 0.945 g / cm. ^{A polyethylene resin of less than 3} can be used, and as the low density polyethylene resin, a polyethylene resin having a density of 0.900 g / cm ³ or more and less than 0.925 g / cm ³ can be used, and the linear low density can be used. As the polyethylene resin, a polyethylene resin having a density of 0.900 g / cm ³ or more and less than 0.925 g / cm ³ can be used, and as an ultra-low density polyethylene resin, a polyethylene having a density of less than ^{0.900 g / cm 3 can be used.} Resin can be used.

The content of the polyethylene resin in the polyethylene resin layer is preferably 70% by mass or more, and more preferably 80% by mass or more. As a result, the laminate of the present invention can be preferably used for producing a monomaterial packaging container.

In one embodiment, the polyethylene resin layer may include at least one layer containing a compatibilizer.
When the polyethylene resin layer contains a compatibilizer to heat-melt and recycle the packaging container produced by using the laminate of the present invention, the resin material contained in the surface resin layer and having a melting point of 150 ° C. or higher and the resin material have a melting point of 150 ° C. or higher. It is possible to effectively prevent the polyethylene resin contained in the polyethylene resin layer from being uniformly mixed and the physical properties thereof being deteriorated. In addition, it is possible to effectively prevent the transparency from being lowered.
When the polyethylene resin layer has a multi-layer structure, the compatibilizer is preferably contained in the layer in contact with the surface resin layer of the polyethylene resin layer. The above effect can be further improved by containing the compatibilizer in the layer of the polyethylene resin layer in contact with the surface resin layer.

As the compatibilizer, conventionally known ones can be appropriately selected and used, but from the viewpoint of recyclability, an unsaturated carboxylic acid-modified polyolefin resin is preferable, and among them, a maleic anhydride-modified polyethylene resin is more preferable.

The content of the compatibilizer in the layer containing the compatibilizer is preferably 5% by mass or more and 30% by mass or less.
The above effect can be further improved by setting the content of the compatibilizer in the polyethylene resin layer to 5% by mass or more.
By setting the content of the compatibilizer in the polyethylene resin layer to 30% by mass or less, the strength and heat resistance of the base material can be improved.

As long as the characteristics of the present invention are not impaired, the polyethylene resin layer may contain a resin material other than the polyethylene resin, for example, a polyolefin resin such as polypropylene resin, (meth) acrylic resin, vinyl resin, cellulose resin, polyamide. Examples thereof include resins, polyester resins and ionomer resins.
From the viewpoint of recycling suitability, it is particularly preferable that the polyethylene resin layer does not contain a resin other than the polyethylene resin.

Further, the polyethylene resin layer can contain an additive as long as the characteristics of the present invention are not impaired, and for example, a cross-linking agent, an antioxidant, an anti-blocking agent, a slip agent, an ultraviolet absorber, and a light stabilizer. Examples include agents, fillers, reinforcing agents, antistatic agents, pigments and modifying resins.

The polyethylene resin layer provided in the base material may have a single-layer structure or a multi-layer structure.

In the polyethylene resin layer having a multi-layer structure, the density of the polyethylene resin constituting each layer may be different, that is, the polyethylene resin layer may be provided with a density gradient.
By providing the density gradient in the polyethylene resin layer, its strength, heat resistance and stretchability are remarkably improved.

In a polyethylene resin layer provided with a density gradient, if the density difference between the layers is large, peeling (delamination) may occur at the interface. Therefore, the density difference between the layers ^{is preferably 0.04 g / cm 3} or less, and more preferably 0.02 g / cm ³ or less.

An embodiment of a polyethylene resin layer provided with a density gradient will be illustrated below. The structure of the polyethylene resin layer is not limited to these.

In one embodiment, the polyethylene resin layer provided with the density gradient is composed of three layers: a layer containing a high-density polyethylene resin, a layer containing a medium-density polyethylene resin, and a layer containing a high-density polyethylene resin.
By forming the polyethylene resin layer into a three-layer structure provided with the density gradient as described above, the strength, heat resistance and stretchability are remarkably improved. In addition, it is possible to effectively prevent curling from occurring on the base material.

In one embodiment, the polyethylene resin layer provided with the density gradient includes a layer containing high density polyethylene, a layer containing medium density polyethylene resin, and at least one of low density polyethylene resin and linear low density polyethylene resin. It is composed of five layers: a layer containing a medium-density polyethylene resin, and a layer containing a high-density polyethylene resin.
By forming the polyethylene resin layer into a five-layer structure provided with the density gradient as described above, the strength, heat resistance and stretchability are remarkably improved. In addition, it is possible to effectively prevent curling from occurring on the base material.
The polyethylene resin layer having such a structure can be stably produced by the following inflation method.
Specifically, from the outside, a high-density polyethylene resin, a medium-density polyethylene resin, and at least one of a low-density polyethylene resin and a linear low-density polyethylene resin are co-extruded into a tube shape.
Next, layers containing at least one of the low-density polyethylene resin and the linear low-density polyethylene resin can be produced by crimping them with a rubber roll or the like.
By manufacturing by such a method, the number of defective products in manufacturing can be remarkably reduced, and finally, the production efficiency can be improved.

In one embodiment, the polyethylene resin layer provided with the density gradient is a layer containing a high density polyethylene resin, a layer containing a blended resin of a high density polyethylene resin and a medium density polyethylene resin, a low density polyethylene resin and a linear chain. It is composed of seven layers: a layer containing at least one of low-density polyethylene resins, a layer containing a blended resin of high-density polyethylene resin and medium-density polyethylene resin, and a layer containing high-density polyethylene resin.
By forming the polyethylene resin layer into a five-layer structure provided with the density gradient as described above, the strength, heat resistance and stretchability are remarkably improved. In addition, it is possible to effectively prevent curling from occurring on the base material. Further, it is possible to effectively prevent the occurrence of delamination in the base material.
Further, the polyethylene resin layer having such a structure can be stably produced by the inflation method described above.

The thickness of the polyethylene resin layer is preferably 10 μm or more and 50 μm or less, and more preferably 10 μm or more and 40 μm or less.
By setting the thickness of the polyethylene resin layer to 10 μm or more, the strength and heat resistance of the base material can be further improved.
Further, by setting the thickness of the polyethylene resin layer to 50 μm or less, the film-forming property and processability of the base material can be further improved.

The polyethylene resin layer may have a printing layer on its surface, and the image formed on the printing layer is not particularly limited, and characters, patterns, symbols, combinations thereof, and the like are represented.
The print layer can be formed on the substrate by using an ink derived from biomass. As a result, the environmental load can be reduced.
The method for forming the print layer is not particularly limited, and examples thereof include conventionally known printing methods such as a gravure printing method, an offset printing method, and a flexographic printing method.

(Surface resin layer)
The base material provided in the laminate of the present invention includes a surface resin layer containing a resin material having a melting point of 150 ° C. or higher (hereinafter, sometimes referred to as a high melting point resin material) on a polyethylene resin layer.

The melting point of the high melting point resin material is more preferably 160 ° C. or higher.
By setting the melting point of the high melting point resin material to 160 ° C. or higher, the adhesion of the vapor-deposited film can be further improved, and the gas barrier property can be further improved. Further, when the sealant layers are laminated, the adhesion to the sealant layer can be improved, and the laminating strength of the packaging container produced by this laminated body can be further improved.

The melting point of the high melting point resin material is preferably 260 ° C. or lower, more preferably 260 ° C. or lower, and even more preferably 250 ° C. or lower. By setting the melting point of the high melting point resin material to 265 ° C. or lower, the film forming property of the base material can be improved.

The difference between the melting point of the refractory resin material contained in the surface resin layer and the melting point of polyethylene contained in the polyethylene resin layer is preferably 20 to 80 ° C, more preferably 20 to 60 ° C.
When the difference between the melting point of the high melting point resin material contained in the surface resin layer and the melting point of polyethylene contained in the polyethylene resin layer is 20 ° C. or higher, the adhesion of the vapor-deposited film can be further improved, and the vapor-deposited film can be further improved. It is possible to further improve the gas barrier property of the base material on which the material is formed. Further, when the sealant layers are laminated, the adhesion to the sealant layer can be improved, and the laminating strength of the packaging container produced by this laminated body can be further improved.
Further, when the difference between the melting point of the refractory resin material contained in the surface resin layer and the melting point of polyethylene contained in the polyethylene resin layer is 80 ° C. or less, the film-forming property of the base material can be further improved. ..

In one embodiment, the melting point resin material consists of a polymer having a polar group. Since the refractory resin material is made of a polymer having a polar group, the adhesion to the vapor-deposited film can be further improved.

In the present invention, the polar group refers to a group containing one or more heteroatoms, for example, an ester group, an epoxy group, a hydroxyl group, an amino group, an amide group, a carboxyl group, a carbonyl group, a carboxylic acid anhydride group, and a sulfone group. , Thiol group and halogen group and the like.
Among these, from the viewpoint of the lamination strength of the packaging container, a hydroxyl group, an ester group, an amino group, an amide group, a carboxyl group and a carbonyl group are preferable, and a hydroxyl group is more preferable.

Examples of the refractory resin material include vinyl resin, polyamide, polyimide, polyester, (meth) acrylic resin, cellulose resin, polyolefin resin, ionomer resin and the like.

In the present invention, a resin material having a melting point of 150 ° C. or higher and having a polar group is particularly preferable, and ethylene vinyl alcohol copolymer, polyvinyl alcohol, nylon 6, nylon 6,6, nylon 6-nylon 6,6 co-weight. Amid resins such as coalesced, MXD nylon and amorphous nylon are preferable, and ethylene vinyl alcohol copolymers and amide resins are particularly preferable.
By using such a resin material, the adhesion of the thin-film deposition film formed on the surface resin layer can be remarkably improved, and the gas barrier property can be effectively improved.

The content of the refractory resin material in the surface resin layer is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more. By setting the content of the refractory resin material in the surface resin layer to 70% by mass or more, the adhesion of the vapor-deposited film formed on the surface resin layer can be remarkably improved, and the base material on which the vapor-deposited film is formed can be remarkably improved. The gas barrier property of the above can be effectively improved.

The surface resin layer may contain a resin material other than the refractory resin material as long as the characteristics of the present invention are not impaired.
From the viewpoint of adhesion to the vapor-deposited film, it is preferable that the surface resin layer does not contain a resin material other than the refractory resin material.

Further, the surface resin layer may contain an additive as long as the characteristics of the present invention are not impaired, and for example, a cross-linking agent, an antioxidant, an anti-blocking agent, a slip agent, an ultraviolet absorber, and a light stabilizer. Examples include agents, fillers, reinforcing agents, antistatic agents, pigments and modifying resins.

The thickness of the surface resin layer is preferably 0.1 μm or more and 5 μm or less, and more preferably 0.1 μm or more and 4 μm or less.
By setting the thickness of the surface resin layer to 0.1 μm or more, the adhesion of the thin-film deposition film can be further improved, and the gas barrier property of the base material on which the thin-film deposition film is formed can be further improved. Further, when the sealant layers are laminated, the adhesion to the sealant layer can be improved, and the laminating strength of the packaging container produced by this laminated body can be further improved.
Further, by setting the thickness of the surface resin layer to 5 μm or less, it can be used as a base material that can be suitably used for manufacturing a monomaterial packaging container. Further, the film-forming property and processability of the base material can be further improved.

Further, the surface resin layer provided on the base material may be surface-treated. Thereby, the adhesion with the adjacent layer can be improved.
The surface treatment method is not particularly limited, for example, corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas and / or nitrogen gas, physical treatment such as glow discharge treatment, and oxidation using chemicals. Examples include chemical treatment such as treatment.

The thickness of the surface resin layer is preferably 0.1 μm or more and 5 μm or less, and more preferably 0.1 μm or more and 4 μm or less.
By setting the thickness of the surface resin layer to 0.1 μm or more, the adhesion of the thin-film deposition film can be further improved, and the gas barrier property of the base material on which the thin-film deposition film is formed can be further improved. Further, when the sealant layers are laminated, the adhesion to the sealant layer can be improved, and the laminating strength of the packaging container produced by this laminated body can be further improved.
Further, by setting the thickness of the surface resin layer to 5 μm or less, it can be used as a base material that can be suitably used for manufacturing a monomaterial packaging container. Further, the film-forming property and processability of the base material can be further improved.

Further, the surface resin layer provided on the base material may be surface-treated. Thereby, the adhesion with the adjacent layer can be improved.
The surface treatment method is not particularly limited, for example, corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas and / or nitrogen gas, physical treatment such as glow discharge treatment, and oxidation using chemicals. Examples include chemical treatment such as treatment.

(Adhesive resin layer)
In one embodiment, the base material can be provided with an adhesive resin layer between the polyethylene resin layer and the surface resin layer, whereby the adhesion between these layers can be improved.

The adhesive resin layer can be formed by using an adhesive resin such as a polyether, a polyester, a silicone resin, an epoxy resin, a polyurethane, a vinyl resin, a phenol resin, and a polyolefin.
Among the above, polyolefin and this acid-modified product are preferable, and polyethylene and this acid-modified product are particularly preferable, because the laminate of the present invention can be configured to be more suitable for a monomaterial packaging container.
As the adhesive polyethylene, commercially available polyethylene can be used, and for example, Admer series manufactured by Mitsui Chemicals, Inc. can be used.

The thickness of the adhesive resin layer is not particularly limited, but can be, for example, 1 μm or more and 15 μm or less. By setting the thickness of the adhesive resin layer to 1 μm or more, the adhesion between the polyethylene resin layer and the surface resin layer can be further improved. By setting the thickness of the adhesive layer to 15 μm or less, the processability of the base material can be improved.

The base material has been subjected to a stretching treatment, and the stretching treatment may be uniaxial stretching or biaxial stretching.
The stretching ratio of the base material in the vertical direction (MD direction) and the horizontal direction (TD direction) is preferably 2 times or more and 15 times or less, and preferably 5 times or more and 13 times or less.
By setting the draw ratio to 2 times or more, the strength and heat resistance of the base material can be further improved. In addition, the printability on the base material can be improved.
Further, from the viewpoint of the breaking limit of the base material, the draw ratio is preferably 15 times or less.

In one embodiment, the base material is a co-pressed film, which can be produced by forming a film by using a T-die method, an inflation method, or the like, forming a resin film, and then stretching the film.
By forming a film by the inflation method, the resin film can be stretched at the same time.

(First sealant layer and second sealant layer)
The sealant layer contains the same resin as the polyethylene resin layer of the base material, that is, polyethylene resin. A laminate having such a structure can be suitably used as a laminate for producing a monomaterial packaging container.
As the polyethylene resin, high-density polyethylene resin (HDPE), medium-density polyethylene resin (MDPE), low-density polyethylene resin (LDPE), linear low-density polyethylene resin (LLDPE) and ultra-low-density polyethylene resin (VLDPE) are used. can do.
Further, as the polyethylene resin, a copolymer of ethylene and other monomers can also be used.
Further, as the polyethylene resin, a polyethylene resin derived from biomass or a polyethylene resin mechanically recycled or chemically recycled can also be used.

The sealant layer can contain the above-mentioned additives as long as the characteristics of the present invention are not impaired.

The sealant layer may have a single-layer structure or may have a multi-layer structure.
In one embodiment, the sealant layer comprises a layer made of low density polyethylene resin, a layer made of high density polyethylene resin and a layer made of low density polyethylene resin. With such a configuration, heat sealability and strength can be improved.

The thickness of the sealant layer is preferably 20 μm or more and 100 μm or less, and more preferably 30 μm or more and 70 μm or less.
By setting the thickness of the sealant layer to 20 μm or more, the lamination strength of the packaging container can be further improved.
Further, by setting the thickness of the sealant layer to 100 μm or less, the moldability of the laminated body can be improved, and the packaging container can be manufactured more easily.

The sealant layer may have a print layer on its surface, and the image formed on the print layer is not particularly limited, and characters, patterns, symbols, combinations thereof, and the like are represented.
The print layer can be formed on the sealant layer by using an ink derived from biomass. As a result, the environmental load can be reduced.
The method for forming the print layer is not particularly limited, and examples thereof include conventionally known printing methods such as a gravure printing method, an offset printing method, and a flexographic printing method.

The sealant layer can be laminated with a base material or the like via the melt extruded resin layer or the adhesive layer described below.

The first sealant layer and the second sealant layer included in the laminate of the present invention may have the same structure or different structures.

(Embedded film)
The laminate of the present invention is provided with a vapor-deposited film on the surface resin layer so as to be adjacent to the laminated body. In the laminated body of the present invention, the vapor-deposited film and the surface resin layer have high adhesion, and have extremely high gas barrier property, specifically, oxygen barrier property and water vapor barrier property.
Further, since the laminated body is provided with the vapor-deposited film, the packaging container produced by using the laminated body can suppress the mass reduction of the contents filled in the laminated body.

The vapor-deposited film is silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead. It can be a vapor-deposited film of one or more kinds of inorganic substances or inorganic oxides such as (Pb), zirconium (Zr), and yttrium (Y). The vapor-deposited film may be composed of two or more layers, and may be composed of the same material or different materials.
Among the above, the vapor-deposited film is preferably made of aluminum, aluminum oxide (alumina) or silicon oxide (silica) from the viewpoint of adhesion to the surface resin layer and gas barrier property. Further, by using a thin-film vapor-deposited film made of aluminum, the glossiness of the packaging container can be improved, and the design property thereof can be improved.

The surface of the vapor-deposited film is preferably subjected to the above surface treatment. Thereby, the adhesion with the adjacent layer can be improved.

The thickness of the thin-film deposition film is preferably 1 nm or more and 150 nm or less, more preferably 5 nm or more and 60 nm or less, and further preferably 10 nm or more and 40 nm or less.
By setting the thickness of the vapor-deposited film to 1 nm or more, the oxygen barrier property and the water vapor barrier property of the laminated body can be further improved.
Further, by setting the thickness of the thin-film deposition film to 150 nm or less, a laminate that can be suitably used for manufacturing a monomaterial packaging container can be obtained. Further, it is possible to prevent the occurrence of cracks in the vapor-deposited film.

As a method for forming the vapor deposition film, a conventionally known method can be adopted, for example, a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum vapor deposition method, a sputtering method, or an ion plating method, or plasma chemical vapor deposition. Examples thereof include chemical vapor deposition methods (Chemical Vapor Deposition method, CVD method) such as phase growth method, thermochemical vapor deposition method, and photochemical vapor deposition method.
Hereinafter, one embodiment of the method for forming the thin-film deposition film will be shown, but the method for forming the thin-film deposition film is not limited thereto.

As an apparatus used in the method for forming a vapor-deposited film by the PVD method, a vacuum film forming apparatus with plasma assist can be used.
An embodiment of a method for forming a vapor-deposited film using a vacuum film forming apparatus with plasma assist will be described below.
In one embodiment, as shown in FIGS. It includes F, a reaction gas supply unit G, a protective box H, a vapor deposition material I, and a plasma gun J.
FIG. 2 is a schematic cross-sectional view of the vacuum film forming apparatus in the XZ plane direction, and FIG. 3 is a schematic cross-sectional view of the vacuum film forming apparatus in the XY plane direction.
As shown in FIG. 2, the base material 10 wound by the film forming drum C method is arranged on the upper part of the vacuum vessel A with the surface resin layer surface facing downward, and is used for film formation in the vacuum vessel A. Below the drum C, an electrically grounded protective box H is arranged. The evaporation source F is arranged on the bottom surface of the protective box H. The film forming drum C is placed in the vacuum vessel A so that the surface resin layer surface of the base material 10 wound around the film forming drum C is located at a position facing the upper surface of the evaporation source F at a certain interval. Is placed.
Further, the transport roll E is arranged between the unwinding portion B and the film forming drum C, and between the film forming drum C and the winding portion D.
The vacuum container is connected to the vacuum pump (not shown).
The evaporation source F is for holding the vaporized material I and includes a heating device (not shown).
The reaction gas supply unit G is a portion that supplies a reaction gas (oxygen, nitrogen, helium, argon, a mixed gas thereof, or the like) that reacts with the evaporated vaporized material.
The vaporized vaporized material I heated and evaporated from the evaporation source F is irradiated toward the surface resin layer of the base material 10, and at the same time, plasma is also irradiated from the plasma gun J toward the surface resin layer to be vaporized. The membrane is formed.
Details of this forming method are disclosed in Japanese Patent Application Laid-Open No. 2011-214089.

As the plasma generator used in the plasma chemical vapor deposition method, a generator such as a high frequency plasma, a pulse wave plasma, or a microwave plasma can be used. Further, an apparatus having two or more film forming chambers may be used. It is preferable that the device is provided with a vacuum pump and can hold each film forming chamber in a vacuum.
The degree of vacuum in each film forming chamber is preferably ^{1 × 10 to 1 × 10-6 Pa.}
An embodiment of a method for forming a vapor-deposited film using a plasma generator will be described below.
First, the base material is sent out to the film forming chamber, and is conveyed onto the cooling / electrode drum at a predetermined speed via an auxiliary roll.
Next, a mixed gas composition containing a film-forming monomer gas containing an inorganic oxide, an oxygen gas, an inert gas, etc. is supplied from the gas supply device into the film-forming chamber, and plasma is generated on the surface resin layer by glow discharge. Is generated and irradiated with this to form a vapor-deposited film containing an inorganic oxide on the surface resin layer.
Details of this forming method are disclosed in Japanese Patent Application Laid-Open No. 2012-076292.

As an apparatus used for the method for forming a vapor-deposited film, a continuous vapor-deposited film-depositing apparatus including a plasma pretreatment chamber and a film-forming chamber can be used.
An embodiment of a method for forming a vapor-deposited film using the apparatus is described below.
First, in the plasma pretreatment chamber, plasma is irradiated from the plasma supply nozzle to the surface resin layer included in the base material. Next, a thin-film deposition film is formed on the plasma-treated surface resin layer in the film-forming chamber.
Details of this forming method will be disclosed in the international publication WO2019 / 0879960 pamphlet.

(Melted extruded resin layer and adhesive layer)
In one embodiment, the laminate of the present invention comprises a melt-extruded resin layer or an adhesive layer between the first sealant layer and the vapor-deposited film, or between the base material and the second sealant layer.
Conventionally known resin materials and adhesives can be used as the materials constituting the melt-extruded resin layer and the adhesive layer. From the viewpoint of recyclability, it is preferable to form a melt-extruded resin layer and an adhesive layer by using a polyethylene resin or a polyethylene-based adhesive.

The thickness of the melt-extruded resin layer and the adhesive layer is not particularly limited, and can be, for example, 1 to 30 μm.

(Barrier coat layer)
The laminate of the present invention can further include a barrier coat layer on the vapor-deposited film. That is, by providing the barrier coat layer between the first sealant layer and the thin-film deposition film, the gas barrier property of the laminated body can be further improved.

In one embodiment, the barrier coat layer is a polyamide resin such as ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol, polyacrylonitrile, nylon 6, nylon 6,6 and polymethoxylylen adipamide (MXD6), polyester. It is composed of a resin, a polyurethane resin, and a gas barrier resin such as a (meth) acrylic resin.

The thickness of the barrier coat layer is preferably 0.01 μm or more and 10 μm or less, and more preferably 0.1 μm or more and 5 μm or less.
By setting the thickness of the barrier coat layer to 0.01 μm or more, the gas barrier property can be further improved. By setting the thickness of the barrier coat layer to 10 μm or less, the processability of the laminated body 20 can be improved. Further, the laminated body 20 can be suitably used for manufacturing a monomaterial packaging container.

The barrier coat layer can be formed by dissolving or dispersing the above-mentioned material in water or a suitable solvent, applying the material, and drying the material.

In another embodiment, the barrier coat layer is a metal alkoxide obtained by polycondensing a mixture of a metal alkoxide and a water-soluble polymer by a sol-gel method in the presence of a sol-gel method catalyst, water, an organic solvent, or the like. A gas barrier coating film containing at least one resin composition such as a hydrolyzate of the above or a hydrolyzed condensate of a metal alkoxide.
By providing such a barrier coat layer on the vapor-deposited film, it is possible to effectively prevent the occurrence of cracks in the vapor-deposited film.

In one embodiment, the metal alkoxide is represented by the following general formula.
R ¹ _n M (OR ² ) _m
(However, in the formula, R ¹ and R ² each represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, and m represents an integer of 1 or more. , N + m represents the valence of M.)

As the metal atom M, for example, silicon, zirconium, titanium, aluminum and the like can be used.
Examples of the organic group represented by R ¹ and R ² include alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group and i-butyl group. Can be done.

Examples of the metal alkoxide satisfying the above general formula include tetramethoxysilane (Si (OCH ₃ ) ₄ ), tetraethoxysilane (mass%) Si (OC ₂ H ₅ ) ₄ ), and tetrapropoxysilane (Si (OC ₃ H)). ₇ ) ₄ ), tetrabutoxysilane (Si (OC ₄ H ₉ ) ₄ ) and the like can be mentioned.

Further, it is preferable to use a silane coupling agent together with the above metal alkoxide.
As the silane coupling agent, known organic reactive group-containing organoalkoxysilanes can be used.

As the water-soluble polymer, polyvinyl alcohol and ethylene-vinyl alcohol copolymer are preferable, and from the viewpoint of oxygen barrier property, water vapor barrier property, water resistance and weather resistance, it is preferable to use these in combination.

The thickness of the gas barrier coating film is preferably 0.01 μm or more and 10 μm or less, and more preferably 0.1 μm or more and 5 μm or less. Thereby, the gas barrier property can be further improved.
By setting the thickness of the gas barrier coating film to 0.01 μm or more, the oxygen barrier property and the water vapor barrier property of the barrier laminate can be improved. In addition, it is possible to prevent the occurrence of cracks in the vapor-deposited film.
By setting the thickness of the gas barrier coating film to 10 μm or less, the laminate 20 can be suitably used for producing a monomaterial packaging container.

The gas barrier coating film is prepared by applying a composition containing the above materials by a conventionally known means such as a roll coating such as a gravure roll coater, a spray coating, a spin coating, dipping, a brush, a bar code, and an applicator, and the composition thereof. The product can be formed by polycondensing the product by the sol-gel method.
As the sol-gel method catalyst, an acid or amine compound is suitable.

The composition may further contain an acid. The acid is used as a catalyst for the sol-gel method, mainly as a catalyst for hydrolysis of alkoxides, silane coupling agents and the like.
As the acid, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid and tartaric acid are used.

Moreover, the said composition may contain an organic solvent. As the organic solvent, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol and the like can be used.

Hereinafter, an embodiment of a method for forming a gas barrier coating film will be described below.
First, a composition is prepared by mixing a metal alkoxide, a water-soluble polymer, a sol-gel method catalyst, water, an organic solvent and, if necessary, a silane coupling agent. The polycondensation reaction gradually proceeds in the composition.
Next, the composition is applied and dried on the thin-film deposition film by the above-mentioned conventionally known method. By this drying, the polycondensation reaction of the alkoxide and the water-soluble polymer (and the silane coupling agent if the composition contains a silane coupling agent) further proceeds to form a layer of the composite polymer. Finally, by heating, a gas barrier coating film can be formed.

(Packaging container)
The packaging container of the present invention is characterized by being made of the above-mentioned laminate.

Specific examples of the packaging container of the present invention include a laminated tube, a packaging bag, and a lid material.

(Laminate tube)
In one embodiment, the packaging container of the present invention is a laminated tube 20.
Hereinafter, the laminated tube 20 of the present invention will be described with reference to the drawings. FIG. 4 is a diagram simply showing the configuration of the laminated tube 20, and FIG. 5 is a cross-sectional view taken along the line aa of FIG. As shown in FIG. 4, the laminated tube 20 includes a laminated tube main body 21 including a head portion 22 and a body portion 23, and the body portion 23 is characterized by being composed of the laminated body 10.

(head)
The head portion 22 includes a shoulder portion 24 connected to one end of the body portion 23 and an extraction port portion 25 connected to the shoulder portion 24.
Further, in one embodiment, the spout portion 25 includes a screw line 27 for screwing the cap 26.

In one embodiment, the head is made of polyethylene resin, which can improve the recyclability of the laminated tube. As the polyethylene resin, a high-density polyethylene resin, a medium-density polyethylene resin, a low-density polyethylene resin, a linear low-density polyethylene resin, and an ultra-low-density polyethylene resin can be used.
Among these, high-density polyethylene resin is preferable from the viewpoint of shape retention.
Further, as the polyethylene resin, a polyethylene resin derived from biomass or a polyethylene resin recycled by mechanical recycling or chemical recycling can be used.
The head may contain the above additives as long as the specification of the present invention is not impaired.

The method for producing the head is not particularly limited, and the head can be produced by a conventionally known method. For example, the head can be manufactured by a compression molding method (compression molding method) or an injection molding method (injection molding method), and can be joined to the body portion.

When manufacturing a laminated tube using a compression molding method (compression molding method), after attaching the body to a male mold having a convex portion at the top, the male mold and the female mold are opposed to each other and melted in the male and female. A laminated tube composed of a head and a body can be manufactured by supplying a material such as polyethylene resin, which is formed by compression molding, to form the head, and joining the material to one opening of the body.
Further, when a laminated tube is manufactured by an injection molding method (injection molding method), after mounting the body on a male mold having a convex portion at the upper part, the male mold and the female mold are opposed to each other, and polyethylene melted from the gate. A laminated tube composed of a head and a body can be manufactured by supplying a material such as resin, injection molding to form the head, and joining the head to one opening of the body.

(Torso)
In the laminated tube body of the present invention, the body portion is connected to the shoulder portion of the head.
The body portion is formed by rolling the laminate into a tubular shape, superimposing the first sealant layer and the second sealant layer, and heat-sealing the polymerized portion to form a welded portion 28. Can be obtained by
Further, the body portion includes a bottom seal portion 29 formed by heat-sealing the opening of the rolled laminate.

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

(cap)
The laminated tube can include a cap.
The cap is detachably attached to the extraction port of the head and plays a role of closing the extraction port.
The cap is made of a thermoplastic resin.
Examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, polyester, cellulose resin, vinyl resin and the like, but polyethylene resin is particularly preferable from the viewpoint of recyclability.
The cap may also contain the above additives as long as the characteristics of the present invention are not impaired.

As shown in FIG. 5, the cap may be a screw type having a concave groove on the inner surface of the cap so as to be screwed into the thread of the extraction port, and the cap is plugged into the extraction port. It may be a plug type that is fitted by this.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Example 1
(Preparation of laminate)
Ethylene vinyl alcohol copolymer (manufactured by Kuraray Co., Ltd., EVAL E171B, melting point: 165 ° C., density: 1.14 g / cm ³ ) and
Adhesive resin (manufactured by Mitsui Chemicals, maleic anhydride-modified polyethylene, Admar NF557, density: 0.920 g / cm ³ ),
With linear density polyethylene resin A (made of prime polymer, SP2520, density 0.925 g / cm ³ , melting point 122 ° C),
Was coextruded by an inflation method to obtain a film composed of a surface resin layer (10 μm), an adhesive resin layer (15 μm), and a polyethylene resin layer (100 μm).
This film was stretched in the longitudinal direction (MD) at a stretching ratio of 5 times to obtain a stretched base material having a thickness of 25 μm. The thickness after stretching was 2 μm for the surface resin layer, 3 μm for the adhesive resin layer, and 20 μm for the polyethylene resin layer.

An aluminum-deposited film having a thickness of 30 nm was formed on the surface of the surface resin layer of the stretched base material at a pressure of 3.0 × ^{10-2 Pa by the PVD method to obtain an aluminum-deposited base material.}

As the first sealant layer
Linear low-density polyethylene resin A (manufactured by Dow Chemical Co., Ltd., Dowlex2098P, density 0.926 g / cm ³ ) and
High-density polyethylene resin (Prime Polymer Hi-Zex 3300F, density 0.949 g / cm ³ ) and
Linear low-density polyethylene resin B (manufactured by Dow Chemical, Dowlex2098P, density 0.926 g / cm ³ ) and
Was coextruded by an inflation method to obtain a first sealant layer having a thickness of 120 μm.
In the first sealant layer thus obtained, the thickness of the layer made of the linear low-density polyethylene resin A is 30 μm, the thickness of the layer made of the high-density polyethylene resin is 60 μm, and the straight chain. The thickness of the layer composed of the low-density polyethylene resin B was 30 μm.

A urethane-based adhesive (manufactured by Rock Paint, RU004 / H1) is applied to the vapor-deposited surface of the base material and dried to form an adhesive layer having a thickness of 3 μm, and the first sealant layer is formed through the adhesive layer. The layer side composed of the linear low-density polyethylene A of No. 1 was bonded.

As a second sealant layer
Linear low-density polyethylene resin A (manufactured by Dow Chemical, Dowlex2098P, density 0.926 g / cm ³ ) and
High-density polyethylene (Prime Polymer Hi-Zex 3300F, density 0.949 g / cm ³ ) and
Linear low-density polyethylene resin B (manufactured by Dow Chemical, Dowlex2098P, density 0.926 g / cm ³ ) and
Was coextruded by an inflation method to obtain a heat-sealed layer having a thickness of 120 μm.
In the surface film thus obtained, the thickness of the linear low-density polyethylene 1 was 30 μm, the thickness of the high-density polyethylene was 60 μm, and the thickness of the linear low-density polyethylene 2 was 30 μm.

A low-density polyethylene resin (manufactured by Nippon Polyethylene, Novatec LC600A, density 0.918 g / cm ³ ) is melt-extruded onto a non-deposited film provided on the base material to form a melt-extruded resin layer with a thickness of 20 μm, and this melt extrusion is performed. The layer side composed of the linear low-density polyethylene resin A of the second heat-sealing layer was bonded to each other via the resin layer to prepare the laminate of the present invention.
The polyethylene content in this laminate was 98%.

Example 2
Linear low density polyethylene resin (Dow Chemical, Elite5538, density: 0.941 g / cm ³ , melting point: 129 ° C) and compatibilizer (Dow Chemical, polyethylene maleic anhydride, retain 3000, density: 0.87 g) A blended resin containing / cm ³ ) at a ratio of 8: 2 on a mass basis was prepared.

Ethylene vinyl alcohol copolymer (manufactured by Kuraray Co., Ltd., EVAL E171B, melting point: 165 ° C., density: 1.14 g / cm ³ ) and
Adhesive resin (manufactured by Mitsui Chemicals, maleic anhydride-modified polyethylene, Admar NF557, density: 0.920 g / cm ³ ),
With the blended resin prepared above
Medium density polyethylene resin (Dow Chemical, Elite5538, density: 0.941 g / cm ³ , melting point: 129 ° C),
Was coextruded by an inflation method to obtain a film having a surface resin layer of 10 μm, an adhesive resin layer of 15 μm, a layer of 50 μm composed of a blended resin, and a layer of 50 μm composed of a medium-density polyethylene resin.
This base film was stretched in the longitudinal direction (MD) at a stretching ratio of 5 times to obtain a stretched base film having a thickness of 25 μm. The thickness after stretching was 2 μm for the gas barrier resin layer, 3 μm for the adhesive resin layer, 10 μm for the layer composed of the blended resin, and 10 μm for the layer composed of the medium density polyethylene resin.

The laminate of the present invention was produced in the same manner as in Example 1 except that the base material was changed to the base material obtained as described above.
The content of the polyethylene resin in this laminate was 98%.

Example 3
Examples except that the ethylene vinyl alcohol copolymer was changed to a polyamide 6-66 copolymer (NY, manufactured by Ube Industries, Ltd., trade name: 5033, density: 1.14 g / cm ³ , melting point: 196 ° C.). A base material and a laminate were prepared in the same manner as in 1.
The content of the polyethylene resin in this laminate was 98%.

Example 4
Linear low density polyethylene (Dow Chemical, Elite5538, density: 0.941 g / cm ³ , melting point: 129 ° C) and compatibilizer (Dow Chemical, polyethylene maleic anhydride, retain 3000, density: 0.87 g / A blended resin containing cm ³ ) at a ratio of 8: 2 on a mass basis was prepared.

Polyamide 6-66 copolymer (manufactured by Ube Industries, Ltd., trade name: 5033, density: 1.14 g / cm ³ , melting point: 196 ° C.)
Adhesive resin (manufactured by Mitsui Chemicals, maleic anhydride-modified polyethylene, Admar NF557, density: 0.920 g / cm ³ ),
With the blended resin prepared above
Medium density polyethylene resin (Dow Chemical, Elite5538, density: 0.941 g / cm ³ , melting point: 129 ° C),
Was co-extruded by an inflation molding method to obtain a film composed of a surface resin layer of 10 μm, an adhesive resin layer of 15 μm, a layer composed of a blended resin of 50 μm, and a layer composed of a medium-density polyethylene resin of 50 μm.
This film was stretched in the longitudinal direction (MD) at a stretching ratio of 5 times to obtain a stretched base material having a thickness of 25 μm. The thickness after stretching was 2 μm for the surface resin layer, 3 μm for the adhesive resin layer, 10 μm for the layer composed of the blended resin, and 10 μm for the layer composed of the medium density polyethylene resin.

The laminate of the present invention was produced in the same manner as in Example 1 except that the base material was changed to the base material obtained as described above.
The content of the polyethylene resin in this laminate was 98%.

Comparative Example 1
A laminate was produced in the same manner as in Example 1 except that the base material was biaxially stretched polyethylene terephthalate (manufactured by Toyobo Co., Ltd., ester film E5100) having a thickness of 12 μm. The polyethylene content in this laminate was 93%.

(Making a tube container)
The laminate obtained as described above is processed into a slit having a width of 120 mm using a bobbin cutter, and both ends in the width direction are overlapped so that the overlap width is about 1.5 mm, and then overlapped. By heat-sealing the two ends together, a cylindrical original fabric with a cylinder attached was obtained. The obtained raw fabric was cut so as to have a length direction of 122 mm to prepare a tubular body portion to be the body portion of the tube container.

The tubular body is attached to a mandrel for forming a tube container, and a head consisting of a conical trapezoidal shoulder and a continuous extraction port on the cylinder is placed at one end of the tubular body at high density. A polyethylene resin (Novatec HJ360 manufactured by Nippon Polyethylene, density 0.951 g / cm ³ ) was molded by an injection molding method to prepare a tube container as shown in FIG.
The spout portion of the head of the obtained tube container body had an outer diameter of 13 mm and a height of 1.5 mm, and a screw was provided on the side surface of the spout portion. The outer diameter of the shoulder was 38 mm.

Next, the high-density polyethylene was injected into a mold for molding a cap and molded to prepare a cap to obtain a tube container of the present invention.

<< Recyclability Evaluation >>
The recyclability of the laminates obtained in the above Examples and Comparative Examples was evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 1.
(Evaluation criteria)
◯: The content of the same polyolefin in the laminate was 95% by mass or more.
X: The content of the same polyolefin in the laminate was less than 95% by mass.

<< Shoulder adhesive strength >>
A test piece was obtained by cutting in a strip shape with a width of 15 mm in the hem direction from the bonded portion between the body and the shoulder.
This test piece was pulled by a tensile tester (RTC-1310A, manufactured by Orientec Co., Ltd.) at a test speed of 300 mm / min, and the peel strength when the body was peeled from the shoulder was measured. The measurement results are summarized in Table 1.

<< Side seam strength >>
It was cut into strips with a width of 15 mm in the direction perpendicular to the side seams (overlapping points) of the body, pulled by a tensile tester at a test speed of 300 mm / min, and the strength at break was measured. The measurement results are summarized in Table 1.

<< Leakage evaluation >>
A cap was spiraled into the extraction port of the tube container body, and then 120 g of commercially available toothpaste as a content was filled through the opening of the tubular body, and then the opening of the tubular body was heat-sealed. The set tightening torque when the cap was closed was 4.7 kg · cm. It was left in a room temperature environment for 2 weeks, and the contents were visually checked every day for leakage. The evaluation criteria for leakability were as follows.
(Evaluation criteria)
〇: No leakage of contents was observed even after 2 weeks. ×: Leakage of contents was observed before 2 weeks.

<< Gas barrier property evaluation >>
^{The oxygen permeability (cc / m 2} · day · atm) and the water vapor transmission rate (g / m ² · day) of the gas barrier laminates and the laminates obtained in Examples and Comparative Examples were measured by the following methods. The results are summarized in Table 1.

[Oxygen permeability]
Using an oxygen permeability measuring device (OX-TRAN2 / 20 manufactured by MOCON), set the test piece so that the base material surface is on the oxygen supply side, and comply with JIS K 7126 at 23 ° C. and relative humidity. Oxygen permeability was measured in a 90% RH environment.

[Moisture vapor transmission rate]
Using a water vapor transmission rate measuring device (MOCON, PERMATRAN-w 3/33), set the test piece so that the base material surface is on the water vapor supply side, and set it at 40 ° C. in accordance with JIS K 7129. The water vapor transmission rate in a 90% relative humidity RH environment was measured.

<< Laminate strength test >>
A sample obtained by cutting the laminates obtained in the above Examples and Comparative Examples into strips having a width of 15 mm was subjected to JIS K6854-2 using a tensile tester (manufactured by Orientec Co., Ltd., Tensilon universal material tester). In accordance with this, the lamination strength (N / 15 mm) between the vapor-deposited film and the surface resin layer (Example) and between the vapor-deposited film and the biaxially stretched polyethylene terephthalate film (Comparative Example) is set at a peeling rate of 50 mm / min. It was measured using 90 ° peeling (T-shaped peeling method). The measurement results are summarized in Table 1.

10: Laminate, 11: First sealant layer, 12: Vapor film, 13: Base material, 14: Second sealant layer, 15: Surface resin layer, 16: Polyethylene resin layer, 17: Weld extruded resin layer or Adhesive layer, 20: Laminate tube, 21: Laminate tube body, 22: Head, 23: Body, 24: Shoulder, 25: Spout, 26: Cap, 27: Screw, 28: Weld, 29: Bottom seal

Claims (13)

A laminate including at least a first sealant layer, a thin-film deposition film, a base material, and a second sealant layer in this order.
The base material comprises at least a polyethylene resin layer and a surface resin layer.
The first sealant layer and the second sealant layer are made of polyethylene resin.
The surface resin layer of the base material contains a resin material having a melting point of 150 ° C. or higher.
The vapor-deposited film is provided on the surface resin layer of the base material, and is provided on the surface resin layer.
A laminate, wherein the base material is stretched. The laminate according to claim 1, wherein the surface resin layer contains a resin material having a melting point of 150 ° C. or higher and 265 ° C. or lower. The laminate according to claim 1 or 2, wherein the difference in melting point between the polyethylene resin and the resin material having a melting point of 150 ° C. or higher contained in the surface resin layer is 20 to 80 ° C. The laminate according to any one of claims 1 to 3, wherein the resin material of the surface resin layer is made of a polymer having a polar group. The resin material of the surface resin layer is selected from ethylene vinyl alcohol copolymer, polyvinyl alcohol, polyester, nylon 6, nylon 6,6, nylon 6-nylon 6,6 copolymer, MXD nylon and amorphous nylon1 The laminate according to any one of claims 1 to 4, which is the above resin material. The laminate according to any one of claims 1 to 5, wherein the polyethylene resin layer of the base material has a multilayer structure. The laminate according to any one of claims 1 to 6, wherein the polyethylene resin layer of the base material includes at least one layer containing a compatibilizer. The laminate according to any one of claims 1 to 7, wherein the base material is a co-pressed film. The laminate according to any one of claims 1 to 8, further comprising a barrier coat layer between the first sealant layer and the vapor-deposited film. The laminate according to any one of claims 1 to 9, which is used for a packaging container. The laminate according to any one of claims 1 to 10, wherein the content of the polyethylene resin in the entire laminate is 95% by mass or more. A packaging container comprising the laminate according to any one of claims 1 to 11. The packaging container according to claim 12, which is a laminated tube.

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