JP2021160259A - Laminate and packaging container - Google Patents

Abstract

To provide a laminate excellent in interlayer adhesion with a vapor-deposited film, as well as having high gas barrier properties.SOLUTION: A laminate at least includes a substrate, a vapor-deposited film and a sealant layer. The sealant layer includes a surface resin layer and a polyethylene resin layer. The substrate is composed of a polyethylene resin. The surface resin layer of the sealant layer includes a resin material with a melting point 150°C or higher. The vapor-deposited film is disposed on the surface resin layer of the sealant layer.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. Is used for.

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

The packaging container obtained by molding the above-mentioned dissimilar resin film, that is, a laminate obtained by laminating a polyester film and a polyethylene film is difficult to separate into each layer, and is recovered after use. The current situation is that these packaging containers are not suitable for recycling and are not actively recycled.

In view of this situation, for the purpose of improving the recyclability of packaging containers, a stretched polyethylene film (stretched polyethylene film) is applied to the base material instead of the polyester film, and laminated made of the same material. The production of packaging containers (monomaterial packaging containers) using the body is being studied.

Japanese Unexamined Patent Publication No. 2005-053223

Recently, the present inventors have attempted to form a vapor-deposited film on the surface of the polyethylene film of the sealant layer in order to compensate for the gas barrier property deteriorated due to the change of the base material from the polyester film to the stretched polyethylene film. We have found a new problem that the adhesion between the film and the vapor-deposited film is not sufficient and a satisfactory gas barrier property cannot be obtained.

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 was found that the adhesion is improved, and the gas barrier property 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 as a laminate for producing a monomaterial packaging container, and the adhesion between layers with a vapor-deposited film. It is to provide a laminate which can be remarkably improved and can achieve a preferable gas barrier property.

Furthermore, an object to be solved by the present invention is to provide a packaging container provided with the laminate.

The laminate of the present invention includes at least a base material, a vapor-deposited film, and a sealant layer.
The sealant layer includes a surface resin layer and a polyethylene resin layer.
The base material is made of polyethylene resin.
The surface resin layer of the sealant layer 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 sealant layer.

In one embodiment, the surface resin layer comprises 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 sealant layer has a multilayer structure.

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

In one embodiment, the surface resin layer is provided so as to be in contact with the layer containing the compatibilizer of the polyethylene resin layer.

In one embodiment, the laminate of the present invention is further provided with a barrier coat layer on the vapor-deposited film.

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

In one embodiment, the content of the polyethylene resin in the entire laminate is 80% 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 packaging bag.

According to the present invention, it can be suitably used as a laminate 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 provide a laminate,
Further, according to the present invention, it is possible to provide a packaging container provided with the laminate.

It is a schematic cross-sectional view which shows one Embodiment of the laminated body of this invention. 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 one Embodiment of the packaging container of this invention. It is a perspective view which shows one Embodiment of the packaging container of this invention. It is a front view which shows one Embodiment of the packaging container of this invention. FIG. 7 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 a base material 11, a vapor-deposited film 12, and a sealant layer 13, and the sealant layer 13 includes a surface resin layer 14 and a polyethylene resin layer 15. Be prepared.
The polyethylene resin layer of the sealant layer included in the laminate and the base material are made of the same resin, that is, a polyethylene resin. A laminate having such a structure can be suitably used as a laminate for producing a monomaterial packaging container.
Further, the laminate of the present invention has a remarkably improved adhesion between the sealant layer and the vapor-deposited film, and has an extremely high gas barrier property.

The content of the polyethylene resin with respect to the total amount of solids contained in the laminate is preferably 80% by mass or more, and more preferably 90% by mass or more. This makes it possible to obtain a laminate that can be suitably used for producing a monomaterial packaging container.

Further, in one embodiment, as shown in FIG. 2, the sealant layer 13 may further include an adhesive resin layer 16 between the surface resin layer 14 and the polyethylene resin layer 15.

Further, in one embodiment, the laminate 10 of the present invention includes a barrier coat layer adjacent to the vapor-deposited film 12 (not shown).

Further, in one embodiment, the laminate 10 of the present invention includes an adhesive layer between arbitrary layers, for example, between the vapor deposition film 12 and the sealant layer 13 (not shown).

Hereinafter, each layer included in the laminate of the present invention will be described.

(Base material)
The base material is composed of the same resin as the polyethylene resin layer of the sealant layer, 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.

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 base material is preferably 80% by mass or more, and more preferably 90% by mass or more. This makes it possible to obtain a laminate that can be suitably used for producing a monomaterial packaging container.

The base material may contain a resin material other than the polyethylene resin as long as the characteristics of the present invention are not impaired. For example, a polyolefin resin such as a polypropylene resin, a (meth) acrylic resin, a vinyl resin, a cellulose resin, and a polyamide resin may be contained. , Polyester resin, ionomer resin and the like.
From the viewpoint of recycling suitability, it is particularly preferable that the base material does not contain a resin other than the polyethylene resin.

The base material may contain the above additives as long as the characteristics of the present invention are not impaired.

The base material may have a single-layer structure or may have a multi-layer structure.

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

In a base material 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.

Hereinafter, embodiments of a base material provided with a density gradient will be illustrated. The composition of the base material is not limited to these.

In one embodiment, the base material provided with the density gradient consists 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 base material 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 substrate provided with the density gradient is a layer containing a high density polyethylene, a layer containing a medium density polyethylene resin, and a layer containing at least one of a low density polyethylene resin and a linear low density polyethylene resin. And a layer containing a medium-density polyethylene resin and a layer containing a high-density polyethylene resin.
By forming the base material 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.
A base material 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 substrate 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 low. It is composed of seven layers: a layer containing at least one of the high-density polyethylene resins, a layer containing a blended resin of the high-density polyethylene resin and the medium-density polyethylene resin, and a layer containing the high-density polyethylene resin.
By forming the base material 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 base material having such a structure can be stably produced by the inflation method described above.

In one embodiment, the base material is stretched, 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.

The base material 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 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.

Further, the base material is preferably 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.
Further, an anchor coat layer may be formed on the surface of the base material by using a conventionally known anchor coat agent.

The thickness of the base material is preferably 9 μm or more and 50 μm or less, and more preferably 12 μm or more and 30 μm or less. By setting the thickness of the base material within the above numerical range, the printability, strength and heat resistance of the base material can be further improved.

(Embedded film)
The laminate of the present invention is between the base material and the sealant layer, and has a vapor-deposited film on the surface resin layer. Thereby, the gas barrier property, specifically, the oxygen barrier property and the water vapor barrier property can be improved.
In addition, it is possible to suppress a decrease in the mass of the contents filled in the packaging container produced by using the laminate of the present invention.

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 thin-film 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.

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 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. 3 and 4, the vacuum film forming apparatus includes the vacuum container A, the sealant layer 10, the unwinding portion B, the film forming drum C, the winding portion D, the transport roll E, and the evaporation source. F, a reaction gas supply unit G, a protective box H, a vapor deposition material I, and a plasma gun J are provided.
3 is a schematic cross-sectional view of the vacuum film forming apparatus in the XZ plane direction, and FIG. 4 is a schematic cross-sectional view of the vacuum film forming apparatus in the XY plane direction.
As shown in FIG. 3, a sealant layer 10 wound by the film forming drum C method is arranged on the upper part of the vacuum vessel A with its 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 sealant layer 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 sealant layer 10, and at the same time, plasma is also irradiated from the plasma gun J toward the surface resin layer for vaporization. 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 sealant layer 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 to the surface resin layer of the sealant layer from the plasma supply nozzle. 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.

(Sealant layer)
The sealant layer includes a surface resin layer and a polyethylene resin layer. Further, in one embodiment, an adhesive resin layer is provided between the surface resin layer and the polyethylene resin layer.

The ratio of the thickness of the surface resin layer to the total thickness of the sealant layer 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 sealant layer 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 sealant layer 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 sealant layer 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.

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 can be more preferably used in the production of the 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, the resin material contained in the surface resin layer having a melting point of 150 ° C. or higher and the polyethylene resin layer It is possible to effectively prevent the polyethylene resin contained in the above 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 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 in the sealant layer.

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 in the sealant layer.
The polyethylene resin layer having such a structure can be stably produced by the inflation method described above.

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 in the sealant layer. Further, it is possible to effectively prevent the occurrence of delamination in the sealant layer.
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 sealant layer 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 sealant layer 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 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 sealant layer included in the laminate includes a surface protective layer containing a resin material having a melting point of 150 ° C. or higher (hereinafter, also referred to as a refractory resin material) on the polyethylene resin layer. A thin-film film having high adhesion can be formed on the surface resin layer, and the gas barrier property can be improved.
Further, the packaging container produced by using the laminate of the present invention has high laminate strength (heat sealability).

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. In addition, the lamination strength of the packaging container produced by this laminate 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 sealant layer 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. In addition, the lamination strength of the packaging container produced by this laminate 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 sealant layer 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 sealant layer 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 sealant layer 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 is possible to obtain a sealant layer that can be suitably used for manufacturing a monomaterial packaging container. Further, the film-forming property and processability of the sealant layer can be further improved.

Further, the surface resin layer 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 sealant layer 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 can be configured to be more suitable for the 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.

In one embodiment, the sealant layer is a co-pressed film and can be produced by forming a film using a T-die method, an inflation method, or the like.

From the viewpoint of heat sealability, the sealant layer is preferably composed of an unstretched film.
Further, when the laminated body is used for manufacturing a laminated tube or the like, the laminated body further includes a sealant layer on the non-deposited film-forming surface of the base material (not shown).

(Barrier coat layer)
The laminate may further include a barrier coat layer on the vapor-deposited film. Thereby, the oxygen barrier property and the water vapor barrier property of the laminated body can be 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. Includes resins, polyurethane resins, and gas barrier resins such as (meth) acrylic resins.

The content of the gas barrier resin in the barrier coat layer is preferably 50% by mass or more and 95% by mass or less, and more preferably 75% by mass or more and 90% by mass or less. By setting the content of the gas barrier resin in the barrier coat layer to 50% by mass or more, the oxygen barrier property and the water vapor barrier property can be further improved.

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 oxygen barrier property and the water vapor barrier property of the laminated body can be further improved. By setting the thickness of the barrier coat layer to 10 μm or less, the processability of the laminated body can be improved. Further, it is possible to improve the recyclability of the packaging container produced by using the laminate of the base material and the sealant layer made of polyethylene resin.

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. The barrier coat layer can also be formed by applying a commercially available barrier coat agent and drying it.

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.
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 laminated body 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, a laminate that can be suitably used for producing a monomaterial packaging container can be obtained.

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.

(Adhesive layer)
The laminate of the present invention may include an adhesive layer between any layers, for example, between the vapor deposition film and the sealant layer.
The adhesive layer contains at least one type of adhesive, and may be a one-component curable type, a two-component curable type, or a non-curable type. Further, the adhesive may be a solvent-free adhesive or a solvent-type adhesive, but from the viewpoint of environmental load, a solvent-free adhesive can be preferably used.
Examples of the solvent-free adhesive include polyether adhesives, polyester adhesives, silicone adhesives, epoxy adhesives and urethane adhesives, and among these, two-component curable urethanes. A system adhesive can be preferably used.
Examples of the solvent-based adhesive include rubber-based adhesives, vinyl-based adhesives, silicone-based adhesives, epoxy-based adhesives, phenol-based adhesives, and olefin-based adhesives.

The thickness of the adhesive layer is preferably 1 μm or more and 15 μm or less, and more preferably 3 μm or more and 10 μm or less. By setting the thickness of the adhesive layer to 1 μm or more, the adhesion between the layers can be improved. Further, by setting the thickness of the adhesive layer to 15 μm or less, it is possible to improve the recyclability of the packaging container produced by using the barrier laminate of the present invention provided with the base material composed of polyethylene and the sealant layer. can.

(Packaging container)
The packaging container of the present invention is characterized by including the above-mentioned laminate. Examples of the packaging container include a packaging product (packaging bag), a lid material, and a laminated tube.

As a packaging bag, for example, standing pouch type, side seal type, two-way seal type, three-way seal type, four-way seal type, envelope-attached seal type, gassho-attached seal type (pillow-seal type), fold-attached seal type, flat-bottom seal type. , Various types of packaging bags such as a square bottom seal type and a gusset type.

As shown in FIG. 5, the packaging container of the present invention is a packaging bag 20 in which two laminated bodies are bonded together (the shaded area is a heat-sealed portion).

For the packaging bag having the form shown in FIG. 5, two laminates including the base material and the vapor-deposited film and the sealant layer provided on one surface of the base material are prepared, and the sealant layers face each other. It can be produced by superimposing them in such a manner and heat-sealing the three sides.

In one embodiment, as shown in FIG. 6, the packaging container of the present invention is a standing pouch type packaging bag 30 (hereinafter, simply referred to as a standing pouch 30), and the standing pouch 30 is a body portion (side sheet). And a bottom (bottom sheet).
The body (side sheet) of the standing pouch 30 is composed of at least a base material and a laminate having a vapor-deposited film and a sealant layer provided on one surface of the base material.
Further, the bottom portion may also be composed of a base material and a laminate having a vapor-deposited film and a sealant layer provided on one surface of the base material. With such a configuration, the gas barrier property of the standing pouch 30 can be further improved.

As shown in FIG. 6, the body (side sheet) of the standing pouch 30 has a base material, and a sealant layer provided by a laminate having a vapor-deposited film and a sealant layer provided on one surface of the base material is the innermost layer. It can be formed by making a bag so as to be.
In another embodiment, two laminated bodies having a base material and a vapor-deposited film and a sealant layer provided on one surface of the base material are prepared, and these are laminated so that the sealant layers face each other and overlapped. Two V-shaped laminates are inserted from both ends of the combined laminate so that the sealant layer is on the outside, and heat-sealed to form the body (side sheet) of the standing pouch 30. can do. According to such a manufacturing method, a stand pouch having a body portion with a side gusset can be obtained.
Further, the bottom portion (bottom sheet) of the standing pouch 30 can be formed by inserting a laminated body between the bag-made body portions (side sheet) and heat-sealing. More specifically, the laminate can be formed by folding it in a V shape so that the sealant layer is on the outside, inserting it between the bag-made side sheets, and heat-sealing it.

Further, as shown in FIG. 5, the packaging container may be provided with the easy-opening means 41.
Examples of the easy-opening means 41 include a notch portion 42 which is a starting point of tearing and a half-cut line 43 formed by laser processing or a cutter as a path for tearing, as shown in FIG.

Further, as shown in FIG. 6, the packaging container may be a stand pouch provided with a nozzle portion 51 for dispensing.
Further, from the viewpoint of ease of opening, the stand pouch 30 may include a curved portion 52 that is curved inward, as shown in FIG.
Further, a cutting portion 53 formed by a laser beam or the like may be provided.

(Laminate tube)
The laminated tube of the present invention is characterized by including the above-mentioned laminated body, specifically, a laminated body composed of a laminated film having a sealant layer on both sides.
Hereinafter, the laminated tube of the present invention will be described with reference to the drawings. FIG. 7 is a diagram simply showing the configuration of the laminated tube 60, and FIG. 8 is a cross-sectional view taken along the line aa of FIG. As shown in FIG. 7, the laminated tube 60 includes a laminated tube main body 61 including a head portion 62 and a body portion 63, and the body portion 63 is characterized by being composed of the laminated body.

(head)
The head portion 62 includes a shoulder portion 64 connected to one end of the body portion 63 and an extraction port portion 65 connected to the shoulder portion 64.
Further, in one embodiment, the spout portion 65 includes a screw line 67 for screwing the cap 66.

In one embodiment, the head is made of a resin composition containing polyethylene, which can improve the recyclability of the tube container.

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.

(Torso)
In the laminated tube main body 61 of the present invention, the body portion 63 is connected to the shoulder portion 64 of the head portion 62.
The body portion 63 includes a welding portion 68 formed by rolling the laminated body into a tubular shape, superimposing the heat-sealing layers on top of each other, and heat-sealing the overlapped portion.
Further, the body portion 63 includes a bottom seal portion 69 formed by heat-sealing the opening of the rolled laminate.

(cap)
The laminated tube 60 can include a screw type or plug type cap 66.
The cap is detachably attached to the extraction port of the head and plays a role of closing the extraction port.
The cap is composed of a resin composition containing a thermoplastic resin.
As the thermoplastic resin, a polyethylene resin is particularly preferable from the viewpoint of recyclability.

The contents to be filled in the packaging container are not particularly limited, and the contents may be a liquid, a powder or a gel. Moreover, it may be food or non-food.

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 1-1
Medium-density polyethylene (Dow Chemical, Elite5538, density: 0.941 g / cm ³ , melting point: 129 ° C.) is extruded into a single-layer film by the inflation method, and then stretched 5 times in the longitudinal direction (MD direction) by a stretching device. Then, a base material having a thickness of 25 μm 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, Inc., maleic anhydride-modified polyethylene, Admar NF557, density: 0.920 g / cm ³ ),
With linear density polyethylene (made of prime polymer, SP1520, density 0.913, melting point 116 ° C),
Was coextruded by the T-die method to obtain a sealant layer having a thickness of 40 μm.
In the sealant layer thus obtained, the surface resin layer composed of the ethylene vinyl alcohol copolymer has a thickness of 2 μm, the adhesive resin layer has a thickness of 3 μm, and is composed of linear low-density polyethylene. The thickness of the polyethylene resin layer was 35 μm.

Surface of Sealant Layer An aluminum vapor deposition film having a thickness of 30 nm was formed on the surface of the resin layer at a pressure of 3.0 × ^{10-2 Pa by the PVD method.}

The base material and the vapor-film-forming surface of the sealant layer were laminated via a two-component curable urethane adhesive (Ru-77T / H-7, manufactured by Rock Paint Co., Ltd.) to obtain the laminate of the present invention. ..
The polyethylene content in the laminate is summarized in Table 1. In addition, the polyethylene contents in the laminates and the laminates obtained in the following Examples and Comparative Examples are also summarized in Table 1.

Example 1-2
High-density polyethylene (manufactured by ExxonMobil, HTA108, density: 0.961 g / cm ³ , melting point: 135 ° C.),
Medium density polyethylene (Dow Chemical, Elite5538, density: 0.941 g / cm ³ , melting point: 129 ° C),
High-density polyethylene (manufactured by ExxonMobil, HTA108, density: 0.961 g / cm ³ , melting point: 135 ° C.),
Was co-extruded by an inflation molding method and then stretched 5 times in the longitudinal direction (MD direction) by a stretching device to prepare a base material.
In the base material thus obtained, the thickness of the layer made of high-density polyethylene is 5 μm, the thickness of the layer made of medium-density polyethylene is 15 μm, and the thickness of the layer made of high-density polyethylene. Was 5 μm.

A laminate was prepared in the same manner as in Example 1-1, except that the base material was changed to a base material having a three-layer structure prepared as described above.

Example 1-3
High-density polyethylene (manufactured by ExxonMobil, HTA108, density: 0.961 g / cm ³ , melting point: 135 ° C.),
High-density polyethylene (ExxonMobil, HTA108, density: 0.961 g / cm ³ , melting point: 135 ° C.) and medium-density polyethylene (Dow Chemical, Elite5538, density: 0.941 g / cm ³ , melting point: 129 ° C.) , With a blended resin containing 4: 6 on a mass basis,
Medium density polyethylene (Dow Chemical, Elite5538, density: 0.941 g / cm ³ , melting point: 129 ° C),
Ultra-low density polyethylene (manufactured by Dow Chemical, Infinity EG8100G, density: 0.870 g / cm ³ , melting point: 55 ° C),
By the inflation molding method, a tubular layer having a layer made of high-density polyethylene, a layer made of blended resin, a layer made of medium-density polyethylene, and a layer made of ultra-low-density polyethylene is provided from the outside. As the film, the layers made of extruded and ultra-low density polyethylene inside were pressure-bonded using a rubber roll.
The film thus obtained is composed of a layer made of high-density polyethylene, a layer made of blended resin, a layer made of medium-density polyethylene, a layer made of ultra-low-density polyethylene, and a layer made of medium-density polyethylene. It was provided with a layer to be formed, a layer made of a blended resin, and a layer made of high-density polyethylene.

The film obtained as described above was stretched 5 times in the longitudinal direction (MD direction) by a stretching device to prepare a base material.
In the film thus obtained, the thickness of the layer made of high-density polyethylene is 2.5 μm, the thickness of the layer made of blended resin is 2.5 μm, and the thickness of the layer made of medium-density polyethylene is 6. .25 μm, the thickness of the layer made of ultra-low density polyethylene is 2.5 μm, the thickness of the layer made of medium density polyethylene is 6.25 μm, the thickness of the layer made of blended resin is 2.5 μm. And the thickness of the layer composed of high density polyethylene was 2.5 μm.

A laminate was prepared in the same manner as in Example 1-1, except that the base material was changed to a base material having a 7-layer structure prepared as described above.

Example 1-4
The sealant was the same as in Example 1-1, except that the ethylene vinyl alcohol copolymer was changed to polyamide (manufactured by Ube Industries, Ltd., 5033, melting point: 196 ° C., density: 1.14 g / cm ^3). Layers were made.
In the sealant layer thus obtained, the thickness of the surface resin layer made of polyamide is 2 μm, the thickness of the adhesive resin layer is 3 μm, and the thickness of the polyethylene resin layer made of medium-density polyethylene is 35 μm. Met.

A laminate was prepared in the same manner as in Example 1-1, except that the sealant layer was changed to the sealant layer prepared as described above.

Example 1-5
Ethylene vinyl alcohol copolymer (manufactured by Kuraray Co., Ltd., EVAL E171B, melting point: 165 ° C., density: 1.14 g / cm ³ ) and
Adhesive resin (Mitsui Chemicals, Inc., Admer NF557) and
Linear low density polyethylene (Prime Polymer, SP1520, density: 0.913 g / cm ³ , melting point: 116 ° C) and compatibilizer (Dow Chemical, polyethylene maleic anhydride, retain 3000, density: 0.87 g / With ^{a blended resin containing cm 3} ) at a ratio of 8: 2 on a mass basis,
With linear density polyethylene (made of prime polymer, SP1520, density: 0.913 g / cm ³ , melting point: 116 ° C),
Was co-extruded by the T-die method to prepare a sealant layer.
In the sealant layer thus obtained, the thickness of the surface resin layer composed of the ethylene vinyl alcohol copolymer is 2 μm, the thickness of the adhesive resin layer is 3 μm, and the second polyethylene composed of the blended resin. The thickness of the resin layer was 15 μm, and the thickness of the first polyethylene resin layer composed of linear low-density polyethylene was 20 μm.

A laminate was prepared in the same manner as in Example 1-1, except that the sealant layer was changed to the sealant layer prepared as described above.

Example 1-6
The sealant was the same as in Example 1-5, except that the ethylene vinyl alcohol copolymer was changed to polyamide (manufactured by Ube Industries, Ltd., 5033, melting point: 196 ° C., density: 1.14 g / cm ^3). Layers were made.
In the sealant layer thus obtained, the thickness of the surface resin layer made of polyamide is 2 μm, the thickness of the adhesive resin layer is 3 μm, and the thickness of the second polyethylene resin layer made of blended resin. The thickness of the first polyethylene resin layer composed of medium-density polyethylene was 10 μm.

A laminate was prepared in the same manner as in Example 1-1, except that the sealant layer was changed to the sealant layer prepared as described above.

Comparative Example 1-1
A linear density polyethylene (made of prime polymer, SP1520, density: 0.913 g / cm ³ , melting point: 116 ° C.) was extruded into a single layer by an inflation forming method to prepare a 40 μm unstretched polyethylene film.

A laminate was prepared in the same manner as in Example 1-1 except that the sealant layer was changed to the unstretched polyethylene film prepared as described above.

Example 2-1
The laminate of the present invention was produced in the same manner as in Example 1-1, except that the aluminum vapor deposition film was changed to an aluminum oxide (alumina) vapor deposition film having a thickness of 20 nm formed by the PVD method.

Example 2-2
The laminate of the present invention was produced in the same manner as in Example 1-2 except that the aluminum vapor deposition film was changed to an aluminum oxide (alumina) vapor deposition film having a thickness of 20 nm formed by the PVD method.

Example 2-3
The laminate of the present invention was produced in the same manner as in Examples 1-3 except that the aluminum vapor-deposited film was changed to an aluminum oxide (alumina) vapor-deposited film having a thickness of 20 nm formed by the PVD method.

Example 2-4
The laminate of the present invention was produced in the same manner as in Examples 1-4 except that the aluminum vapor deposition film was changed to an aluminum oxide (alumina) vapor deposition film having a thickness of 20 nm formed by the PVD method.

Example 2-5
The laminate of the present invention was produced in the same manner as in Example 1-5, except that the aluminum vapor deposition film was changed to an aluminum oxide (alumina) vapor deposition film having a thickness of 20 nm formed by the PVD method.

Example 2-6
The laminate of the present invention was produced in the same manner as in Example 1-6, except that the aluminum vapor deposition film was changed to an aluminum oxide (alumina) vapor deposition film having a thickness of 20 nm formed by the PVD method.

Comparative Example 2-1
A laminate was produced in the same manner as in Comparative Example 1-1, except that the aluminum vapor deposition film was changed to an aluminum oxide (alumina) vapor deposition film having a thickness of 20 nm formed by the PVD method.

<< Gas barrier property evaluation >>
^{The oxygen permeability (cc / m 2} · day · atm) and the water vapor transmission rate (g / m ² · day) of the laminate and the laminate obtained in Examples and Comparative Examples were measured by the following methods, and the same was measured. 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 >>
Using a tensile tester (manufactured by Orientec Co., Ltd., Tencilon universal material tester), JIS K6854 was used to cut the laminates obtained in the above Examples and Comparative Examples into strips having a width of 15 mm. According to -2, the lamination strength (N / 15 mm) between the thin-film film and the surface resin layer (Example) and between the thin-film film and the polyethylene film (Comparative Example) is 90 at a peeling speed of 50 mm / min. Measured using ° peeling (T-shaped peeling method). The measurement results are summarized in Table 1.

10: Laminate, 11: Base material, 12: Vapor deposition film, 13: Sealant layer, 14: Surface resin layer, 15: Polyethylene resin layer, 16: Adhesive resin layer, 20: Packaging bag, 30: Standing pouch, 41 : Easy opening means, 42: Notch part, 43: Half cut line, 51: Extraction nozzle part, 52: Curved part, 53: Cut part, 60: Laminated tube, 61: Laminated tube body, 62: Head, 63 : Body, 64: Shoulder, 65: Outlet, 66: Cap, 67: Screw, 68: Weld, 69: Bottom seal

Claims (13)

A laminate having at least a base material, a vapor-deposited film, and a sealant layer.
The sealant layer includes a surface resin layer and a polyethylene resin layer.
The base material is made of polyethylene resin.
The surface resin layer of the sealant layer contains a resin material having a melting point of 150 ° C. or higher.
A laminate characterized in that the vapor-deposited film is provided on the surface resin layer of the sealant layer. 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 sealant layer has a multilayer structure. The laminate according to claim 6, wherein the polyethylene resin layer of the sealant layer includes at least one layer containing a compatibilizer. The laminate according to claim 7, wherein the surface resin layer is provided so as to be in contact with the layer containing the compatibilizer of the polyethylene resin layer. The laminate according to any one of claims 1 to 8, wherein a barrier coat layer is further provided on 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 80% by mass or more. A packaging container made of the laminate according to any one of claims 1 to 11. The packaging container according to claim 12, which is a packaging bag.

Images