JP2023073246A - Laminate, packaging material, packaging bag and stand pouch - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate that can achieve a packaging material that has sufficient strength and heat resistance as a packaging material and also has excellent recyclability.

SOLUTION: A laminate has a base material and a heat seal layer. Each of the base material and the heat seal layer is composed of polyethylene. The base material comprises a five-layer co-extruded stretched film of: high-density polyethylene layer; middle-density polyethylene layer; low-density polyethylene layer, linear low-density polyethylene layer or ultra low-density polyethylene layer; middle-density polyethylene layer; and high-density polyethylene layer.

SELECTED DRAWING: Figure 1

COPYRIGHT: (C)2023,JPO&INPIT

Description

TECHNICAL FIELD The present invention relates to a laminate, a packaging material, a packaging bag and a stand pouch composed of the laminate.

Conventionally, packaging materials and the like are produced using resin films made of resin materials. For example, a resin film made of polyethylene is widely used as a packaging material because it has appropriate flexibility and transparency and excellent heat-sealing properties.

Generally, resin films made of polyethylene cannot be used as base materials because they are inferior in terms of strength and heat resistance. Therefore, ordinary packaging materials and the like are composed of laminated films in which the base material and the heat seal layer are made of different resin materials (for example, Patent Document 1).

In recent years, along with the increasing demand for building a recycling-oriented society, packaging materials with high recyclability are in demand. However, as described above, conventional packages are made of different types of resin materials, and it is difficult to separate them into different resin materials, so currently they are not recycled.

JP 2009-202519 A

The present inventors have found that polyethylene, which has been conventionally used as a heat seal layer, can be used as a base material by making it into a stretched film, and the base material is laminated with a heat seal layer composed of polyethylene. By doing so, it was found that it is possible to manufacture a packaging material that has sufficient strength and heat resistance and is recyclable.

The present invention has been made in view of the above findings, and the problem to be solved is to realize a packaging material that has sufficient strength and heat resistance that can be applied as a packaging material and has excellent recyclability. An object of the present invention is to provide a laminate that can
Another problem to be solved by the present invention is to provide a packaging material composed of the laminate.
Moreover, the problem to be solved by the present invention is to provide a packaging bag made from the laminate.
Furthermore, the problem to be solved by the present invention is to provide a standing pouch made from the laminate.

The laminate of the present invention is a laminate comprising a substrate and a heat seal layer,
Both the substrate and the heat seal layer are composed of polyethylene,
The substrate comprises a high-density polyethylene layer, a medium-density polyethylene layer, a low-density polyethylene layer, a linear low-density polyethylene layer or an ultra-low-density polyethylene layer, and a medium-density polyethylene layer;
It is characterized by comprising a high-density polyethylene layer and a five-layer co-extruded stretched film.

In one embodiment of the invention, the laminate comprises a deposited film between the substrate and the heat seal layer.

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

In one embodiment of the present invention, the laminate further comprises an intermediate layer between the substrate and the heat seal layer, the intermediate layer consisting of a stretched polyethylene film provided with a vapor deposited film on one side.

In one embodiment of the invention, the laminate comprises an adhesive layer between the substrate and the intermediate layer and between the intermediate layer and the heat seal layer.

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

In one embodiment of the present invention, the substrate is produced by the inflation method.

In one embodiment of the present invention, the content of polyethylene in the entire laminate is 90% by mass or more.

In one embodiment of the invention, the laminate is used for packaging applications.

A packaging material of the present invention is characterized by being produced using the laminate.

The packaging bag of the present invention is produced using the laminate,
The thickness of the heat seal layer is 20 μm or more and 60 μm or less.

The stand pouch of the present invention is produced using the laminate,
The thickness of the heat seal layer is 50 μm or more and 200 μm or less.

ADVANTAGE OF THE INVENTION According to this invention, the laminated body which can implement|achieve the packaging material which has the intensity|strength and heat resistance as a packaging material, and is excellent also in recyclability can be provided.

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

<Laminate>
A laminate according to the present invention will be described with reference to the drawings.
As shown in FIG. 1, the laminate 10 includes a base material 11 and a heat seal layer 12,
The substrate 11 comprises a high density polyethylene layer 13, a medium density polyethylene layer 14, a low density polyethylene layer, a linear low density polyethylene layer or an ultra low density polyethylene layer 15, a medium density polyethylene layer 16 and a high density polyethylene. layer 17;

Moreover, in one embodiment of the present invention, the laminate 10 can be provided with a deposited film 18 between the substrate 11 and the heat seal layer 12, as shown in FIG.

In one embodiment of the present invention, the laminate 10 can also include an adhesive layer 19 between the base material 11 and the heat seal layer 12 or vapor deposited film 18, as shown in FIG.

Moreover, in one embodiment of the present invention, as shown in FIG. 4, the laminate 10 comprises an intermediate layer 21 comprising a deposited film 18 and a stretched polyethylene film 20 between the substrate 11 and the heat seal layer 12. be able to.

Furthermore, in one embodiment of the present invention, the laminate 10 includes an adhesive layer 19 between the substrate 11 and the intermediate layer 21 and between the intermediate layer 21 and the heat seal layer 12, as shown in FIG. be prepared.

The content of polyethylene in the laminate of the present invention is preferably 90% by mass or more.
By setting the content of polyethylene in the entire laminate of the present invention to 90% by mass or more, the recyclability of the laminate of the present invention can be improved.
The content of polyethylene in the laminate means the ratio of the content of polyethylene to the sum of the contents of the resin materials in the layers constituting the laminate.

Each layer constituting the laminate of the present invention will be described below.

<Base material>
The base material of the laminate of the present invention is made of polyethylene, and the heat seal layer described below is also made of polyethylene. With such a configuration, it is possible to improve the recyclability of the laminate.

A stretched film made of polyethylene is used as the substrate, which can improve the heat resistance and strength of the laminate. Moreover, the printability to the base material can be improved.
The stretched film may be a uniaxially stretched film or a biaxially stretched film.

The stretching ratio in the longitudinal direction (MD) of the stretched film is preferably 2 times or more and 10 times or less, and preferably 3 times or more and 7 times or less.
By setting the stretch ratio of the stretched film in the longitudinal direction (MD) to 2 times or more, the strength and heat resistance of the laminate of the present invention can be improved. Furthermore, the printability to the base material can be improved. Moreover, since the transparency of the base material can be improved, the visibility of an image formed on the surface of the base material on the heat seal layer side can be improved. On the other hand, the upper limit of the stretching ratio in the longitudinal direction (MD) of the stretched film is not particularly limited, but from the viewpoint of the breaking limit of the stretched film, it is preferably 10 times or less.

The stretch ratio in the transverse direction (TD) of the stretched film is preferably 2 times or more and 10 times or less, and preferably 3 times or more and 7 times or less.
By setting the stretch ratio of the stretched film in the transverse direction (TD) to 2 times or more, the strength and heat resistance of the laminate of the present invention can be improved. Furthermore, the printability to the base material can be improved. Moreover, since the transparency of the base material can be improved, the visibility of an image formed on the surface of the base material on the heat seal layer side can be improved. On the other hand, the upper limit of the stretching ratio in the transverse direction (TD) of the stretched film is not particularly limited, but from the viewpoint of the breaking limit of the stretched film, it is preferably 10 times or less.

The haze value of the stretched film is preferably 30% or less, more preferably 20% or less. Thereby, the transparency of a stretched film can be improved.
In addition, in this invention, the haze value of a stretched film is measured based on JISK7105.

The substrate may have an image formed on its surface.
Since it is possible to prevent contact with the outside air and prevent deterioration over time, it is preferable that an image is formed on the side on which the heat seal layer described below is provided.
The image to be formed is not particularly limited, and may represent characters, patterns, symbols, combinations thereof, and the like.
Image formation on the substrate is preferably carried out using a biomass-derived ink, so that the laminate of the present invention can be used to produce a packaging material with less environmental impact.
The image forming method is not particularly limited, and conventionally known printing methods such as gravure printing, offset printing, and flexographic printing can be used. Among these, the flexographic printing method is preferable from the viewpoint of environmental load.

The base material included in the laminate of the present invention includes a high-density polyethylene layer, a medium-density polyethylene layer, a low-density polyethylene layer, a linear low-density polyethylene layer, or an ultra-low-density polyethylene layer (hereinafter, for simplification of the description, the paragraph has a configuration consisting of a five-layer coextruded stretched film of a substrate intermediate layer), a medium density polyethylene layer and a high density polyethylene layer.
With such a configuration, the stretchability of the film can be improved. Moreover, the strength and heat resistance of the laminate of the present invention can be improved. Moreover, it is possible to prevent curling in the base material.
Furthermore, film production efficiency can be improved as described below.
At this time, the thickness of the high-density polyethylene layer is preferably thinner 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 1/10 or more and 1/1 or less, more preferably 1/5 or more and 1/2 or less.
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 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 film can be improved.
Also, the thickness of the high-density polyethylene layer is preferably the same as or thicker than the thickness of the substrate intermediate layer.
The ratio of the thickness of the high-density polyethylene layer to the thickness of the substrate intermediate layer is preferably 1/0.25 or more and 1/2 or less, more preferably 1/0.5 or more and 1/1 or less. preferable.
Heat resistance can be improved by setting the ratio of the thickness of the high-density polyethylene layer to the thickness of the substrate intermediate layer to 1/0.25 or more. Further, by setting the ratio of the thickness of the high-density polyethylene layer to the thickness of the substrate intermediate layer to 1/1 or less, the adhesion between the layers can be improved.
The thickness of each high-density polyethylene layer is preferably 1 μm or more and 20 μm or less, more preferably 2 μm or more and 10 μm or less.
By setting the thickness of the high-density polyethylene layer to 1 μm or more, the strength and heat resistance of the laminate of the present invention can be further improved. Further, by setting the thickness of the high-density polyethylene layer to 20 μm or less, the processability of the laminate of the present invention can be further improved.
The thickness of each medium-density polyethylene layer is preferably 1 μm or more and 30 μm or less, more preferably 5 μm or more and 20 μm or less.
By setting the thickness of the medium-density polyethylene layer to 1 μm or more, the stretchability of the film can be further improved. Further, by setting the thickness of the medium-density polyethylene layer to 30 μm or less, the processability of the laminate of the present invention can be further improved.
The thickness of the substrate intermediate layer is preferably 1 μm or more and 10 μm or less, more preferably 2 μm or more and 5 μm or less.
By setting the thickness of the substrate intermediate layer to 1 μm or more, the adhesion between the high-density polyethylene layer and the medium-density polyethylene layer can be further improved. Further, by setting the thickness of the substrate intermediate layer to 10 μm or less, the processability of the laminate of the present invention can be further improved.

In one embodiment, a substrate having such a configuration can be produced, for example, by an inflation method.
Specifically, from the outside, a high-density polyethylene, a medium-density polyethylene layer, and a low-density polyethylene layer, a linear low-density polyethylene layer, or an ultra-low-density polyethylene layer are coextruded into a tubular shape, and then facing each other. A low-density polyethylene layer, a linear low-density polyethylene layer, or an ultra-low-density polyethylene layer can be produced by pressing them together 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 addition, stretching can also be performed in the inflation film forming machine, thereby further improving production efficiency.

In the present invention, as the high-density polyethylene, polyethylene having a density of 0.945 g/cm ³ or more can be used, and as the medium-density polyethylene, a density of 0.925 g/cm ³ or more and less than 0.945 g/cm ³ can be used. As the low-density polyethylene, polyethylene having a density of 0.900 g/cm ³ or more and less than 0.925 g/cm ³ can be used, and as the linear low-density polyethylene, the density of 0.900 g/cm ³ or more and less than 0.925 g/cm ³ can be used, and polyethylene with a density of less than 0.900 g/cm ³ can be used as the ultra-low density polyethylene.

Polyethylenes having different densities and branches as described above can be obtained by appropriately selecting a polymerization method. For example, using a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst as a polymerization catalyst, by any of gas phase polymerization, slurry polymerization, solution polymerization, and high pressure ion polymerization, It is preferable to carry out in one stage or in multiple stages of two or more stages.

The above-mentioned single-site catalyst is a catalyst capable of forming uniform active species, and is usually prepared by contacting a metallocene-based transition metal compound or a non-metallocene-based transition metal compound with an activating cocatalyst. . A single-site catalyst has a more uniform active site structure than a multi-site catalyst, and is therefore preferable because it can polymerize a polymer having a high molecular weight and a highly uniform structure. As the single-site catalyst, it is particularly preferable to use a metallocene-based catalyst. The metallocene catalyst is a catalyst containing a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, a cocatalyst, an organometallic compound if necessary, and each catalyst component of a carrier. be.

In the transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, the cyclopentadienyl skeleton is a cyclopentadienyl group, a substituted cyclopentadienyl group, or the like. . Substituted cyclopentadienyl groups include hydrocarbon groups having 1 to 30 carbon atoms, silyl groups, silyl-substituted alkyl groups, silyl-substituted aryl groups, cyano groups, cyanoalkyl groups, cyanoaryl groups, halogen groups, haloalkyl groups and halosilyl groups. It has at least one substituent selected from groups and the like. The substituted cyclopentadienyl group may have two or more substituents, and the substituents are bonded to each other to form a ring, such as an indenyl ring, a fluorenyl ring, an azulenyl ring, and hydrogenated forms thereof. may be formed. A ring formed by combining substituents with each other may further have a substituent with each other.

In the transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, examples of the transition metal include zirconium, titanium and hafnium, with zirconium and hafnium being particularly preferred. The transition metal compound usually has two ligands having a cyclopentadienyl skeleton, and each ligand having a cyclopentadienyl skeleton is preferably bonded to each other by a bridging group. The bridging group includes an alkylene group having 1 to 4 carbon atoms, a silylene group, a dialkylsilylene group, a substituted silylene group such as a diarylsilylene group, and a substituted germylene group such as a dialkylgermylene group and a diarylgermylene group. A substituted silylene group is preferred. One or a mixture of two or more of the transition metal compounds of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton can be used as a catalyst component.

The co-catalyst is one that can make the above Group IV transition metal compound of the periodic table effective as a polymerization catalyst, or one that can balance the ionic charges in a catalytically activated state. Examples of co-catalysts include benzene-soluble aluminoxanes of organoaluminumoxy compounds, benzene-insoluble organoaluminumoxy compounds, ion-exchange layered silicates, boron compounds, cations containing or not containing active hydrogen groups, and non-coordinating anions. ionic compounds, lanthanide salts such as lanthanum oxide, tin oxide, and phenoxy compounds containing a fluoro group.

The transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton may be supported on an inorganic or organic compound carrier and used. As the carrier, porous oxides of inorganic or organic compounds are preferred, and specific examples include ion-exchange layered silicates such as montmorillonite, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ and B ₂ O. ₃ , CaO, ZnO, BaO, _ThO2 , etc. or mixtures thereof. Examples of organometallic compounds that may be used if necessary include organoaluminum compounds, organomagnesium compounds, and organozinc compounds. Of these, organic aluminum is preferably used.

Copolymers of ethylene and other monomers can also be used as long as the properties of the present invention are not impaired. Ethylene copolymers include copolymers composed of ethylene and α-olefins having 3 to 20 carbon atoms, and α-olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 4-methyl-1-pentene and 6-methyl- 1-heptene and the like. In addition, it may be a copolymer with vinyl acetate or acrylic acid ester as long as it does not impair the purpose of the present invention.

In addition, in the present invention, biomass-derived ethylene may be used instead of ethylene obtained from fossil fuels as a raw material for obtaining the polyethylene or the like. Since such biomass-derived polyethylene is a carbon-neutral material, it can be used as a packaging material with even less environmental impact. Such biomass-derived polyethylene can be produced, for example, by a method as described in JP-A-2013-177531. Also, commercially available biomass-derived polyethylenes, such as Green PE from Braskem, may be used.

Polyethylene recycled by mechanical recycling can also be used. Here, mechanical recycling generally means that the recovered polyethylene film or the like is pulverized and washed with alkali to remove dirt and foreign matter from the film surface, and then dried for a certain period of time under high temperature and reduced pressure to remain inside the film. In this method, the contaminants are diffused to decontaminate the polyethylene film, and then the dirt is removed from the polyethylene film, which is then returned to polyethylene.

The base material may contain additives as long as they do not impair the characteristics of the present invention. agents, reinforcing agents, antistatic agents, pigments and modifying resins.

Moreover, it is preferable that the base material is surface-treated. This can improve adhesion with adjacent layers.
The method of surface treatment is not particularly limited, and examples include 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 treatments such as treatments are included.
Moreover, you may form an anchor-coat layer on the base-material surface using a conventionally well-known anchor-coat agent.

The thickness of the substrate is preferably 10 μm or more and 50 μm or less, more preferably 12 μm or more and 30 μm or less.
By setting the thickness of the substrate to 10 μm or more, the strength of the laminate of the present invention can be improved. Further, by setting the thickness of the base material to 50 μm or less, the processability of the laminate of the present invention can be improved.

The substrate can be produced by forming a polyethylene film by a T-die method, an inflation method, or the like, producing a film, and then stretching the film.

When the substrate is produced by the T-die method, the MFR of polyethylene constituting each layer is preferably 3 g/10 minutes or more and 20 g/10 minutes or less.
By setting the MFR of polyethylene to 3 g/10 minutes or more, the processability of the laminate of the present invention can be improved. Further, by setting the MFR of polyethylene 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 polyethylene constituting each layer is preferably 0.5 g/10 min or more and 5 g/10 min or less.
By setting the MFR of polyethylene to 0.5 g/10 minutes or more, the processability of the laminate of the present invention can be improved. Further, by setting the MFR of polyethylene to 5 g/10 minutes or less, the film formability can be improved.

In addition, the base material is not limited to the one produced by the above method, and a commercially available one may be used.

<Heat seal layer>
The heat-sealing layer provided in the laminate of the present invention is characterized by being made of polyethylene, like the base material described above. With such a configuration, it is possible to obtain a packaging material that has sufficient strength and heat resistance as a packaging material and is recyclable.
However, the stretched polyethylene film is formed from an unstretched polyethylene resin film or by melt extrusion of polyethylene.

Low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and very high density polyethylene (VLDPE) are preferable from the viewpoint of heat sealability.
Copolymers of ethylene and other monomers can be used as long as the characteristics of the present invention are not impaired.
Moreover, from the viewpoint of environmental load, polyethylene derived from biomass or recycled polyethylene is preferable.

The heat-sealing layer can contain the above-mentioned additives as long as the properties of the present invention are not impaired.

In one embodiment, the heat-seal layer has a multi-layer structure and comprises, as an intermediate layer, a layer containing at least one of medium density polyethylene and high density polyethylene.
Specifically, a layer containing at least one of low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene/layer containing at least one of medium-density polyethylene and high-density polyethylene/low-density polyethylene, linear It can be configured by a layer containing at least one of low-density polyethylene and ultra-low-density polyethylene.
With such a configuration, the bag-making aptitude and strength of the laminate of the present invention can be further improved while maintaining the heat-sealing property.

Also, in other embodiments, the heat seal layer is a layer comprising at least one of low density polyethylene, linear low density polyethylene, and ultra-low density polyethylene/layer comprising biomass-derived polyethylene/low density polyethylene, straight It can be configured by a layer containing at least one of linear low-density polyethylene and ultra-low-density polyethylene.
With such a configuration, the environmental load of packaging materials and the like produced using the laminate of the present invention can be further reduced.

It is preferable that the thickness of the heat seal layer is appropriately changed according to the weight of the contents to be filled in the packaging material produced from the laminate of the present invention.
For example, when producing a packaging bag 20 as shown in FIG. 6 filled with contents of 1 g or more and 200 g or less, the thickness of the heat seal layer is preferably 20 μm or more and 60 μm or less.
By setting the thickness of the heat-seal layer to 20 μm or more, it is possible to prevent the filled content from leaking due to breakage of the heat-seal layer. Further, by setting the heat seal layer to 60 μm or less, the workability of the laminate of the present invention can be improved.

Further, for example, when producing a stand-up pouch 30 as shown in FIG. 7 filled with contents of 50 g or more and 2000 g or less, the thickness of the heat seal layer is preferably 50 μm or more and 200 μm or less.
By setting the thickness of the heat-seal layer to 50 μm or more, it is possible to prevent the filled content from leaking due to breakage of the heat-seal layer. Further, by setting the thickness of the heat seal layer to 200 μm or less, the workability of the laminate of the present invention can be improved.
6 and 7 are heat-sealed portions.

<Deposited film>
The laminate of the present invention can have a deposited film between the substrate and the heat seal layer. Thereby, the gas barrier property of the laminate, specifically, the oxygen barrier property and the water vapor barrier property can be improved.

As the deposited film, a deposited film composed of 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 is used. can be mentioned.

Also, the thickness of the deposited film is preferably 1 nm or more and 150 nm or less, more preferably 5 nm or more and 60 nm or less, and even more preferably 10 nm or more and 40 nm or less.
By setting the thickness of the deposited film to 1 nm or more, the oxygen barrier property and water vapor barrier property of the laminate of the present invention can be further improved. Further, by setting the thickness of the vapor deposition film to 150 nm or less, it is possible to prevent the generation of cracks in the vapor deposition film and improve the recyclability of the laminate of the present invention.

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 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 using 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 a plasma chemical method. Chemical vapor deposition methods (Chemical Vapor Deposition method, CVD method) such as vapor deposition method, thermal chemical vapor deposition method, and photochemical vapor deposition method can be mentioned.

Further, for example, both physical vapor deposition and chemical vapor deposition may be used in combination to form a composite film composed of two or more layers of deposited films of different inorganic oxides. The degree of vacuum in the deposition chamber is preferably about 10-2 to 10-8 mbar before introducing oxygen, and about 10-1 to 10-6 mbar after introducing oxygen. The amount of oxygen to be introduced and the like differ depending on the size of the vapor deposition machine and the like. As the oxygen to be introduced, an inert gas such as argon gas, helium gas, nitrogen gas, or the like may be used as a carrier gas as long as it does not interfere. 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 surface treatment described above. This can improve adhesion with adjacent layers.

<Adhesive layer>
In one embodiment, the laminate of the present invention can have an adhesive layer between any layers. Thereby, the adhesion between these layers can be improved.

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

Further, when the adhesive layer is provided so as to be adjacent to the evaporated aluminum film, it is preferable that the adhesive layer is composed of a cured product of a resin composition containing a polyester polyol, an isocyanate compound and a phosphoric acid-modified compound. .
By configuring the adhesive layer in such a manner, the layered product of the present invention can be further improved in oxygen barrier properties and water vapor barrier properties.
In addition, when a laminate having a vapor deposition film is applied to a packaging material, a bending load is applied to the laminate by a molding machine or the like, and cracks or the like may occur in the aluminum vapor deposition film. By using the specific adhesive as described above, it is possible to suppress deterioration of oxygen barrier properties and water vapor barrier properties even when cracks occur in the aluminum deposition film.

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

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

The resin composition may further contain plate-like inorganic compounds, coupling agents, cyclodextrins and/or derivatives thereof, and the like.

As polyester polyols having two or more hydroxyl groups in one molecule as functional groups, for example, the following [first example] to [third example] can be used.
[Example 1] Polyester polyol obtained by polycondensation of an ortho-oriented polycarboxylic acid or its anhydride and a polyhydric alcohol [Example 2] Polyester polyol having a glycerol skeleton [Example 3] Having an isocyanuric ring Polyester Polyol Each polyester polyol will be described below.

The polyester polyol according to the first example is selected from the group consisting of a polyvalent carboxylic acid component containing at least one or more of orthophthalic acid and its anhydride, and ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol. It is a polycondensate obtained by polycondensation with a polyhydric alcohol component containing at least one of the polycondensates.
In particular, a polyester polyol having a content of 70 to 100% by mass of orthophthalic acid and its anhydride relative to the total polyvalent carboxylic acid component is preferred.

The polyester polyol according to the first example essentially contains orthophthalic acid and its anhydride as the polyvalent carboxylic acid component. may
Specifically, aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid and dodecanedicarboxylic acid, unsaturated bond-containing polycarboxylic acids such as maleic anhydride, 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 polybasic acids such as aromatic polycarboxylic acids such as polyvalent derivatives, p-hydroxybenzoic acid, p-(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 polyhydric carboxylic acid.

一般式（１）において、Ｒ１、Ｒ２、Ｒ３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 a polyester polyol according to the second example, a polyester polyol having a glycerol skeleton represented by general formula (1) can be mentioned.

In general formula (1), R1, R2 and R3 are each independently H (hydrogen atom) or a group represented by general formula (2) below.

In formula (2), n represents an integer of 1 to 5, X is a 1,2-phenylene group which may have a substituent, a 1,2-naphthylene group, a 2,3-naphthylene group, 2, 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).
At least one of R1, R2 and R3 represents a group represented by general formula (2).

In general formula (1), at least one of R1, R2 and R3 must be a group represented by general formula (2). Among them, it is preferable that all of R1, R2 and R3 are groups represented by general formula (2).

Further, a compound in which any one of R1, R2, and R3 is a group represented by general formula (2), and a compound in which any two of R1, R2, and R3 are groups represented by general formula (2) and a compound in which all of R1, R2, and R3 are groups represented by general formula (2).

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 arylene group which may be
When X is substituted by substituents, it may be substituted by one or more substituents, which are attached to any carbon atom on X that is different from the radical. The substituents include chloro, bromo, methyl, ethyl, i-propyl, hydroxyl, methoxy, ethoxy, phenoxy, methylthio, phenylthio, cyano, nitro, amino, phthalimido group, carboxyl group, carbamoyl group, N-ethylcarbamoyl group, phenyl group, naphthyl group and the like.

In general formula (2), Y is 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, methylpentylene. and alkylene groups having 2 to 6 carbon atoms such as dimethylbutylene group. Among them, Y is preferably a propylene group or an ethylene group, most preferably an ethylene group.

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

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

Further, the polyhydric alcohol component includes alkylenediol having 2 to 6 carbon atoms. Diols such as, for example, 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、Ｒ１、Ｒ２、Ｒ３は、各々独立に、「－（ＣＨ２）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 general formula (3), R1, R2, and R3 each independently represent "-(CH2)n1-OH (where n1 represents an integer of 2 to 4)", or the structure of general formula (4) show.

In 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, a 1,2-naphthylene group, a 2,3-naphthylene group, represents an optionally substituted arylene group selected from the group consisting of a 2,3-anthraquinonediyl group and a 2,3-anthracenediyl group, and Y represents an alkylene group having 2 to 6 carbon atoms) Represents a group represented by However, at least one of R1, R2 and R3 is a group represented by general formula (4).

In general formula (3), the alkylene group represented by -(CH2)n1- may be linear or branched. n1 is preferably 2 or 3, most preferably 2.

In general formula (4), n2 represents an integer of 2-4, and n3 represents an integer of 1-5.
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 arylene group which may be

When X is substituted by substituents, it may be substituted by one or more substituents, which are attached to any carbon atom on X that is different from the radical. The substituents include chloro, bromo, methyl, ethyl, i-propyl, hydroxyl, methoxy, ethoxy, phenoxy, methylthio, phenylthio, cyano, nitro, amino, phthalimido group, carboxyl group, carbamoyl group, N-ethylcarbamoyl group, phenyl group, naphthyl group and the like.
Among the substituents of X, hydroxyl group, cyano group, nitro group, amino group, phthalimido group, carbamoyl group, N-ethylcarbamoyl group and phenyl group are preferable. Phenyl groups are most preferred.

In general formula (4), Y is 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, methylpentylene. and alkylene groups having 2 to 6 carbon atoms such as dimethylbutylene group. Among them, Y is preferably a propylene group or an ethylene group, most preferably an ethylene group.

In general formula (3), at least one of R1, R2 and R3 is a group represented by general formula (4). Among them, it is preferable that all of R1, R2 and R3 are groups represented by general formula (4).

Further, a compound in which any one of R1, R2, and R3 is a group represented by general formula (4), and a compound in which any two of R1, R2, and R3 are groups represented by general formula (4) and a compound in which all of R1, R2, and R3 are groups represented by general formula (4), and any two or more compounds may form 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 the carboxylic acid is substituted at the ortho position, and a polyhydric alcohol component. can be synthesized by reacting as an essential component

Examples of triols 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. etc.

Further, the aromatic polyvalent carboxylic acid or its anhydride in which the carboxylic acid is substituted at the ortho-position includes orthophthalic acid or its anhydride, naphthalene 2,3-dicarboxylic acid or its anhydride, and naphthalene 1,2-dicarboxylic acid. or its anhydride, anthraquinone 2,3-dicarboxylic acid or its anhydride, and 2,3-anthracenecarboxylic acid or its anhydride. These compounds may have a substituent at any carbon atom of the aromatic ring.

The substituents include chloro, bromo, methyl, ethyl, i-propyl, hydroxyl, methoxy, ethoxy, phenoxy, methylthio, phenylthio, cyano, nitro, amino, phthalimido group, carboxyl group, carbamoyl group, N-ethylcarbamoyl group, phenyl group and naphthyl group;

Further, the polyhydric alcohol component includes alkylenediol having 2 to 6 carbon atoms. Diols such as, for example, 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 a triol compound having an isocyanuric ring, and the carboxylic acid is at the ortho position. A polyester polyol compound with an isocyanuric ring that uses orthophthalic anhydride as the substituted aromatic polycarboxylic acid or its anhydride and ethylene glycol as the polyhydric alcohol has particularly excellent oxygen barrier properties and adhesion. preferable.

The isocyanuric ring is highly polar and trifunctional, which can increase the polarity of the overall system and increase the crosslink density. From this point of view, it is preferable that the isocyanuric ring content is 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 its molecule.
Also, the isocyanate compound may be aromatic or aliphatic, and may be a low-molecular-weight compound or a high-molecular-weight compound.
Furthermore, the isocyanate compound may be a blocked isocyanate compound obtained by addition reaction using a known isocyanate blocking agent by a known and commonly used appropriate method.
Among them, a polyisocyanate compound having 3 or more isocyanate groups is preferable from the viewpoint of adhesiveness and retort resistance, and an aromatic compound is preferable from the viewpoint of oxygen barrier properties and water vapor barrier properties.

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

一般式（５）において、Ｒ１、Ｒ２、Ｒ３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、Ｒ４、Ｒ５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。 A phosphoric acid-modified compound is, for example, a compound represented by the following general formula (5) or (6).

In general formula (5), R1, R2, and R3 are 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 (meth)acryloyloxy group. A group selected from alkyl groups having 1 to 4 carbon atoms, at least one of which is a hydrogen atom, and n represents an integer of 1 to 4.

In the formula, R4 and R5 are hydrogen atoms, alkyl groups having 1 to 30 carbon atoms, (meth)acryloyl groups, optionally substituted phenyl groups and (meth)acryloyloxy groups having 1 to 4 carbon atoms. wherein 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 both x and y are 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 Ethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, polyoxyethylene alkyl ether phosphoric acid and the like can be mentioned, and one or more of these can be used.

The content of the phosphoric acid-modified compound in the resin composition is preferably 0.005% by mass or more and 10% by mass or less, and more preferably 0.01% by mass or more and 1% by mass or less.
By setting the content of the phosphoric acid-modified compound to 0.005% by mass or more, the laminate of the present invention can have improved oxygen barrier properties and water vapor barrier properties. Also, 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.

A resin composition containing a polyester polyol, an isocyanate compound and a phosphoric acid-modified compound may contain a plate-like inorganic compound, thereby improving the adhesiveness of the adhesive layer. Moreover, the bending load resistance of the laminate of the present invention can be improved.
Plate-like inorganic compounds include, for example, kaolinite-serpentine clay minerals (halloysite, kaolinite, endellite, dickite, nacrite, antigorite, chrysotile, etc.) and pyrophyllite-talcs (pyrophyllite, talc, Kerorai, etc.).

Examples of the coupling agent include silane-based coupling agents, titanium-based coupling agents and aluminum-based coupling agents represented by the following general formula (7). These coupling agents may be used alone or in combination of two or more.

Examples of silane coupling agents 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 (amino ethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyl trimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane and 3-triethoxysilyl-N-(1,3-dimethyl-butylidene), and the like.

Examples of titanium-based coupling agents include isopropyltriisostearoyl titanate, isopropyltri(N-aminoethyl-aminoethyl)titanate, isopropyltridodecylbenzenesulfonyltitanate, isopropyltris(dioctylpyrophosphate)titanate, tetraoctylbis (didodecylphosphite) titanate, tetraoctylbis(ditridecylphosphite) titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate, isopropyltrioctynortitanate, isopropyldimethacrylisostearoyl titanate , isopropyl isostearoyl diacryl titanate, diisostearoyl ethylene titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate and dicumylphenyloxyacetate titanate.

Specific examples of aluminum-based coupling agents include acetoalkoxyaluminum diisopropylate, diisopropoxyaluminum ethylacetoacetate, diisopropoxyaluminum monomethacrylate, isopropoxyaluminum alkylacetoacetate mono(dioctylphosphate), aluminum -2-ethylhexanoate oxide trimer, aluminum stearate oxide trimer and alkylacetoacetate aluminum oxide trimer, and the like.

The resin composition can contain cyclodextrin and/or its derivatives, which can improve the adhesion of the adhesive layer. In addition, the bending load resistance of the laminate of the present invention can be further improved.
Specifically, for example, cyclodextrins such as cyclodextrin, alkylated cyclodextrin, acetylated cyclodextrin and hydroxyalkylated cyclodextrin in which the hydrogen atom of the hydroxyl group of the glucose unit of the cyclodextrin is substituted with another functional group can be used. can be done. Branched cyclic dextrins can also be used.
The cyclodextrin backbone in cyclodextrins and cyclodextrin derivatives is α-cyclodextrin consisting of 6 glucose units, β-cyclodextrin consisting of 7 glucose units, and γ-cyclodextrin consisting of 8 glucose units. Either can be used.
These compounds may be used alone or in combination of two or more. Moreover, hereinafter, these cyclodextrins and/or derivatives thereof may be 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.

Alkylated cyclodextrins include, for example, methyl-α-cyclodextrin, methyl-β-cyclodextrin and methyl-γ-cyclodextrin. These compounds may be used alone or in combination of two or more.

Acetylated cyclodextrins include, for example, monoacetyl-α-cyclodextrin, monoacetyl-β-cyclodextrin and monoacetyl-γ-cyclodextrin. These compounds may be used alone or in combination of two or more.

Hydroxyalkylated cyclodextrins include, for example, 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. Further, when an adhesive layer made of a cured product of a resin composition containing a polyester polyol, an isocyanate compound and a phosphoric acid-modified compound is provided adjacent to the aluminum deposition film, the bending load resistance of the laminate is improved. be able to.
By setting the thickness of the adhesive layer to 6 μm or less, the workability of the laminate can be improved.

The adhesive layer is applied onto a base material 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, and then dried. can be formed by

<Middle layer>
In one embodiment, the laminate of the present invention can comprise an intermediate layer between the substrate and the heat-sealable layer, consisting of a stretched polyethylene film with a deposited film on one side. This can further improve the strength, oxygen barrier properties, and water vapor barrier properties of the laminate.

(evaporation film)
The intermediate layer comprises a vapor-deposited film, which can improve gas barrier properties, especially oxygen barrier properties and water vapor barrier properties.

The deposited film includes metals such as aluminum and inorganic oxides such as aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, and barium oxide. can be mentioned.

Also, the thickness of the deposited film is preferably 1 nm or more and 150 nm or less, more preferably 5 nm or more and 60 nm or less, and even more preferably 10 nm or more and 40 nm or less.
By setting the thickness of the deposited film to 1 nm or more, the oxygen barrier property and water vapor barrier property of the laminate of the present invention can be further improved. Further, by setting the thickness of the vapor deposition film to 150 nm or less, it is possible to prevent the generation of cracks in the vapor deposition film and improve the recyclability of the laminate of the present invention.

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 laminate of the present invention. In the present invention, the OD value can be measured according to JIS-K-7361.

A vapor deposition film can be formed by the above method.

The surface of the deposited film is preferably subjected to the surface treatment described above. This can improve adhesion with adjacent layers.

(stretched polyethylene film)
The stretched polyethylene film forming the intermediate layer is characterized by being made of polyethylene, like the substrate and the heat-sealing layer described above. With such a configuration, a recyclable packaging material can be obtained while maintaining strength and heat resistance as a packaging material.

A stretched polyethylene film made of polyethylene is used in order to improve strength and heat resistance as a packaging material. The stretched film may be a uniaxially stretched film or a biaxially stretched film.

The stretching ratio in the longitudinal direction (MD) of the stretched film is preferably 2 times or more and 10 times or less, and preferably 3 times or more and 7 times or less.
By setting the stretch ratio of the stretched film in the longitudinal direction (MD) to 2 times or more, the strength and heat resistance of the laminate of the present invention can be improved. On the other hand, the upper limit of the stretching ratio in the longitudinal direction (MD) of the stretched film is not particularly limited, but from the viewpoint of the breaking limit of the stretched film, it is preferably 10 times or less.

The stretch ratio in the transverse direction (TD) of the stretched film is preferably 2 times or more and 10 times or less, and preferably 3 times or more and 7 times or less.
By setting the stretch ratio of the stretched film in the transverse direction (TD) to 2 times or more, the strength and heat resistance of the laminate of the present invention can be improved. On the other hand, the upper limit of the stretching ratio in the transverse direction (TD) of the stretched film is not particularly limited, but from the viewpoint of the breaking limit of the stretched film, it is preferably 10 times or less.

As the polyethylene contained in the stretched polyethylene film, among those mentioned above, high-density polyethylene and medium-density polyethylene are preferable from the viewpoint of strength, heat resistance, and film stretching suitability, and medium-density polyethylene is more preferable from the viewpoint of stretching suitability.
Further, the intermediate layer may be composed of the multi-layer structure described above, like the base material.

The stretched polyethylene film can contain the above additives as long as the properties of the present invention are not impaired.

The thickness of the stretched polyethylene film is preferably 9 μm or more and 50 μm or less, more preferably 12 μm or more and 30 μm or less.
By setting the thickness of the stretched polyethylene film to 9 μm or more, the strength and heat resistance of the laminate of the present invention can be further improved. Also, by setting the thickness of the stretched polyethylene film to 50 μm or less, the processability of the laminate of the present invention can be improved.

The stretched polyethylene film may be produced by the T-die method or the inflation method, or may be commercially available.

<Application>
The laminate of the present invention can be used particularly preferably for packaging materials.
The packaging material is not particularly limited, and may be a packaging bag 30 as shown in FIG. 6 or a stand pouch 40 having a body portion 41 and a bottom portion 42 as shown in FIG. In the case of the stand-up pouch, even if only the body part is formed of the above laminate, only the bottom part is formed of the above laminate, or both the body part and the bottom part are formed of the above laminate. good.

The packaging bag can be produced by folding the laminated body in two and overlapping them so that the heat-sealed layer of the laminate is on the inside, and heat-sealing the ends thereof.
The packaging bag can also be produced by stacking two laminates so that the heat-seal layers face each other and heat-sealing the edges.

The stand pouch is heat-sealed in a cylindrical shape so that the heat-seal layer of the laminate is on the inside to form a body, and then the laminate is V-shaped so that the heat-seal layer is on the inside. It can be manufactured by folding into a letter shape, pinching from one end of the trunk, and heat-sealing to form the bottom.

The heat sealing method is not particularly limited, and known methods such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing, and ultrasonic sealing can be used.

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

EXAMPLES The present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples.

<Example 1-1>
High-density polyethylene (density: 0.960 g/cm ³ , melting point 130° C., MFR: 0.85 g/10 min, manufactured by Dowchemical, trade name: Elite 5960), medium-density polyethylene (density: 0.940 g/cm ³ , melting point 126° C., MFR: 0.85 g/10 min, manufactured by Dowchemical, trade name: Elite 5940) and ultra-low density polyethylene (density: 0.870 g/cm ³ , melting point: 55° C., MFR: 1.0 g/10 min, Dowchemical Company, trade name: Affinity EG8100G) is provided with a high-density polyethylene layer (12.5 μm), a medium-density polyethylene layer (43.75 μm), and an ultra-low-density polyethylene layer (6.25 μm) from the outside by an inflation molding method. After extruding as a tube-shaped film, the inner ultra-low density polyethylene layers were pressed against each other with a rubber roll to form a high-density polyethylene layer (12.5 μm), a medium-density polyethylene layer (43.75 μm), and an ultra-low density polyethylene layer. A 125 μm thick polyethylene film was obtained comprising a (12.5 μm), a medium density polyethylene layer (43.75 μm) and a high density polyethylene layer (12.5 μm).
This polyethylene film was stretched in the longitudinal direction (MD) at a draw ratio of 5 times to obtain a substrate A having a thickness of 25 μm.
When the haze value of the base material A was measured according to JIS K 7105, the haze value was 6.2%.

An image was formed on one surface of the base material A by gravure printing using an oil-based gravure ink (manufactured by DIC Graphics, trade name: Finart).

Linear low-density polyethylene A (density: 0.923 g/cm ³ , melting point 121° C., MFR: 1.5 g/10 min, manufactured by Prime Polymer Co., Ltd., trade name: SP2510), linear low-density polyethylene A and A mixture (2:8 (by mass)) of biomass-derived polyethylene (density: 0.916 g/cm ³ , MFR: 1.3 g/10 min, biomass degree: 87%, manufactured by Braskem, trade name: SLL118) and , Linear low-density polyethylene B (density: 0.913 g/cm ³ , melting point: 116° C., MFR: 2.0 g/10 min, manufactured by Prime Polymer Co., Ltd., trade name: SP1520), and film formation by inflation molding. A layer made of linear low-density polyethylene A with a thickness of 17 μm, a layer made of linear low-density polyethylene A with a thickness of 16 μm and biomass-derived polyethylene, and a linear low-density polyethylene B with a thickness of 17 μm A heat seal layer A having a thickness of 50 μm was produced, comprising a layer consisting of

The image forming surface of the substrate A and the linear low-density polyethylene A layer of the heat seal layer A were bonded together with a two-component curable urethane adhesive (manufactured by Rock Paint Co., Ltd., trade name: RU- 77T/H-7) to obtain the laminate of the present invention.
The thickness of the adhesive layer formed by the two-component curable urethane adhesive was 3.0 μm.
Moreover, the ratio of polyethylene in the laminate thus obtained was 95% by mass.

<Comparative Example 1-1>
The high-density polyethylene, the medium-density polyethylene, and the ultra-low-density polyethylene are extruded from the outside by an inflation molding method as a tubular film having a high-density polyethylene layer, a medium-density polyethylene layer, and an ultra-low-density polyethylene layer, The inner ultra-low density polyethylene layers were crimped together with a rubber roll to form a high-density polyethylene layer (2.5 μm), a medium-density polyethylene layer (8.75 μm), an ultra-low-density polyethylene layer (2.5 μm), and a medium-density polyethylene. A 25 μm thick substrate a was obtained, comprising a layer (8.75 μm) and a high density polyethylene layer (2.5 μm).
When the haze value of the base material a was measured according to JIS K 7105, the haze value was 21.3%.

An image was formed on one surface of the base material a by gravure printing using the oil-based gravure ink.

The image forming surface of the substrate a and the layer made of linear low-density polyethylene A of the heat seal layer A were laminated via the two-component curable urethane adhesive to obtain a laminate. .
The thickness of the adhesive layer formed by the two-component curable urethane adhesive was 3.0 μm.
Moreover, the ratio of polyethylene in the laminate thus obtained was 95% by mass.

<Comparative Example 1-2>
A laminate was produced in the same manner as in Example 1-1, except that the substrate A was changed to a 12 μm thick biaxially stretched PET film (manufactured by Toyobo Co., Ltd., trade name: E5100).
Moreover, the ratio of polyethylene in the laminate thus obtained was 75% by mass.

<Example 2-1>
The base material A was prepared.

An image was formed on one surface of the base material A by gravure printing using an oil-based gravure ink (manufactured by DIC Graphics, trade name: Finart).

Inflation molding of the linear low-density polyethylene A, the mixture of the linear low-density polyethylene A and the biomass-derived polyethylene (2:8 (by mass)), and the linear low-density polyethylene B A layer made of linear low-density polyethylene A with a thickness of 34 μm, a layer made of linear low-density polyethylene A and biomass-derived polyethylene with a thickness of 32 μm, and a linear film with a thickness of 34 μm. A 100 μm thick heat seal layer B comprising a layer of low density polyethylene B was produced.

The image forming surface of the base material A and the layer made of the linear low-density polyethylene A of the heat seal layer B are laminated via the two-component curable urethane adhesive to obtain the laminate of the present invention. got
The thickness of the adhesive layer formed by the two-component curable urethane adhesive was 3.0 μm.
The ratio of polyethylene in the laminate thus obtained was 97% by mass.

<Comparative Example 2-1>
The base material a was prepared.

An image was formed on one surface of the base material a by gravure printing using the oil-based gravure ink.

The image forming surface of the substrate a and the layer made of linear low-density polyethylene A of the heat seal layer B were laminated via the two-liquid curing urethane adhesive to obtain a laminate. .
The thickness of the adhesive layer formed by the two-component curable urethane adhesive was 3.0 μm.
The ratio of polyethylene in the laminate thus obtained was 97% by mass.

<Comparative Example 2-2>
A laminate was produced in the same manner as in Example 2-1, except that the base material A was changed to the biaxially stretched PET film having a thickness of 12 μm.
Moreover, the ratio of polyethylene in the laminate thus obtained was 86% by mass.

<Example 3-1>
The base material A was prepared.

An image was formed on one surface of the base material A by gravure printing using an oil-based gravure ink (manufactured by DIC Graphics, trade name: Finart).

A heat seal layer A was prepared, and a 20 nm-thick aluminum deposition film was formed on this linear low-density polyethylene A by PVD.

The image forming surface of the base material A and the deposition surface of the heat seal layer A were laminated via the two-component curable urethane adhesive to obtain the laminate of the present invention.
The thickness of the adhesive layer formed by the two-component curable urethane adhesive was 3.0 μm.
Moreover, the ratio of polyethylene in the laminate thus obtained was 95% by mass.

<Example 3-2>
In Example 3-1, the image forming surface of the substrate A and the deposition surface of the heat seal layer A were adhered using a two-component curing adhesive containing an isocyanate compound and a phosphoric acid-modified compound (manufactured by DIC Corporation, A laminate of the present invention was produced in the same manner as in Example 3-1 except that it was performed using PASLIM VM001/VM102CP).

<Comparative Example 3-1>
The base material a was prepared.

An image was formed on one surface of the base material a by gravure printing using the oil-based gravure ink.

A heat seal layer A was prepared, and a 20 nm-thick aluminum deposition film was formed on this linear low-density polyethylene A by PVD.

The image forming surface of the base material a and the deposition surface of the heat seal layer A were laminated via the two-component curable urethane adhesive to obtain a laminate.
The thickness of the adhesive layer formed by the two-component curable urethane adhesive was 3.0 μm.
Moreover, the ratio of polyethylene in the laminate thus obtained was 95% by mass.

<Comparative Example 3-2>
A laminate was produced in the same manner as in Example 3-1, except that the base material A was changed to the biaxially stretched PET film having a thickness of 12 μm.
Moreover, the ratio of polyethylene in the laminate thus obtained was 76% by mass.

<Example 4-1>
The base material A was prepared.

An image was formed on one surface of the base material A by gravure printing using an oil-based gravure ink (manufactured by DIC Graphics, trade name: Finart).

The medium-density polyethylene was formed into a film by an inflation molding method to obtain a polyethylene film having a thickness of 100 μm, and then stretched in the longitudinal direction (MD) at a draw ratio of 5 times to obtain a stretched polyethylene film A having a thickness of 20 μm. rice field. Then, on one surface of the stretched polyethylene film A, an aluminum deposition film having a thickness of 20 nm was formed by PVD method to obtain an intermediate layer A.

The image forming surface of the base material A was laminated on the deposition surface of the intermediate layer A via the two-liquid curing urethane adhesive. The thickness of the adhesive layer formed by the two-component curable urethane adhesive was 3.0 μm.

A heat seal layer A was prepared. Next, a layer made of linear low-density polyethylene A of the heat seal layer A is laminated on the non-vapor-deposited surface of the intermediate layer A via the two-liquid curing urethane adhesive to obtain the laminate of the present invention. Obtained.
The thickness of the adhesive layer formed by the two-component curable urethane adhesive was 3.0 μm.
Also, the ratio of polyethylene in the laminate thus obtained was 93% by mass.

<Example 4-2>
In Example 4-1, the image forming surface of the substrate A and the deposition surface of the intermediate layer A were adhered with a two-component curing adhesive containing an isocyanate compound and a phosphoric acid-modified compound (manufactured by DIC Corporation, PASLIM A laminate of the present invention was produced in the same manner as in Example 4-1, except that VM001/VM102CP) was used.

<Comparative Example 4-1>
The base material a was prepared.

An image was formed on one surface of the base material a by gravure printing using an oil-based gravure ink (manufactured by DIC Graphics, trade name: Finart).

A stretched polyethylene film a having a thickness of 20 μm was obtained by forming a film from the medium-density polyethylene by an inflation molding method. Next, on one surface of the stretched polyethylene film a, a 20 nm-thick aluminum deposition film was formed by PVD to obtain an intermediate layer a.

The image forming surface of the base material a was laminated on the deposition surface of the intermediate layer a via the two-liquid curing urethane adhesive. The thickness of the adhesive layer formed by the two-component curable urethane adhesive was 3.0 μm.

A heat seal layer A is prepared, and a layer made of this linear low-density polyethylene A is laminated on the non-vapor-deposited surface of the intermediate layer a via the two-liquid curing urethane adhesive to obtain a laminate. rice field.
The thickness of the adhesive layer formed by the two-component curable urethane adhesive was 3.0 μm.
Also, the ratio of polyethylene in the laminate thus obtained was 93% by mass.

<Comparative Example 4-2>
A laminate was prepared in the same manner as in Example 4-1, except that the stretched polyethylene films of the substrate A and the intermediate layer A were changed to a 12 μm-thick biaxially stretched polyester film (Toyobo Co., Ltd. trade name: E5100). Obtained. The proportion of polyethylene in the laminate thus obtained was 62% by mass.

<Recyclability evaluation>
The recyclability of the laminates obtained in the above examples and comparative examples was evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 1.
(Evaluation criteria)
○: The content of polyethylene in the laminate was 90% by mass or more.
x: The content of polyethylene in the laminate was less than 90% by mass.

<Heat resistance evaluation>
Examples 1-1 and Comparative Examples 1-1 to 1-2, Examples 3-1 to 3-2 and Comparative Examples 3-1 to 3-2 and Examples 4-1 to 4-2 and Comparative Example 4 Two test pieces each having a length of 80 mm and a width of 80 mm were produced from each of the laminates obtained in 1 to 4-2.
Two test pieces were superimposed so that the heat-seal layers faced each other, and three sides were heat-sealed at 140° C. to prepare a packaging bag.
Two test pieces each having a length of 110 mm and a width of 150 mm were prepared from the laminates obtained in Example 2-1 and Comparative Examples 2-1 and 2-2.
Two test pieces were superimposed so that the heat-seal layers faced each other, and two sides were heat-sealed at 140° C. to form a tubular body.
Next, from the laminates obtained in Example 2-1 and Comparative Examples 2-1 and 2-2, one test piece having a length of 110 mm and a width of 150 mm was prepared, and the heat seal layer was placed on the outside. Then, the pouch was folded into a V shape and heat-sealed with the tubular body at 140° C. to form a bottom and a stand pouch.
The produced packaging materials were visually observed and evaluated based on the following evaluation criteria. The evaluation results are summarized in Tables 1-4.
(Evaluation criteria)
◯: No wrinkles occurred on the surface of the packaging material, and no adhesion to the heat seal bar was observed.
x: Wrinkles occurred on the surface of the packaging material, and adhesion to the heat seal bar was observed, and the bag could not be made.

<Printability evaluation>
The images formed on the substrates included in the laminates produced in the above examples and comparative examples were visually observed and evaluated based on the following evaluation criteria. The evaluation results are summarized in Tables 1-4.
(Evaluation criteria)
◯: Dimensional stability during printing was good, and a good image free from rubbing and bleeding could be formed.
x: Expansion and contraction of the film occurred during printing, and rubbing and blurring occurred in the formed image.

<Rigidity evaluation>
The laminates produced in the above Examples and Comparative Examples were used as test pieces having a width of 10 mm, and the stiffness thereof was measured using a loop stiffness measurement tester (manufactured by Toyo Seiki Seisakusho, trade name: Loop Stiffness Tester). In addition, the length of the loop was set to 60 mm. The measurement results are summarized in Tables 1-4.

<Strength test>
The laminates produced in the above examples and comparative examples were measured for strength when a needle with a diameter of 0.5 mm was pierced by a tensile tester (trade name: RTC-1310A manufactured by Orientec). The puncture speed was set to 50 mm/min. The measurement results are summarized in Tables 1-4.

<Bending load resistance test>
First, the oxygen Permeability and water vapor transmission rates were measured.
For the measurement of oxygen permeability, OXTRAN2/20 manufactured by MOCON is used under the conditions of 23°C and 90% RHn. were measured under the conditions of
Furthermore, regarding the laminates obtained in Examples 3-1 to 3-2 and Comparative Examples 3-1 to 3-2 and Examples 4-1 to 4-2 and Comparative Examples 4-1 to 4-2, Using a gelbo flextator (manufactured by Tester Sangyo Co., Ltd., trade name: BE1006BE), a bending load (stroke: 155 mm, bending motion: 440°) was applied five times according to ASTM F392.
After bending load, the oxygen permeability and water vapor permeability of the laminate were measured.
Tables 3 and 4 show the oxygen permeability and water vapor permeability of the laminate before and after the bending load resistance test.

10: Laminate, 11: Substrate, 12: Heat seal layer, 13: High density polyethylene layer, 14: Medium density polyethylene layer, 15: Low density polyethylene layer, linear low density polyethylene layer or ultra low density polyethylene layer , 16: Medium density polyethylene layer, 17: High density polyethylene layer, 18: Deposited film, 19: Adhesive layer, 20: Stretched polyethylene film, 21: Intermediate layer, 30: Packaging bag, 40: Stand pouch, 41: Body , 42: bottom

Claims (11)

A laminate comprising a substrate and a heat seal layer,
Both the base material and the heat seal layer are made of polyethylene, and the content of polyethylene in the entire laminate is 90% by mass or more,
A printing process is applied to the surface of the base material,
The substrate is made of a coextruded stretched film,
The coextruded stretched film is
a layer comprising high density polyethylene;
a layer comprising medium density polyethylene;
a layer comprising low density polyethylene, a layer comprising linear low density polyethylene or a layer comprising ultra-low density polyethylene;
a layer comprising medium density polyethylene;
a layer comprising high density polyethylene;
A laminate, comprising: The laminate according to claim 1, comprising a vapor-deposited film between the substrate and the heat seal layer. An adhesive layer is provided between the base material and the deposited film,
The vapor deposited film is an aluminum vapor deposited film,
3. The laminate according to claim 2, wherein the adhesive layer is composed of a cured resin composition containing a polyester polyol, an isocyanate compound, and a phosphoric acid-modified compound. An intermediate layer is further provided between the base material and the heat seal layer,
The laminate according to any one of claims 1 to 3, wherein the intermediate layer is made of a stretched polyethylene film having a deposited film on one side. 5. The laminate of claim 4, comprising adhesive layers between the substrate and the intermediate layer and between the intermediate layer and the heat seal layer. The vapor deposited film is an aluminum vapor deposited film,
6. The laminate according to claim 5, wherein the adhesive layer adjacent to the vapor-deposited film is composed of a cured resin composition containing a polyester polyol, an isocyanate compound, and a phosphoric acid-modified compound. The laminate according to any one of claims 1 to 5, wherein the substrate is produced by an inflation method. The laminate according to any one of claims 1 to 7, which is used as a packaging material. A packaging material produced using the laminate according to any one of claims 1 to 8. A packaging bag,
Produced using the laminate according to any one of claims 1 to 8,
A packaging bag, wherein the heat seal layer has a thickness of 20 μm or more and 60 μm or less. It is a standing pouch,
Produced using the laminate according to any one of claims 1 to 8,
A stand-up pouch, wherein the heat seal layer has a thickness of 50 μm or more and 200 μm or less.

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