JP2020040258A - Gas barrier laminate, packaging material laminate and packaging material - Google Patents

Abstract

To provide a gas barrier laminate that can be used as an intermediate layer constituting a packaging material laminate and has high oxygen barrier properties and water vapor barrier properties.SOLUTION: A gas barrier laminate has a gas barrier resin layer, and a polyolefin resin layer, the gas barrier resin layer and polyolefin resin layer being co-extruded stretched resin films.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a gas barrier laminate, a laminate for packaging materials provided with the gas barrier laminate, and a packaging material composed of the laminate for packaging materials.

  BACKGROUND ART Conventionally, a resin film made of a resin material has been used as a constituent material of a packaging material, and a packaging material laminate composed of a plurality of resin films has been widely used. Various functions are required for the packaging material depending on the content to be filled. For example, gas barrier properties such as oxygen barrier properties and water vapor barrier properties are required in order to prevent the contents from deteriorating over time.

For example, as a packaging material laminate having improved gas barrier properties, a gas barrier layer made of polyamide or the like is provided as an intermediate layer between a base material such as a polyester film and a heat seal layer.
However, the laminate for packaging materials has been required to further improve gas barrier properties.

  The present invention has been made in view of the above circumstances, and a problem to be solved is that it can be used as an intermediate layer constituting a laminate for packaging materials, and has high oxygen barrier properties and water vapor barrier properties. It is to provide a gas barrier laminate.

  Another object of the present invention is to provide a packaging material laminate having the gas barrier laminate and having significantly improved oxygen barrier properties and water vapor barrier properties.

  A further object of the present invention is to provide a packaging material comprising the laminate for packaging material.

  The gas barrier laminate of the present invention includes a gas barrier resin layer and a polyolefin resin layer, wherein the gas barrier resin layer and the polyolefin resin layer are co-stretched resin films.

  In one embodiment of the present invention, the gas barrier laminate includes an adhesive resin layer between the gas barrier resin layer and the polyolefin resin layer.

  In one embodiment of the present invention, the thickness of the gas barrier resin layer is smaller than the thickness of the polyolefin resin layer.

The packaging material laminate of the present invention includes a base material, the gas barrier laminate, and a heat seal layer.
The base material is a stretched resin film composed of polyolefin,
The heat seal layer is made of polyolefin,
The polyolefin constituting the base material, the polyolefin constituting the polyolefin resin layer of the gas barrier laminate, and the polyolefin constituting the heat seal layer are the same polyolefin.

  In one embodiment of the present invention, the packaging material laminate includes a vapor-deposited film on at least one of the substrate and the gas barrier laminate, and between the gas barrier laminate and the heat seal layer. .

  In one embodiment of the present invention, the packaging material laminate includes an adhesive layer between the substrate and the vapor-deposited film, and between the gas barrier laminate and the vapor-deposited film.

In one embodiment of the present invention, the deposited film is an aluminum deposited film,
The adhesive layer contains a cured product of a resin composition containing a polyester polyol, an isocyanate compound, and a phosphoric acid-modified compound.

  In one embodiment of the present invention, the content of the polyolefin in the entire packaging material laminate is 80% by mass or more.

  The packaging material of the present invention is characterized by comprising the above-mentioned laminate for packaging material.

  ADVANTAGE OF THE INVENTION According to this invention, it can be used as an intermediate | middle layer which comprises the laminated body for packaging materials, and can provide the gas-barrier laminated body which has a high oxygen barrier property and a water vapor barrier property.

  Further, according to the present invention, it is possible to provide a packaging material laminate including the gas barrier laminate.

  Further, according to the present invention, it is possible to provide a packaging material composed of the laminate for packaging material.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional schematic which shows one Embodiment of the gas-barrier laminated body of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional schematic which shows one Embodiment of the gas-barrier laminated body of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional schematic which shows one Embodiment of the laminated body for packaging materials of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional schematic which shows one Embodiment of the laminated body for packaging materials of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional schematic which shows one Embodiment of the laminated body for packaging materials of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional schematic which shows one Embodiment of the laminated body for packaging materials of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional schematic which shows one Embodiment of the laminated body for packaging materials of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional schematic which shows one Embodiment of the laminated body for packaging materials of this invention. It is a perspective view showing one Embodiment of the packaging material produced using the laminated body for packaging materials of this invention. It is a perspective view showing one Embodiment of the packaging material produced using the laminated body for packaging materials of this invention.

(Gas barrier laminate)
The gas barrier laminate 10 of the present invention includes a gas barrier resin layer 11 and a polyolefin resin layer 12, as shown in FIG.

In one embodiment, the gas barrier laminate 10 may include an adhesive resin layer 13 between the gas barrier resin layer 11 and the polyolefin resin layer 12, as shown in FIG.
By further providing an adhesive resin layer between the gas barrier resin layer and the polyolefin resin layer, the adhesion between these layers can be further improved.

In the present invention, the thickness of the gas barrier resin layer is preferably smaller than the thickness of the polyolefin resin layer. With this configuration, when the gas barrier laminate of the present invention is used as an intermediate layer of a packaging material laminate, the recyclability of the packaging material laminate can be improved.
The thickness of the gas barrier resin layer is preferably at least 5 μm, more preferably at least 10 μm, smaller than the thickness of the polyolefin resin layer. When the thickness of the gas barrier resin layer is smaller than the thickness of the polyolefin resin layer by 5 μm or more, the recyclability of the packaging material laminate can be further improved.

  The gas barrier laminate is composed of a stretched resin film, and the stretched resin film may be a uniaxially stretched resin film or a biaxially stretched resin film.

The stretch ratio in the machine direction (MD) of the stretched resin film is preferably 2 times or more and 10 times or less, and more preferably 3 times or more and 7 times or less.
By setting the stretching ratio in the longitudinal direction (MD) of the stretched resin film to 2 times or more, the strength can be improved while maintaining the oxygen barrier property and the water vapor barrier property of the gas barrier laminate of the present invention. On the other hand, the upper limit of the stretching ratio in the longitudinal direction (MD) of the stretched resin film is not particularly limited, but is preferably 10 times or less from the viewpoint of the breaking limit of the stretched resin film.

The stretching ratio in the transverse direction (TD) of the stretched resin film is preferably 2 times or more and 10 times or less, and more preferably 3 times or more and 7 times or less.
By setting the stretching ratio in the transverse direction (TD) of the stretched resin film to 2 times or more, the strength can be improved while maintaining the oxygen barrier property and the water vapor barrier property of the gas barrier laminate of the present invention. On the other hand, the upper limit of the stretching ratio in the transverse direction (TD) of the stretched resin film is not particularly limited, but is preferably 10 times or less from the viewpoint of the breaking limit of the stretched resin film.

(Gas barrier resin layer)
The gas barrier resin layer constituting the gas barrier laminate of the present invention contains at least one kind of gas barrier resin, for example, ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol, polyacrylonitrile, nylon 6, nylon 6 , 6, and polymethaxylylene adipamide (MXD6), such as polyamide, polyester, polyurethane, and (meth) acrylic resin. Among them, EVOH is preferable from the viewpoint of oxygen barrier properties and water vapor barrier properties. .

The ethylene content in EVOH is preferably from 20% by mass to 60% by mass, and more preferably from 27% by mass to 48% by mass.
By setting the ethylene content in the EVOH to 20% by mass or more, the processability of the gas barrier laminate of the present invention can be improved. When the ethylene content in the EVOH is 60% by mass or less, the oxygen barrier property and the water vapor barrier property of the gas barrier laminate of the present invention can be improved.

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

  The gas barrier resin layer can contain an additive as long as the properties of the present invention are not impaired. Examples of the additives include a cross-linking agent, an antioxidant, an anti-blocking agent, a slip agent, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a compatibilizer, and a pigment. Can be

The thickness of the gas barrier resin layer is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 7 μm or less.
When the thickness of the gas barrier resin layer is 0.5 μm or more, the oxygen barrier property and the water vapor barrier property of the gas barrier laminate of the present invention can be improved. Further, by setting the thickness of the gas barrier resin layer to 10 μm or less, when the gas barrier laminate of the present invention is used as an intermediate layer of the packaging material laminate, the recyclability of the packaging material laminate is improved. be able to.

(Polyolefin resin layer)
The polyolefin resin layer is composed of polyolefin, and examples thereof include polyethylene, polypropylene, polymethylpentene, ethylene-propylene copolymer, and propylene-butene copolymer. Of these, polyethylene and polypropylene are preferable.

The thickness of the polyolefin resin layer is preferably 5 μm or more and 100 μm or less, more preferably 10 μm or more and 50 μm or less.
By setting the thickness of the polyolefin resin layer to 5 μm or more, the strength and heat resistance of the gas barrier laminate of the present invention can be improved. Further, when the gas barrier laminate of the present invention is used as an intermediate layer of a laminate for packaging materials, the recyclability of the laminate for packaging materials can be improved.
By setting the thickness of the polyolefin resin layer to 100 μm or less, the workability of the gas barrier laminate of the present invention can be improved.

(Adhesive resin layer)
In one embodiment, the gas barrier laminate may include an adhesive resin layer between the gas barrier resin layer and the polyolefin resin layer. Thereby, the adhesion between the gas barrier resin layer and the polyolefin resin layer can be improved.

  The adhesive resin layer contains at least one kind of resin material, and examples thereof include polyolefin, modified polyolefin, polyester, vinyl resin, and polyamide. Among these, polyolefin and modified polyolefin are preferable from the viewpoint of adhesion.

  The adhesive resin layer may contain the above-mentioned additives as long as the properties of the present invention are not impaired.

The thickness of the adhesive resin is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less.
By setting the thickness of the adhesive resin layer to 0.5 μm or more, the adhesion between the gas barrier resin layer and the polyolefin resin layer can be improved. Further, by setting the thickness of the adhesive resin layer to 10 μm or less, when the gas barrier laminate of the present invention is used as a constituent layer of the packaging material laminate, the recyclability of the packaging material laminate is improved. Can be.

  The gas barrier laminate is obtained by combining the material constituting the gas barrier resin layer, the material constituting the polyolefin resin layer, and (if the adhesive resin layer is provided, the material constituting the layer) the T-die method. Alternatively, it is a co-extrusion stretched resin film produced by stretching a film obtained by co-extrusion film formation by a conventionally known method such as an inflation method.

(Lamination for packaging materials)
As shown in FIG. 3, the packaging material laminate 14 of the present invention includes a base material 15, the gas barrier laminate 10, and a heat seal layer 16.
The base material 15 and the heat seal layer 16 are composed of the same polyolefin as the polyolefin constituting the polyolefin resin layer 12 of the gas barrier laminate 10, and the base material 15 is a stretched resin film composed of the polyolefin. And
Normally, resin films composed of polyolefin are inferior in strength and heat resistance, so they cannot be used as a base material, and are used by laminating with resin films composed of polyester, polyamide, etc. An ordinary packaging material is composed of a laminated film in which a base material and a heat seal layer are made of different types of resin materials.
In recent years, with the increasing demand for building a recycling-based society, packaging materials having high recyclability have been demanded. However, conventional packaging materials are composed of different kinds of resin materials as described above, and it is difficult to separate them for each resin material.
The present inventors can use a polyolefin conventionally used as a heat seal layer as a base material by forming a stretched resin film, and laminating the base material with a heat seal layer composed of the same polyolefin. It has been found that by using such a material, it is possible to obtain a packaging material having sufficient strength and heat resistance as a packaging material and having high recyclability.
Moreover, the packaging material laminate of the present invention includes the gas barrier laminate, has high oxygen barrier properties and water vapor barrier properties, and can be a packaging material having both barrier properties and recyclability. I got the knowledge that I can do it.
That is, according to the packaging material laminate of the present invention, it is possible to provide a packaging material laminate capable of realizing a packaging material having sufficient strength and barrier properties as a packaging material and having excellent recyclability. it can

  Further, in one embodiment, as shown in FIGS. 4 and 5, the packaging material laminate 14 of the present invention is provided between the base material 15 and the gas barrier laminate 10 and between the gas barrier laminate 10 and the heat barrier laminate. A vapor deposition film 17 can be provided on at least one of the seal layers 16.

  Further, in one embodiment, as shown in FIG. 6, the packaging material laminate 14 of the present invention is formed between the base material 15 and the vapor deposition film 17 or, as shown in FIG. And an adhesive layer 18 can be provided between the substrate and the deposition film 17.

  In one embodiment, in the packaging material laminate 14 of the present invention, as shown in FIG. 8, the heat seal layer 16 includes a first heat seal layer 19 and a second heat seal layer 20. Is also good.

  Further, in one embodiment of the present invention, the laminate for packaging material may include a gas barrier coating film between any layers (not shown).

The content of the polyolefin in the whole laminate for packaging materials of the present invention is preferably 80% by mass or more, and more preferably 90% by mass or more.
By setting the content of the polyolefin in the entire laminate for packaging material of the present invention to 80% by mass or more, the recyclability of the laminate for packaging material of the present invention can be improved.
In addition, the content of the polyolefin in the packaging material laminate refers to the ratio of the polyolefin content to the sum of the content of the resin material in each layer constituting the packaging material laminate.

  Hereinafter, each layer constituting the laminate for packaging materials of the present invention will be described.

(Base material)
The substrate provided in the packaging material laminate of the present invention is composed of polyolefin, and this polyolefin is the same polyolefin as the polyolefin resin layer of the gas barrier laminate and the polyolefin constituting the following heat seal layer.
By making the polyolefin constituting the base material, the polyolefin constituting the polyolefin resin layer, and the polyolefin constituting the heat seal layer the same, the recyclability of the laminate for packaging materials can be improved.

  As the base material, a stretched resin film composed of polyolefin is used in order to impart sufficient strength and heat resistance as a packaging material. The stretched resin film may be a uniaxially stretched resin film or a biaxially stretched resin film.

The stretch ratio in the machine direction (MD) of the stretched resin film is preferably 2 times or more and 10 times or less, and more preferably 3 times or more and 7 times or less.
By setting the stretching ratio in the longitudinal direction (MD) of the stretched resin film to 2 times or more, the strength and heat resistance of the laminate for packaging materials of the present invention can be improved. Further, since the transparency of the base material can be improved, when an image is formed on the gas-barrier laminate side surface of the base material, the visibility can be improved.
On the other hand, the upper limit of the stretching ratio in the longitudinal direction (MD) of the stretched resin film is not particularly limited, but is preferably 10 times or less from the viewpoint of the breaking limit of the stretched film.

The stretching ratio in the transverse direction (TD) of the stretched resin film is preferably 2 times or more and 10 times or less, and more preferably 3 times or more and 7 times or less.
By setting the stretching ratio in the transverse direction (TD) of the stretched resin film to 2 times or more, the strength and heat resistance of the laminate for packaging materials of the present invention can be improved. Further, since the transparency of the base material can be improved, when an image is formed on the gas-barrier laminate side surface of the base material, the visibility can be improved.
On the other hand, the upper limit of the stretching ratio in the transverse direction (TD) of the stretched resin film is not particularly limited, but is preferably 10 times or less from the viewpoint of the breaking limit of the stretched film.

  As the polyolefin that can be used as the base material, it is necessary to use the same polyolefin that constitutes the polyolefin resin layer and the heat seal layer of the gas barrier laminate as described above. Examples of such a polyolefin include polyethylene and polypropylene. , Polymethylpentene, an ethylene-propylene copolymer and a propylene-butene copolymer, among which polyethylene and polypropylene are preferred.

As the polyethylene, high density polyethylene (HDPE) having a density of more than 0.945 g / cm ³ , medium density polyethylene (MDPE) having a density of 0.925 to 0.945 g / cm ³ , and a density of less than 0.925 g / cm ³ Low density polyethylene (LDPE) and linear low density polyethylene (LLDPE).

In one embodiment, the base is provided with a layer composed of high-density polyethylene (hereinafter, referred to as a high-density polyethylene layer) and a layer composed of medium-density polyethylene (hereinafter, referred to as a medium-density polyethylene layer). Things can be used.
By providing the high-density polyethylene layer outside the base material, the strength and heat resistance of the laminate for packaging materials of the present invention can be improved. Further, by providing the medium density polyethylene layer, the stretchability of the resin film constituting the base material can be improved.

For example, it has a configuration of a high-density polyethylene layer / medium-density polyethylene layer from the outside.
With such a configuration, the stretchability of the resin film can be improved. Further, the strength and heat resistance of the laminate for packaging materials of the present invention can be improved.
At this time, the thickness of the high-density polyethylene layer is preferably smaller than the thickness of the medium-density polyethylene layer.
The ratio of the thickness of the high-density polyethylene layer to the thickness of the medium-density polyethylene layer is preferably from 1/10 to 1/1, more preferably from 1/5 to 1/2.
By setting the ratio of the thickness of the high-density polyethylene layer to the thickness of the medium-density polyethylene layer to 1/10 or more, the strength and heat resistance of the laminate for packaging materials of the present invention can be improved. Further, by setting the ratio of the thickness of the high-density polyethylene layer to the thickness of the medium-density polyethylene layer to 1/1 or less, the stretchability of the resin film can be improved.

In addition, for example, a configuration including a high-density polyethylene layer / a medium-density polyethylene layer / a high-density polyethylene layer from the outside may be employed.
With such a configuration, the stretchability of the resin film can be improved. Further, the strength and heat resistance of the laminate for packaging materials of the present invention can be improved. Further, it is possible to prevent the occurrence of curl in the substrate.
At this time, the thickness of the high-density polyethylene layer is preferably smaller than the thickness of the medium-density polyethylene layer.
The ratio of the thickness of the high-density polyethylene layer to the thickness of the medium-density polyethylene layer is preferably from 1/10 to 1/1, more preferably from 1/5 to 1/2.
By setting the ratio of the thickness of the high-density polyethylene layer to the thickness of the medium-density polyethylene layer to 1/10 or more, the strength and heat resistance of the laminate for packaging materials of the present invention can be improved. Further, by setting the ratio of the thickness of the high-density polyethylene layer to the thickness of the medium-density polyethylene layer to 1/1 or less, the stretchability of the resin film can be improved.

Further, for example, from the outside, a configuration of a high-density polyethylene layer / medium-density polyethylene layer / low-density polyethylene layer or a linear low-density polyethylene layer / medium-density polyethylene layer / high-density polyethylene layer may be employed.
With such a configuration, the stretchability of the film can be improved. Further, the strength and heat resistance of the laminate for packaging materials of the present invention can be improved. Further, it is possible to prevent the occurrence of curl in the base material. Further, the processability of the resin film can be improved.
At this time, the thickness of the high-density polyethylene layer is preferably smaller than the thickness of the medium-density polyethylene layer.
The ratio of the thickness of the high-density polyethylene layer to the thickness of the medium-density polyethylene layer is preferably from 1/10 to 1/1, more preferably from 1/5 to 1/2.
By setting the ratio of the thickness of the high-density polyethylene layer to the thickness of the medium-density polyethylene layer to 1/10 or more, the strength and heat resistance of the laminate for packaging materials of the present invention can be improved. Further, by setting the ratio of the thickness of the high-density polyethylene layer to the thickness of the medium-density polyethylene layer to 1/1 or less, the stretchability of the resin film can be improved.
Further, the thickness of the high-density polyethylene layer is preferably smaller than the thickness of the low-density polyethylene layer or the linear low-density polyethylene layer.
The ratio of the thickness of the high-density polyethylene layer to the thickness of the low-density polyethylene layer or the linear low-density polyethylene layer is preferably 1/10 or more and 1/1 or less, and is 1/5 or more and 1/2 or less. More preferably, there is.
Heat resistance can be improved by setting the ratio of the thickness of the high-density polyethylene layer to the thickness of the low-density polyethylene layer or the linear low-density polyethylene layer to 1/10 or more. Further, by setting the ratio of the thickness of the high-density polyethylene layer to the thickness of the low-density polyethylene layer or the linear low-density polyethylene layer to be equal to or less than 1/1, the stretchability can be improved.

The polypropylene may be any of a homopolymer, a random copolymer and a block copolymer.
The polypropylene homopolymer is a polymer of only propylene, and the polypropylene random copolymer is a copolymer of propylene and another α-olefin other than propylene (eg, ethylene, butene-1, 4-methyl-1-pentene, etc.). A random copolymer, a polypropylene block copolymer is a copolymer having a polymer block composed of propylene and a polymer block composed of an α-olefin other than the above-mentioned propylene.
Among these polypropylenes, the transparency of the substrate can be improved, and when an image is formed on the gas barrier laminate side surface of the substrate, from the viewpoint of improving the visibility, a homopolymer or Preferably, a random copolymer is used. When importance is placed on the rigidity and heat resistance of the packaging material, a homopolymer can be used, and when importance is placed on impact resistance, a random copolymer can be used.

Further, as a raw material for obtaining a polyolefin, an olefin monomer derived from biomass may be used instead of an olefin monomer obtained from a fossil fuel. Since such an olefin monomer derived from biomass is a carbon-neutral material, it can be used as a packaging material with even less environmental load.
Such a biomass-derived polyolefin, for example, polyethylene, can be produced by a method as described in JP-A-2013-177531. A commercially available polyolefin derived from biomass (eg, green PE commercially available from Braskem) may be used.

  Further, a polyolefin recycled by mechanical recycling can also be used. Here, mechanical recycling generally means that the recovered polyolefin film or the like is crushed, washed with alkali to remove dirt and foreign matter on the film surface, and then dried under high temperature and reduced pressure for a certain time to remain inside the film. This is a method in which contaminants are diffused to perform decontamination, remove stains from the polyolefin film, and return to polyolefin again.

The substrate may have an image formed on its surface. The image may be formed on any surface of the substrate, but it is preferable to form the image on the gas barrier laminate side surface since contact with the outside air and deterioration with time can be prevented.
The image to be formed is not particularly limited, and includes characters, patterns, symbols, combinations thereof, and the like.
The image can be formed using a conventionally known ink, but is preferably performed using a biomass-derived ink. This makes it possible to produce a packaging material having a lower environmental load by using the packaging material laminate of the present invention.
The method for forming an image is not particularly limited, and includes a conventionally known printing method such as a gravure printing method, an offset printing method, and a flexographic printing method. Among these, the flexographic printing method is preferable because the environmental load can be reduced.

Further, the substrate is preferably subjected to a surface treatment. Thereby, the adhesiveness with an 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 Chemical treatment such as treatment.
Further, an anchor coat layer may be formed on the surface of the base material using a conventionally known anchor coat agent.

The thickness of the substrate is preferably 5 μm or more and 300 μm or less, more preferably 7 μm or more and 100 μm or less.
By setting the thickness of the base material to 5 μm or more, the strength of the laminate for packaging materials of the present invention can be improved. Further, by setting the thickness of the base material to 300 μm or less, the workability of the laminate for packaging materials of the present invention can be improved.

The substrate can be produced by forming a film of a polyolefin by a T-die method or an inflation method, producing a film, and then stretching the film.
According to the inflation method, film formation and stretching can be performed simultaneously.

When a substrate is produced by the T-die method, the MFR of the polyolefin is preferably 5 g / 10 min or more and 20 g / 10 min or less.
By setting the MFR of the polyolefin to 5 g / 10 min or more, the processability of the laminate for packaging materials of the present invention can be improved. Further, by setting the MFR of the polyolefin to 20 g / 10 minutes or less, it is possible to prevent the resin film from breaking.

When the substrate is produced by the inflation method, the MFR of the polyolefin is preferably 0.5 g / 10 min or more and 5 g / 10 min or less.
By setting the MFR of the polyolefin to 0.5 g / 10 minutes or more, the processability of the laminate for packaging materials of the present invention can be improved. Further, by setting the MFR of the polyolefin to 5 g / 10 minutes or less, the film forming property can be improved.

  The substrate is not limited to the one produced by the above method, and a commercially available substrate may be used.

(Gas barrier laminate)
The description of the configuration of the gas barrier laminate is omitted here because it has been described above.

(Heat seal layer)
The heat seal layer is characterized by being composed of the same polyolefin as the polyolefin constituting the polyolefin resin layer of the substrate and the gas barrier laminate. With such a configuration, a recyclable packaging material having sufficient strength and heat resistance as a packaging material can be obtained.
However, the heat seal layer is formed of an unstretched polyolefin resin film or formed by melt extrusion of polyolefin.

  When polypropylene is used as the resin constituting the heat seal layer, a heat seal modifier may be included in order to improve heat sealability. The heat seal modifier is not particularly limited as long as it has excellent compatibility with the polyolefin constituting the heat seal layer, and examples thereof include an olefin copolymer.

The thickness of the heat seal layer is preferably from 5 μm to 100 μm, more preferably from 10 μm to 50 μm.
By setting the thickness of the heat seal layer to 5 μm or more, the heat seal property and the recyclability of the heat seal layer can be improved. Further, by setting the thickness of the heat seal layer to 100 μm or less, the processability of the laminate for packaging materials of the present invention can be improved.

In one embodiment, the heat seal layer may have a multilayer structure. In particular, when a heat seal modifier is added to polypropylene as a heat seal layer, the heat seal layer may have two or more layers because the modifier may migrate (leach) to the gas barrier laminate side. The side to be heat-sealed (the innermost layer side of the laminate) can be a layer containing polyolefin and a heat seal modifier, and the outer layer can be a layer made of polyolefin.
That is, examples of the multilayer structure include a multilayer structure including a first heat seal layer composed of polyolefin and a second heat seal layer composed of polyolefin and a heat seal modifier.

The content of the heat seal modifier in the second heat seal layer is preferably from 10% by mass to 50% by mass, more preferably from 20% by mass to 40% by mass.
By setting the content of the heat seal modifier in the second heat seal layer to 10% by mass or more, the heat seal property of the second heat seal layer can be improved. Further, by setting the content of the heat seal modifier in the second heat seal layer to 50% by mass or less, the recyclability of the laminate for packaging materials of the present invention can be improved.

When the heat seal layer has the two-layer structure, the thickness of the first heat seal layer is preferably 5 μm or more and 50 μm or less, and more preferably 7 μm or more and 45 μm or less.
By setting the thickness of the first heat seal layer to 5 μm or more, the recyclability of the packaging material laminate of the present invention and the heat seal property of the first heat seal layer can be improved. Further, by setting the thickness of the first heat seal layer to 50 μm or less, the processability of the laminate for packaging materials of the present invention can be improved.
Further, the thickness of the second heat seal layer is preferably 5 μm or more and 20 μm or less, more preferably 7 μm or more and 15 μm or less.
By setting the thickness of the second heat seal layer to 5 μm or more, the heat seal property of the second heat seal layer can be improved. In addition, by setting the thickness of the second heat seal layer to 20 μm or less, both the recyclability and the processability of the laminate for packaging materials of the present invention can be achieved.

(Evaporated film)
The laminate for packaging materials of the present invention may further include a vapor deposition layer at least between the substrate and the gas barrier laminate and between at least one of the gas barrier laminate and the heat seal layer. By providing the vapor-deposited film, the gas barrier properties, particularly the oxygen barrier properties and the water vapor barrier properties of the laminate for packaging materials of the present invention can be further improved.

  Examples of the deposited film include a metal such as aluminum, and an inorganic oxide such as aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, and barium oxide. Can be mentioned.

The thickness of the deposited film is preferably from 1 nm to 150 nm, more preferably from 5 nm to 60 nm, even more preferably from 10 nm to 40 nm.
By setting the thickness of the deposited film to 1 nm or more, the oxygen barrier property and the water vapor barrier property of the laminate for packaging materials of the present invention can be further improved. Further, by setting the thickness of the deposited film to 150 nm or less, generation of cracks in the deposited film can be prevented, and the recyclability of the packaging material laminate of the present invention can be improved.

  In order for the deposited film to be an aluminum deposited film, the OD value is preferably 2 or more and 3.5 or less. Thereby, the oxygen barrier property and the water vapor barrier property can be improved while maintaining the productivity of the packaging material laminate of the present invention. In the present invention, the OD value can be measured according to JIS-K-7361.

  The deposited film can be formed by a conventionally known method. For example, a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum deposition method, a sputtering method and an ion plating method, and plasma chemistry Chemical vapor deposition methods (Chemical Vapor Deposition method, CVD method) such as a vapor phase growth method, a thermal chemical vapor deposition method, and a photochemical vapor deposition method can be given.

Further, for example, a composite film composed of two or more layers of vapor deposited films of different kinds of inorganic oxides can be formed and used by using both physical vapor deposition and chemical vapor deposition. The degree of vacuum of the deposition chamber is preferably about 10 ⁻² to 10 ⁻⁸ mbar before oxygen introduction, and about 10 ⁻¹ to 10 ⁻⁶ mbar after oxygen introduction. Note that the amount of oxygen introduced differs depending on the size of the vapor deposition machine. As the oxygen to be introduced, an inert gas such as an argon gas, a helium gas, or a nitrogen gas may be used as a carrier gas within a range that does not cause any trouble. The transport speed of the film can be about 10 to 800 m / min.

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

(Adhesive layer)
The laminate for packaging materials of the present invention may be provided with an adhesive layer for the purpose of improving the adhesion between the surface on which the vapor deposition layer is provided and the surface that adheres to the vapor deposition layer (adhered surface).

The adhesive layer contains at least one type of adhesive, and may be any of a one-component curable type, a two-component curable type, and a non-curable type. The adhesive may be a solventless adhesive or a solvent adhesive, but from the viewpoint of environmental load, a solventless adhesive can be preferably used.
Examples of the non-solvent type adhesive include a polyether-based adhesive, a polyester-based adhesive, a silicone-based adhesive, an epoxy-based adhesive, and a urethane-based adhesive. A system adhesive can be preferably used.
Examples of the solvent-based adhesive include a rubber-based adhesive, a vinyl-based adhesive, a silicone-based adhesive, an epoxy-based adhesive, a phenol-based adhesive, and an olefin-based adhesive.

When the packaging material laminate of the present invention is provided with an aluminum vapor-deposited film, the cured product of a resin composition containing a polyester polyol, an isocyanate compound, and a phosphoric acid-modified compound, which is a two-component curable adhesive, is used. It is preferable to form an adhesive layer.
When the adhesive layer has such a structure, the oxygen barrier property and the water vapor barrier property of the laminate for a packaging material of the present invention can be further improved.
When a laminate having a vapor-deposited film is applied to a packaging material, a bending load is applied to the laminate by a molding machine or the like, so that a crack or the like may occur in the aluminum vapor-deposited film. By using the specific adhesive as described above, it is possible to suppress a decrease in the oxygen barrier property and the water vapor barrier property even when a crack occurs in the aluminum deposited film.

  The polyester polyol has two or more hydroxyl groups in one molecule as a functional group. Further, the isocyanate compound has two or more isocyanate groups in one molecule as a functional group. The polyester polyol has, for example, a polyester structure or a polyester polyurethane structure as a main skeleton.

  As a specific example of a resin composition (adhesive) containing a polyester polyol, an isocyanate compound, and a phosphoric acid-modified compound, a series of PASLIMs sold by DIC Corporation can be used.

  The resin composition may further include a plate-like inorganic compound, a coupling agent, cyclodextrin and / or a derivative thereof, and the like.

As the polyester polyol having two or more hydroxyl groups in one molecule as a functional group, for example, the following [First Example] to [Third Example] can be used.
[Example 1] Polyester polyol obtained by polycondensation of ortho-oriented polycarboxylic acid or anhydride thereof and polyhydric alcohol [Example 2] Polyester polyol having glycerol skeleton [Example 3] Having isocyanuric ring Polyester polyol Hereinafter, each polyester polyol will be described.

The polyester polyol according to the first example is selected from the group consisting of a polycarboxylic acid component containing at least one or more of orthophthalic acid and its anhydride, and ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexane dimethanol. A polycondensate obtained by polycondensation with a polyhydric alcohol component containing at least one of the above.
Particularly, a polyester polyol in which the content of orthophthalic acid and its anhydride relative to all components of the polycarboxylic acid is 70 to 100% by mass is preferable.

The polyester polyol according to the first example essentially requires orthophthalic acid and its anhydride as the polyvalent carboxylic acid component, but copolymerizes other polyvalent carboxylic acid components within a range that does not impair the effects of the present embodiment. You may.
Specifically, aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid and dodecanedicarboxylic acid, maleic anhydride, polycarboxylic acids containing unsaturated bonds such as maleic acid and fumaric acid, 1, Alicyclic polycarboxylic acids such as 3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5- Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid, anhydrides of these dicarboxylic acids and ester formation of these dicarboxylic acids Aromatic polycarboxylic acids such as a carboxylic acid derivative, p-hydroxybenzoic acid, p- ( And polybasic acids such as 2-hydroxyethoxy) benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids. Among these, succinic acid, 1,3-cyclopentanedicarboxylic acid, and isophthalic acid are preferred.
In addition, you may use 2 or more types of said other polyvalent carboxylic acids.

一般式（１）において、Ｒ_１、Ｒ_２、Ｒ_３は、各々独立に、Ｈ（水素原子）または下記の一般式（２）で表される基である。

As the polyester polyol according to the second example, a polyester polyol having a glycerol skeleton represented by the general formula (1) can be given.

In the general formula (1), R ₁ , R ₂ , and R ₃ are each independently H (hydrogen atom) or a group represented by the following general formula (2).

In the formula (2), n represents an integer of 1 to 5, and X represents an optionally substituted 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, Represents an arylene group selected from the group consisting of a 3-anthraquinonediyl group and a 2,3-anthracenediyl group, and Y represents an alkylene group having 2 to 6 carbon atoms.
However, at least one of R ₁ , R ₂ and R ₃ represents a group represented by the general formula (2).

In the general formula (1), at least one of R ₁ , R ₂ and R ₃ needs to be a group represented by the general formula (2). Among them, it is preferable that all of R ₁ , R ₂ and R ₃ are groups represented by the general formula (2).

_Also, tables in the compound R _1, R 2, one of _{R 3} is a group represented by the general formula _(2), R _1, R 2, either _{R 3} 2 two generally formula (2) A mixture of any two or more of the compound represented by the general formula (2) and the compound represented by the general formula (2) wherein all of R ₁ , R ₂ and R ₃ may be a mixture.

X is selected from the group consisting of a 1,2-phenylene group, a 1,2-naphthylene group, a 2,3-naphthylene group, a 2,3-anthraquinonediyl group and a 2,3-anthracenediyl group, and has a substituent. Represents an optionally substituted arylene group.
When X is substituted by a substituent, it may be substituted with one or more substituents, which is attached to any carbon atom on X different from the free radical. As the substituent, chloro, bromo, methyl, ethyl, i-propyl, hydroxyl, methoxy, ethoxy, phenoxy, methylthio, phenylthio, cyano, nitro, amino, Examples include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group and a naphthyl group.

  In the general formula (2), Y represents ethylene group, propylene group, butylene group, neopentylene group, 1,5-pentylene group, 3-methyl-1,5-pentylene group, 1,6-hexylene group, methylpentylene. And an alkylene group having 2 to 6 carbon atoms such as a dimethylbutylene group. Y is preferably a propylene group or an ethylene group, and most preferably an ethylene group.

  The polyester resin compound having a glycerol skeleton represented by the general formula (1) is an essential component comprising glycerol, an aromatic polycarboxylic acid or an anhydride thereof in which a carboxylic acid is substituted at an ortho position, and a polyhydric alcohol component. And can be synthesized by reacting

Examples of the aromatic polycarboxylic acid or an anhydride thereof in which a carboxylic acid is substituted at an ortho position include orthophthalic acid or an anhydride thereof, naphthalene 2,3-dicarboxylic acid or an anhydride thereof, naphthalene 1,2-dicarboxylic acid or an anhydride thereof. Anhydrides, anthraquinone 2,3-dicarboxylic acids or anhydrides thereof, and 2,3-anthracene carboxylic acids or anhydrides thereof are exemplified.
These compounds may have a substituent at any carbon atom of the aromatic ring. As the substituent, chloro, bromo, methyl, ethyl, i-propyl, hydroxyl, methoxy, ethoxy, phenoxy, methylthio, phenylthio, cyano, nitro, amino, Examples include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group and a naphthyl group.

  Examples of the polyhydric alcohol component include alkylene diols having 2 to 6 carbon atoms. For example, diols such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol and dimethylbutanediol Can be exemplified.

一般式（３）において、Ｒ_１、Ｒ_２、Ｒ_３は、各々独立に、「−（ＣＨ_２）ｎ１−ＯＨ（但しｎ１は２〜４の整数を表す）」、または、一般式（４）の構造を表す。

The polyester polyol according to the third example is a polyester polyol having an isocyanuric ring represented by the following general formula (3).

In the general formula (3), R ₁ , R ₂ , and R ₃ each independently represent “— (CH ₂ ) n 1-OH (where n 1 represents an integer of 2 to 4)” or the general formula (4 ).

In the general formula (4), n2 represents an integer of 2 to 4, n3 represents an integer of 1 to 5, X represents a 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, Selected from the group consisting of a 2,3-anthraquinonediyl group and a 2,3-anthracenediyl group, which represents an arylene group which may have a substituent, and Y represents an alkylene group having 2 to 6 carbon atoms. Represents a group represented by However, at least one of R ₁ , R ₂ and R ₃ is a group represented by the general formula (4).

In the general formula (3), - (CH 2 ) alkylene group represented by _n1- may be branched be linear. n1 is preferably 2 or 3, and most preferably 2.

In the general formula (4), n2 represents an integer of 2 to 4, and n3 represents an integer of 1 to 5.
X is selected from the group consisting of a 1,2-phenylene group, a 1,2-naphthylene group, a 2,3-naphthylene group, a 2,3-anthraquinonediyl group, and a 2,3-anthracenediyl group, and has a substituent. Represents an optionally substituted arylene group.

When X is substituted by a substituent, it may be substituted with one or more substituents, which is attached to any carbon atom on X different from the free radical. As the substituent, chloro, bromo, methyl, ethyl, i-propyl, hydroxyl, methoxy, ethoxy, phenoxy, methylthio, phenylthio, cyano, nitro, amino, Examples include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group and a naphthyl group.
X is preferably a hydroxyl group, a cyano group, a nitro group, an amino group, a phthalimide group, a carbamoyl group, an N-ethylcarbamoyl group and a phenyl group, among which a hydroxyl group, a phenoxy group, a cyano group, a nitro group, a phthalimide group and A phenyl group is most preferred.

  In the general formula (4), Y represents an ethylene group, a propylene group, a butylene group, a neopentylene group, a 1,5-pentylene group, a 3-methyl-1,5-pentylene group, a 1,6-hexylene group, a methylpentylene group. And an alkylene group having 2 to 6 carbon atoms such as a dimethylbutylene group. Y is preferably a propylene group or an ethylene group, and most preferably an ethylene group.

In the general formula (3), at least one of R ₁ , R ₂ and R ₃ is a group represented by the general formula (4). Among them, it is preferable that all of R ₁ , R ₂ and R ₃ are groups represented by the general formula (4).

_Also, tables in the compound R _1, R 2, one of _{R 3} is a group represented by the general formula _(4), R _1, R 2, either _{R 3} 2 two generally formula (4) A mixture of any two or more of the compounds represented by the general formula (4) and the compounds represented by the general formula (4) in which all of R ₁ , R ₂ and R ₃ may be a mixture.

  The polyester polyol having an isocyanuric ring represented by the general formula (3) includes a triol having an isocyanuric ring, an aromatic polycarboxylic acid or an anhydride thereof in which a carboxylic acid is substituted at an ortho position, and a polyhydric alcohol component. Can be synthesized by reacting

  Examples of the triol having an isocyanuric ring include alkylene oxide adducts of isocyanuric acid such as 1,3,5-tris (2-hydroxyethyl) isocyanuric acid and 1,3,5-tris (2-hydroxypropyl) isocyanuric acid And the like.

  Examples of the aromatic polycarboxylic acid in which the carboxylic acid is substituted at the ortho position or an anhydride thereof include orthophthalic acid or an anhydride thereof, naphthalene 2,3-dicarboxylic acid or an anhydride thereof, and naphthalene 1,2-dicarboxylic acid. Or an anhydride thereof, anthraquinone 2,3-dicarboxylic acid or anhydride thereof, and 2,3-anthracene carboxylic acid or anhydride thereof. These compounds may have a substituent at any carbon atom of the aromatic ring.

  Examples of the substituent include chloro, bromo, methyl, ethyl, i-propyl, hydroxyl, methoxy, ethoxy, phenoxy, methylthio, phenylthio, cyano, nitro, amino, Examples include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group and a naphthyl group.

Examples of the polyhydric alcohol component include alkylene diols having 2 to 6 carbon atoms. For example, diols such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol and dimethylbutanediol Is mentioned.
Among them, 1,3,5-tris (2-hydroxyethyl) isocyanuric acid or 1,3,5-tris (2-hydroxypropyl) isocyanuric acid is used as the triol compound having an isocyanuric ring, and the carboxylic acid is in the ortho position. Orthophthalic anhydride is used as the aromatic polycarboxylic acid or its anhydride substituted with, and a polyester polyol compound having an isocyanuric ring using ethylene glycol as the polyhydric alcohol is particularly excellent in oxygen barrier properties and adhesiveness. preferable.

  The isocyanuric ring is highly polar and trifunctional, can increase the polarity of the entire system, and can increase the crosslink density. From such a viewpoint, it is preferable to contain the isocyanuric ring in an amount of 5% by mass or more based on the total solid content of the adhesive resin.

The isocyanate compound has two or more isocyanate groups in the molecule.
The isocyanate compound may be aromatic or aliphatic, and may be a low molecular compound or a high molecular compound.
Further, the isocyanate compound may be a blocked isocyanate compound obtained by an addition reaction using a known isocyanate blocking agent by a known and appropriate method.
Above all, a polyisocyanate compound having three or more isocyanate groups is preferable from the viewpoint of adhesion and retort resistance, and aromatic is preferable from the viewpoint of oxygen barrier properties and water vapor barrier properties.

Specific examples of the isocyanate compound include, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, metaxylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and these isocyanate compounds. And adducts, burettes and allophanates obtained by reacting these isocyanate compounds with low molecular weight active hydrogen compounds or their alkylene oxide adducts or high molecular weight active hydrogen compounds.
Examples of the low-molecular active hydrogen compound include ethylene glycol, propylene glycol, metaxylylene alcohol, 1,3-bishydroxyethylbenzene, 1,4-bishydroxyethylbenzene, trimethylolpropane, glycerol, pentaerythritol, erythritol, sorbitol, Examples include ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, and meta-xylylenediamine. Examples of the molecularly active hydrogen compound include various polyester resins, polyether polyols, and high molecular weight active hydrogen compounds of polyamide.

一般式（５）において、Ｒ_１、Ｒ_２、Ｒ_３は、水素原子、炭素数１〜３０のアルキル基、（メタ）アクリロイル基、置換基を有してもよいフェニル基および（メタ）アクリロイルオキシ基を有する炭素数１〜４のアルキル基から選ばれる基であるが、少なくとも一つは水素原子であり、ｎは、１〜４の整数を表す。

式中、Ｒ_４、Ｒ_５は、水素原子、炭素数１〜３０のアルキル基、（メタ）アクリロイル基、置換基を有してもよいフェニル基および（メタ）アクリロイルオキシ基を有する炭素数１〜４のアルキル基から選ばれる基であり、ｎは１〜４の整数、ｘは０〜３０の整数、ｙは０〜３０の整数を表すが、ｘとｙが共に０である場合を除く。 The phosphoric acid-modified compound is, for example, a compound represented by the following general formula (5) or (6).

In the general formula (5), R ₁ , R ₂ , and R ₃ represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a (meth) acryloyl group, a phenyl group which may have a substituent, and (meth) acryloyl. It is a group selected from an alkyl group having 1 to 4 carbon atoms having an oxy group, at least one of which is a hydrogen atom, and n represents an integer of 1 to 4.

In the formula, R ₄ and R ₅ represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a (meth) acryloyl group, a phenyl group which may have a substituent, and a carbon atom having 1 atom having a (meth) acryloyloxy group. And n is an integer of 1 to 4, x is an integer of 0 to 30, and y is an integer of 0 to 30 except when x and y are both 0. .

  More specifically, phosphoric acid, pyrophosphoric acid, triphosphoric acid, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis (2-ethylhexyl) phosphate, isododecyl acid phosphate, butoxy Examples thereof include ethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, and polyoxyethylene alkyl ether phosphoric acid, and one or more of these can be used.

The content of the phosphoric acid-modified compound in the resin composition is preferably from 0.005% by mass to 10% by mass, and more preferably from 0.01% by mass to 1% by mass.
When the content of the phosphoric acid-modified compound is 0.005% by mass or more, the oxygen barrier property and the water vapor barrier property of the laminate for a packaging material of the present invention can be improved. Further, by setting the content of the phosphoric acid-modified compound to 10% by mass or less, the adhesiveness of the adhesive layer can be improved.

The resin composition containing the polyester polyol, the isocyanate compound and the phosphoric acid-modified compound may contain a plate-like inorganic compound, whereby the adhesiveness of the adhesive layer can be improved. Moreover, the bending load resistance of the laminate for packaging materials of the present invention can be improved.
Examples of the plate-like inorganic compound include kaolinite-serpentine group clay minerals (halloysite, kaolinite, enderite, dickite, nacrite, antigolite, chrysotile, etc.) and pyrophyllite-talc family (pyrophyllite, talc, Kerolai, etc.).

Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, and an aluminum coupling agent represented by the following general formula (7). In addition, these coupling agents may be used alone or in combination of two or more.

  Examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ -Glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxytrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxy Propylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (Aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ- Examples include mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-triethoxysilyl-N- (1,3-dimethyl-butylidene).

  Examples of the titanium-based coupling agent include isopropyl triisostearoyl titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, and tetraoctyl bis. (Didodecyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctaino nortitanate, isopropyl dimethacryl isostearyl titanate , Isopropylisostearoyldiacryl titanate, diisostearoylethyl Nchitaneto, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate and dicumyl phenyloxy acetate titanate.

  Specific examples of the aluminum-based coupling agent include, for example, acetoalkoxyaluminum diisopropylate, diisopropoxyaluminum ethyl acetoacetate, diisopropoxyaluminum monomethacrylate, isopropoxyaluminum alkyl acetoacetate mono (dioctyl phosphate), aluminum -2-ethylhexanoate oxide trimer, aluminum stearate oxide trimer and alkyl acetoacetate aluminum oxide trimer.

The resin composition can include cyclodextrin and / or a derivative thereof, whereby the adhesiveness of the adhesive layer can be improved. Moreover, the bending load resistance of the laminate for packaging materials of the present invention can be further improved.
Specifically, for example, a cyclodextrin such as cyclodextrin, alkylated cyclodextrin, acetylated cyclodextrin, and hydroxyalkylated cyclodextrin in which a hydrogen atom of a hydroxyl group of a glucose unit of a glucose unit is substituted with another functional group is used. Can be. Also, a branched cyclic dextrin can be used.
The cyclodextrin skeleton in cyclodextrin and the cyclodextrin derivative is composed of α-cyclodextrin consisting of six glucose units, β-cyclodextrin consisting of seven glucose units, and γ-cyclodextrin consisting of eight glucose units. Any of them may be used.
These compounds may be used alone or in combination of two or more. In addition, these cyclodextrins and / or derivatives thereof may be hereinafter collectively referred to as dextrin compounds.

  From the viewpoint of compatibility and dispersibility in the resin composition, it is preferable to use a cyclodextrin derivative as the cyclodextrin compound.

  Examples of the alkylated cyclodextrin include methyl-α-cyclodextrin, methyl-β-cyclodextrin, methyl-γ-cyclodextrin, and the like. These compounds may be used alone or in combination of two or more.

  As the acetylated cyclodextrin, for example, monoacetyl-α-cyclodextrin, monoacetyl-β-cyclodextrin, monoacetyl-γ-cyclodextrin and the like can be mentioned. These compounds may be used alone or in combination of two or more.

  Examples of the hydroxyalkylated cyclodextrin include hydroxypropyl-α-cyclodextrin, hydroxypropyl-β-cyclodextrin, and hydroxypropyl-γ-cyclodextrin. These compounds may be used alone or in combination of two or more.

The thickness of the adhesive layer is preferably 0.5 μm or more and 6 μm or less, more preferably 0.8 μm or more and 5 μm or less, and even more preferably 1 μm or more and 4.5 μm or less.
By setting the thickness of the adhesive layer to 0.5 μm or more, the adhesiveness of the adhesive layer can be improved. When the adhesive layer is formed of a cured product of a resin composition containing a polyester polyol, an isocyanate compound, and a phosphoric acid-modified compound, the load resistance of the laminate for packaging materials can be improved.
By setting the thickness of the adhesive layer to 6 μm or less, the processability of the laminate for packaging materials can be improved.

  The adhesive layer may be applied and dried on a substrate or the like by a conventionally known method such as a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a Fonten method, and a transfer roll coating method. Can be formed.

(Gas barrier coating film)
Within a range that does not impair the properties of the present invention, the laminate for packaging materials of the present invention may be a mixture of a metal alkoxide and a water-soluble polymer between any layers in the presence of a sol-gel method catalyst, water and an organic solvent. And a gas barrier coating film containing at least one resin composition such as a hydrolyzate of a metal alkoxide or a hydrolyzed condensate of a metal alkoxide obtained by polycondensation by a sol-gel method.
Thereby, the oxygen barrier property and the water vapor barrier property of the laminate for packaging materials of the present invention can be further improved.
Further, in the case where the deposited film is composed of an inorganic oxide, by providing the gas barrier coating film so as to be adjacent to the deposited film, it is possible to effectively prevent cracks in the deposited film.

In one embodiment, the metal alkoxide is represented by the following general formula.
R ¹ _n M (OR ² ) _m
(Wherein, 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 a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group and an i-butyl group. Can be.

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

Further, it is preferable to use a silane coupling agent together with the metal alkoxide.
As the silane coupling agent, a known organoalkoxysilane containing an organic reactive group can be used, and an organoalkoxysilane having an epoxy group is particularly preferable. Examples of the organoalkoxysilane having an epoxy group include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Can be

  Two or more silane coupling agents as described above may be used, and the silane coupling agent is used in an amount of about 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the alkoxide. Is preferred.

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

The content of the water-soluble polymer in the gas barrier coating film is preferably 5 parts by mass or more and 500 parts by mass or less based on 100 parts by mass of the metal alkoxide.
By setting the content of the water-soluble polymer in the gas barrier coating film to 5 parts by mass or more based on 100 parts by mass of the metal alkoxide, the oxygen barrier property and the water vapor barrier property of the laminate for packaging materials of the present invention are further improved. can do. Further, by setting the content of the water-soluble polymer in the gas barrier coating film to 500 parts by mass or less based on 100 parts by mass of the metal alkoxide, the film forming property of the gas barrier coating film can be improved.

The thickness of the gas barrier coating film is preferably from 0.01 μm to 100 μm, more preferably from 0.1 μm to 50 μm.
When the thickness of the gas barrier coating film is 0.01 μm or more, the oxygen barrier property and the water vapor barrier property of the packaging material laminate of the present invention can be improved. In addition, when provided so as to be adjacent to a deposition film formed of an inorganic oxide, generation of cracks in the deposition film can be prevented.
Further, by setting the thickness of the gas barrier coating film to 100 μm or less, the recyclability and processability of the laminate for packaging materials of the present invention can be improved.

The gas barrier coating film is formed by coating a composition containing the above-mentioned material on a substrate by a conventionally known means such as a roll coat such as a gravure roll coater, a spray coat, a spin coat, a dipping, a brush, a bar code, and an applicator. However, the composition can be formed by polycondensing the composition by a sol-gel method.
As the sol-gel method catalyst, an acid or amine compound is preferable. As the amine-based compound, a tertiary amine which is substantially insoluble in water and soluble in an organic solvent is preferable, for example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentyl. Amines and the like. Among these, N, N-dimethylbenzylamine is preferred.
The sol-gel method catalyst is preferably used in a range of 0.01 to 1.0 part by mass, and preferably in a range of 0.03 to 0.3 part by mass, per 100 parts by mass of the metal alkoxide. Is more preferable.
By setting the amount of the sol-gel method catalyst to 0.01 parts by mass or more per 100 parts by mass of the metal alkoxide, the catalytic effect can be improved.
Further, by setting the amount of the sol-gel method catalyst to 1.0 parts by mass or less per 100 parts by mass of the metal alkoxide, the thickness of the formed gas barrier coating film can be made uniform.

The composition may further include an acid. The acid is used as a catalyst for the sol-gel method, mainly as a catalyst for hydrolysis of an alkoxide or a silane coupling agent.
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.
The amount of the acid to be used is preferably 0.001 mol or more and 0.05 mol or less with respect to the total mol amount of the alkoxide portion (for example, silicate portion) of the alkoxide and the silane coupling agent.
The catalytic effect can be improved by setting the amount of the acid to be 0.001 mol or more with respect to the total molar amount of the alkoxide component (for example, the silicate portion) of the alkoxide and the silane coupling agent.
In addition, the thickness of the gas barrier coating film to be formed can be made uniform by controlling the amount of the alkoxide and the silane coupling agent to be 0.05 mol or less based on the total molar amount of the alkoxide component (for example, the silicate portion). it can.

Further, the composition may contain water in a ratio of preferably 0.1 mol or more and 100 mol or less, more preferably 0.8 mol or more and 2 mol or less, based on 1 mol of the total molar amount of the alkoxide. preferable.
By setting the content of water to 0.1 mol or more based on 1 mol of the total molar amount of the alkoxide, the oxygen barrier property and the water vapor barrier property of the laminate for packaging materials of the present invention can be improved.
Further, by setting the content of water to 100 mol or more based on 1 mol of the total molar amount of the alkoxide, the hydrolysis reaction can be promptly performed.

  Further, the 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 of 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 catalyst, water, an organic solvent, and if necessary, a silane coupling agent. The polycondensation reaction proceeds gradually in the composition.
Next, the composition is applied and dried on a substrate by the above-mentioned conventionally known method.
By this drying, the polycondensation reaction of the alkoxide and the water-soluble polymer (when the composition contains a silane coupling agent, also the silane coupling agent) further proceeds, and a composite polymer layer is formed.
Finally, the composition is heated at a temperature of 20 to 250 ° C., preferably 50 to 220 ° C. for 1 second to 10 minutes to form a gas barrier coating film.

(Packaging material)
The packaging material of the present invention is characterized by comprising the above-mentioned laminate for packaging material.
The shape of the packaging material is not particularly limited, and may be a bag-like shape as shown in FIG.
In one embodiment, the bag-shaped packaging material can be manufactured by folding and stacking the laminate of the present invention in two so that the heat seal layer is on the inside, and heat-sealing the end thereof. .
In another embodiment, the bag-shaped packaging material can also be manufactured by stacking two laminates so that the heat seal layers face each other, and heat sealing the ends thereof.
In the drawings, the hatched portions represent the heat seal portions.

  The method of heat sealing is not particularly limited, and can be performed by a known method such as a bar seal, a rotating roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal.

In one embodiment, as shown in FIG. 10, the packaging material has a shape of a stand pouch having a body and a bottom.
The stand-pouch-shaped packaging material is heat-sealed in a tubular shape so that the heat-sealing layer of the above-mentioned packaging material laminate is on the inside, thereby forming a body portion, and then, for another packaging material. The laminate can be manufactured by folding the laminate into a V-shape such that the heat seal layer is on the inside, sandwiching the laminate from one end of the body, and heat sealing to form a bottom.

The content filled in the packaging material is not particularly limited, and the content may be a liquid, a powder, or a gel. Further, the food may be a food or a non-food.
After filling the contents, the opening can be heat sealed to form a package.

  Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1
Ethylene-vinyl alcohol copolymer (EVOH, manufactured by Kuraray Co., Ltd., trade name: EVAL E171B, density: 1.14 g / cm ³ , melting point: 165 ° C., MFR: 1.7 g /) constituting the gas barrier resin layer 10 minutes, ethylene content: 44% by mass)
Polyolefin (trade name: Admer QF551, manufactured by Mitsui Chemicals, Inc., density: 0.89 g / cm ³ , melting point: 135 ° C., MFR: 2.5 g / 10 minutes) constituting an adhesive resin layer;
Polypropylene (manufactured by TPC Corporation, trade name: FL7540L, density: 0.90 g / cm ³ , melting point: 138 ° C., MFR: 7.0 g / 10 minutes) constituting the polyolefin resin layer,
Is formed by co-extrusion using the T-die method, and stretched 3.1 times in the longitudinal direction (MD) and the width direction (TD), respectively, to obtain a gas barrier resin layer (1 μm) / adhesive resin layer (2 μm) / A gas barrier laminate having a configuration composed of a polyolefin resin layer (15 μm) was produced.

  On the gas barrier resin layer of the gas barrier laminate produced as described above, a 30 nm-thick aluminum vapor-deposited film was formed by a PVD method. In addition, when the vapor deposition concentration (OD value) of the formed vapor deposition film was measured, it was 3.0.

A 18 μm-thick biaxially oriented polypropylene film (manufactured by Toyobo Co., Ltd., trade name: P2108) was prepared as a base material.
An image was formed on one surface of the biaxially stretched polypropylene film by a gravure printing method using a solvent-type gravure ink (Finart, manufactured by DIC Graphics Co., Ltd.).

  A two-component curable polyurethane adhesive (trade name: RU-3600 / H-689, manufactured by Rock Paint Co., Ltd.) ).

  Subsequently, the polypropylene was extruded into a film by a T-die method to obtain an unstretched polypropylene film having a thickness of 35 μm which constitutes a heat seal layer.

  On one surface of the heat seal layer produced as described above, a 30 nm-thick aluminum vapor-deposited film was formed by a PVD method. In addition, when the vapor deposition concentration (OD value) of the formed vapor deposition film was measured, it was 3.0.

  A two-component curable polyurethane adhesive (trade name: RU-3600 / H-689, manufactured by Rock Paint Co., Ltd.) was used to bond the polyolefin resin layer included in the gas barrier laminate and the aluminum vapor-deposited film forming surface of the heat seal layer with each other. To obtain a laminate for packaging material of the present invention. The proportion of the same polyolefin (PP) in the laminate thus obtained was 92% by mass.

Example 2
The same procedure as in Example 1 was carried out except that the thickness of the aluminum vapor-deposited film provided on the gas barrier laminate and the heat seal layer was both changed to 20 nm and the OD value of the vapor-deposited film was changed to 2.0. A laminate for packaging material of the present invention was produced. The proportion of the same polyolefin (PP) in the laminate thus obtained was 92% by mass.

Example 3
The gas barrier laminate was used for adhesion between the aluminum deposited film forming surface and the image forming surface of the substrate, and for bonding the polyolefin resin layer included in the gas barrier laminate and the heat sealing layer to the aluminum deposited film forming surface. Except that the two-component curable polyurethane adhesive was changed to a two-component curable adhesive (manufactured by DIC Corporation, trade name: PASLIM VM001 / VM102CP) containing a polyester polyol, an isocyanate compound and a phosphoric acid-modified compound. In the same manner as in Example 1, a laminate for packaging material of the present invention was produced. The proportion of the same polyolefin (PP) in the laminate thus obtained was 92% by mass.

Comparative Example 1
A laminate for packaging material was obtained in the same manner as in Example 1 except that an unstretched polypropylene film (manufactured by Toyobo Co., Ltd., trade name: P1108) having a thickness of 18 μm was used as the base material. The proportion of the same polyolefin (PP) in the laminate thus obtained was 92% by mass.

Comparative Example 2
The above polypropylene was extruded into a film by a T-die method to produce an unstretched polypropylene film having a thickness of 180 μm, and then stretched 3.1 times in the machine direction (MD) and the width direction (TD), respectively. An 18 μm-thick stretched polypropylene film a was obtained.

  An image was formed on one surface of the stretched polypropylene film produced as described above by a gravure printing method using a solvent-type gravure ink (finart, manufactured by DIC Graphics Co., Ltd.).

  The above polypropylene was extruded into a film by a T-die method to produce an unstretched polypropylene film having a thickness of 180 μm, and then stretched 3.1 times in the machine direction (MD) and the width direction (TD), respectively. An 18 μm-thick stretched polypropylene film b was obtained.

  The image forming surface of the stretched polypropylene film a and the stretched polypropylene film b were laminated via a two-component curable polyurethane adhesive (trade name: RU-3600 / H-689, manufactured by Rock Paint Co., Ltd.).

  Next, the polypropylene was extruded into a film by a T-die method to obtain an unstretched polypropylene film having a thickness of 35 μm.

  On one surface of the unstretched polypropylene film produced as described above, a 30 nm-thick aluminum vapor-deposited film was formed by a PVD method. In addition, when the vapor deposition concentration (OD value) of the formed vapor deposition film was measured, it was 3.0.

  A two-component curable polyurethane adhesive (manufactured by Rock Paint Co., Ltd., trade name: RU-) 3600 / H-689) to obtain a laminate for packaging material. The proportion of the same polyolefin (PP) in the laminate thus obtained was 92% by mass.

Comparative Example 3
A laminate for packaging material was obtained in the same manner as in Example 1, except that a stretched polyester film having a thickness of 12 μm (manufactured by Toyobo Co., Ltd., trade name: E5100) was used as a substrate. The proportion of the same polyolefin (PP) in the thus obtained laminate was 74% by mass.

<< Recyclability evaluation >>
The recyclability of the laminate for packaging materials 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 for packaging material was 80% by mass or more.
X: The content of the same polyolefin in the packaging material laminate was less than 80% by mass.

<< strength evaluation >>
Using a tensile tester (trade name: RTC-1310A, manufactured by Orientec Co., Ltd.), the strength when the needle having a diameter of 0.5 mm was pierced was measured on the laminate for packaging materials produced in the above Examples and Comparative Examples. The piercing speed was 50 mm / min. The measurement results are summarized in Table 1.

<< heat resistance evaluation >>
From the laminate for packaging material obtained in the above Examples and Comparative Examples, two test pieces each having a length of 80 mm and a width of 80 mm were produced.
The two test pieces were overlapped so that the heat-seal layers faced each other, and three sides were heat-sealed at 150 ° C. to produce a pouch-shaped packaging material.
The prepared packaging material was visually observed, and the heat resistance of the packaging material laminate was evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 1.
(Evaluation criteria)
：: No wrinkles or the like were generated on the surface of the packaging material, and no adhesion to the heat seal bar was observed.
×: Wrinkles and the like were generated on the surface of the packaging material, and adhesion to the heat seal bar was observed, and bag making could not be performed.

<< Printability evaluation >>
In the above Examples and Comparative Examples, the image formed on the base material was visually observed, and its printability was evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 1.
(Evaluation criteria)
：: Good dimensional stability at the time of printing, and a good image free from rubbing, bleeding, etc. could be formed.
X: Elongation or shrinkage of the film occurred during printing, and the formed image was rubbed or blurred.

<< oxygen barrier property evaluation >>
The laminate for packaging materials obtained in the above Examples and Comparative Examples was cut into A4 size, and OXTRAN2 / 20 manufactured by MOCON, USA, was used. The oxygen permeability (cc) under the environment of 23 ° C. and 90% relative humidity was used. / M ² / day / atm). Table 1 summarizes the measurement results.

<< Evaluation of water vapor barrier property >>
The laminates obtained in the above Examples and Comparative Examples were cut into A4 size, and water vapor permeability (g / m ^{2) in} an environment of 40 ° C. and 90% relative humidity was used using PERMATRAN 3/31 manufactured by MOCON, USA. / Day / atm) was measured. Table 1 summarizes the measurement results.

<Bending load resistance evaluation>
The bending load (stroke: 155 mm, bending operation: 440) is applied to the laminate for packaging material obtained above using a gelbo flex tester (manufactured by Tester Sangyo Co., Ltd., trade name: BE1006BE) in accordance with ASTM F392. °) 5 times.
After the bending load, the oxygen permeability and the water vapor permeability of the laminate were measured. Table 1 summarizes the measurement results.

<< Heat sealability test >>
The laminate for packaging materials obtained in the above Examples and Comparative Examples was cut into 10 cm × 10 cm to prepare sample pieces. This sample piece was folded in two so that the heat seal layer was on the inside, and a region of 1 cm × 10 cm was heat-sealed under the conditions of a temperature of 150 ° C., a pressure of 1 kgf / cm ² , and one second.
The heat-sealed sample piece was cut into a strip having a width of 15 mm, and both ends that were not heat-sealed were gripped by a tensile tester, and the peel strength (N / 15 mm) was measured at a speed of 300 mm / min and a load range of 50 N. It was measured. Table 1 summarizes the measurement results.
Note that the packaging material laminate obtained in Comparative Example 1 was attached to the heat seal bar, and the peel strength could not be measured.

10: gas barrier laminate, 11: gas barrier resin, 12: polyolefin resin layer, 13: adhesive resin layer, 14: laminate for packaging material, 15: base material, 16: heat seal layer, 17: vapor deposition film, 18: adhesive layer, 19: first heat seal layer, 20: second heat seal layer

Claims (9)

Including a gas barrier resin layer and a polyolefin resin layer,
A gas barrier laminate, wherein the gas barrier resin layer and the polyolefin resin layer are co-extrusion stretched resin films.   The gas barrier laminate according to claim 1, further comprising an adhesive resin layer between the gas barrier resin layer and the polyolefin resin layer.   The gas barrier laminate according to claim 1 or 2, wherein the thickness of the gas barrier resin layer is smaller than the thickness of the polyolefin resin layer. A substrate, comprising the gas barrier laminate according to any one of claims 1 to 3, and a heat seal layer,
The substrate is a stretched resin film composed of polyolefin,
The heat seal layer is composed of polyolefin,
The polyolefin constituting the base material, the polyolefin constituting the polyolefin resin layer of the gas barrier laminate, and the polyolefin constituting the heat seal layer are the same polyolefin, and the laminate for packaging materials is characterized in that: .   The packaging material laminate according to claim 4, further comprising a vapor-deposited film between the substrate and the gas barrier laminate, and at least one of the gas barrier laminate and the heat seal layer. .   The laminate for packaging materials according to claim 5, further comprising an adhesive layer between the substrate and the vapor-deposited film, and between the gas-barrier laminate and the vapor-deposited film. The deposited film is an aluminum deposited film,
The packaging material laminate according to claim 6, wherein the adhesive layer comprises a cured product of a resin composition containing a polyester polyol, an isocyanate compound, and a phosphoric acid-modified compound.   The packaging material laminate according to any one of claims 4 to 7, wherein the content of the polyolefin in the entire packaging material laminate is 80% by mass or more.   A packaging material comprising the packaging material laminate according to any one of claims 4 to 8.

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