JP2020055156A - Laminate, packaging material, packaging bag and stand pouch - Google Patents

Abstract

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

Description

  The present invention relates to a laminate, a packaging material formed from the laminate, a packaging bag, and a stand pouch.

  Conventionally, packaging materials and the like have been manufactured using a resin film made of a resin material. For example, a resin film composed of polyethylene has moderate flexibility and transparency, and is excellent in heat sealability, and thus is widely used as a packaging material.

  Usually, a resin film composed of polyethylene cannot be used as a base material because it is inferior in strength and heat resistance, and is used by being bonded to a resin film composed of polyester, polyamide, or the like. Therefore, an ordinary packaging material or the like is composed of a laminated film in which a base material and a heat seal layer are made of different types of resin materials (for example, Patent Document 1).

  In recent years, with the increasing demand for building a recycling-based society, packaging materials having high recyclability have been demanded. However, the conventional package is made of a different kind of resin material as described above, and it is difficult to separate each resin material.

JP 2009-202519 A

  The present inventors can use polyethylene which has been conventionally used as a heat seal layer as a base material by forming a stretched film, and use the base material laminated with a heat seal layer made of polyethylene. By doing so, it has been found that a packaging material having sufficient strength and heat resistance and which can be recycled can be produced.

The present invention has been made in view of the above findings, and a problem to be solved is to provide a packaging material having sufficient strength and heat resistance applicable as a packaging material and the like, and also having excellent recyclability. It is to provide a laminate that can be used.
Another object of the present invention is to provide a packaging material composed of the laminate.
Another object of the present invention is to provide a packaging bag made from the laminate.
A further object of the present invention is to provide a stand pouch made from the laminate.

The laminate of the present invention is a laminate comprising a substrate and a heat seal layer,
Both the base material and the heat seal layer are made of polyethylene,
Base material, high-density polyethylene layer, medium-density polyethylene layer, low-density polyethylene layer, linear low-density polyethylene layer or ultra-low-density polyethylene layer, and medium-density polyethylene layer,
It comprises a high-density polyethylene layer and a five-layer co-stretched film.

  In one embodiment of the present invention, the laminate includes a deposition film between the base material and the heat seal layer.

In one embodiment of the present invention, the laminate includes a substrate and an adhesive layer between the deposited film,
The deposited film is an aluminum deposited film,
The adhesive layer is constituted by 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 laminate further includes an intermediate layer between the base material and the heat seal layer, and the intermediate layer is formed of a stretched polyethylene film having a vapor-deposited film on one surface.

  In one embodiment of the present invention, the laminate includes an adhesive layer between the base material 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,
The adhesive layer adjacent to the deposited film is constituted by 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 substrate is manufactured by an 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 present invention, the laminate is used for packaging materials.

  The packaging material of the present invention is characterized by being produced using the above-mentioned laminate.

The packaging bag of the present invention is produced using the above laminate,
The thickness of the heat seal layer is from 20 μm to 60 μm.

The stand pouch of the present invention is produced using the above-mentioned 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, it has the intensity | strength and heat resistance as a packaging material, and can provide the laminated body which can implement | achieve the packaging material excellent also in recyclability.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional schematic which shows one Embodiment of the laminated body of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional schematic which shows one Embodiment of the laminated body of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional schematic which shows one Embodiment of the laminated body of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional schematic which shows one Embodiment of the laminated body of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional schematic which shows one Embodiment of the laminated body of this invention. It is a perspective view showing one Embodiment of the packaging material produced using the laminated body of this invention. 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 base material 11 includes 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. And a layer 17.

  Further, in one embodiment of the present invention, as shown in FIG. 2, the laminate 10 can include a vapor deposition film 18 between the base material 11 and the heat seal layer 12.

  Further, in one embodiment of the present invention, as shown in FIG. 3, the laminate 10 can include an adhesive layer 19 between the base material 11 and the heat seal layer 12 or the vapor deposition film 18.

  Further, in one embodiment of the present invention, as shown in FIG. 4, the laminate 10 includes an intermediate layer 21 including a vapor-deposited film 18 and a stretched polyethylene film 20 between the base material 11 and the heat seal layer 12. be able to.

  Furthermore, in one embodiment of the present invention, as shown in FIG. 5, the laminate 10 includes an adhesive layer 19 between the base material 11 and the intermediate layer 21 and between the intermediate layer 21 and the heat seal layer 12. Can be prepared.

In the laminate of the present invention, the content of polyethylene 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.
In addition, the content of polyethylene in the laminate means the ratio of the content of polyethylene to the sum of the content of the resin material in each layer constituting the laminate.

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

<Substrate>
The substrate 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, the recyclability of the laminate can be improved.

As the base material, a stretched film made of polyethylene is used, whereby the heat resistance and strength of the laminate can be improved. In addition, the suitability for printing on 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 machine direction (MD) of the stretched 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 film to 2 times or more, the strength and heat resistance of the laminate of the present invention can be improved. Further, the suitability for printing on the base material can be improved. Further, since the transparency of the base material can be improved, when an image is formed on the surface of the base material on the heat seal layer side, the visibility 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 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 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 film to 2 times or more, the strength and heat resistance of the laminate of the present invention can be improved. Further, the suitability for printing on the base material can be improved. Further, since the transparency of the base material can be improved, when an image is formed on the surface of the base material on the heat seal layer side, the visibility 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 is preferably 10 times or less from the viewpoint of the breaking limit of the stretched film.

The haze value of the stretched film is preferably 30% or less, more preferably 20% or less. Thereby, the transparency of the stretched film can be improved.
In the present invention, the haze value of the stretched film is measured according to JIS K7105.

The substrate may have an image formed on its surface.
Since the contact with the outside air can be prevented and the deterioration with time can be prevented, 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 includes characters, patterns, symbols, combinations thereof, and the like.
The image formation on the base material is preferably performed using a biomass-derived ink, whereby a packaging material with less environmental load can be produced using the 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 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 simplicity, the paragraph Has a configuration comprising a five-layer co-stretched film of a base material 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. Further, the strength and heat resistance of the laminate of the present invention can be improved. Further, it is possible to prevent the occurrence of curl in the substrate.
Further, the film production efficiency can be improved as described below.
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 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.
Further, the thickness of the high-density polyethylene layer is preferably the same as or larger than the thickness of the intermediate layer of the base material.
The ratio of the thickness of the high-density polyethylene layer to the thickness of the intermediate substrate 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 intermediate substrate layer to 1 / 0.25 or more. In addition, by setting the ratio of the thickness of the high-density polyethylene layer to the thickness of the base material 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 base material 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 base material 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. By setting the thickness of the base material intermediate layer to 10 μm or less, the processability of the laminate of the present invention can be further improved.

In one embodiment, the substrate having such a configuration can be produced by, for example, 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 in a tube shape, and then opposed. The low-density polyethylene layer, the linear low-density polyethylene layer, or the ultra-low-density polyethylene layer can be produced by press-bonding these with a rubber roll or the like.
By manufacturing by such a method, the number of defective products in manufacturing can be significantly reduced, and ultimately, the production efficiency can be improved.
Further, in an inflation film forming machine, stretching can be performed at the same time, whereby the production efficiency can be further improved.

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

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

  The single-site catalyst is a catalyst capable of forming a uniform active species, and is usually adjusted by contacting a metallocene-based transition metal compound or a non-metallocene-based transition metal compound with an activating cocatalyst. . Single-site catalysts are preferable because they have a more uniform active site structure than multi-site catalysts and can polymerize a polymer having a high molecular weight and a highly uniform structure. It is particularly preferable to use a metallocene catalyst as the single-site 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 co-catalyst, an organic metal compound as required, and each catalyst component of a carrier. is there.

  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. . Examples of the substituted cyclopentadienyl group include a hydrocarbon group having 1 to 30 carbon atoms, a silyl group, a silyl-substituted alkyl group, a silyl-substituted aryl group, a cyano group, a cyanoalkyl group, a cyanoaryl group, a halogen group, a haloalkyl group, and a halosilyl group. 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, and include an indenyl ring, a fluorenyl ring, an azulenyl ring, a hydrogenated product thereof, and the like. It may be formed. The ring formed by bonding the substituents to each other may further have a substituent to 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, and zirconium and hafnium are particularly preferred. The transition metal compound usually has two ligands each having a cyclopentadienyl skeleton, and it is preferable that each ligand having a cyclopentadienyl skeleton be bonded to each other by a crosslinking group. Examples of the cross-linking group include a substituted silylene group such as an alkylene group having 1 to 4 carbon atoms, a silylene group, a dialkylsilylene group, and a diarylsilylene group, and a substituted germylene group such as a dialkylgermylene group and a diarylgermylene group. Preferably, it is a substituted silylene group. As the transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, one kind or a mixture of two or more kinds can be used as a catalyst component.

  The co-catalyst refers to a co-catalyst capable of effectively using the above-mentioned transition metal compound of Group IV of the periodic table as a polymerization catalyst or equalizing ionic charges in a catalytically activated state. As the co-catalyst, benzene-soluble aluminoxane or benzene-insoluble organic aluminum oxy compound of an organic aluminum oxy compound, an ion-exchanged layered silicate, a boron compound, a cation containing or not containing an active hydrogen group and a non-coordinating anion are used. Lanthanide salts such as lanthanum oxide, tin oxide, and a phenoxy compound containing a fluoro group.

The transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton may be used by being supported on a carrier of an inorganic or organic compound. As the carrier, a porous oxide of an inorganic or organic compound is preferable, and specifically, an ion-exchange layered silicate such as montmorillonite, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _{2 and the} like, or a mixture thereof. Further, examples of the organometallic compound used as necessary include an organoaluminum compound, an organomagnesium compound, and an organozinc compound. Of these, organoaluminum is preferably used.

  Further, a copolymer of ethylene and another monomer may be used as long as the properties of the present invention are not impaired. Examples of the ethylene copolymer include a copolymer composed of ethylene and an α-olefin having 3 to 20 carbon atoms. Examples of the α-olefin 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, a copolymer with vinyl acetate or an acrylate ester may be used as long as the object of the present invention is not impaired.

  In the present invention, biomass-derived ethylene may be used as a raw material for obtaining the above-mentioned polyethylene or the like, instead of ethylene obtained from a fossil fuel. Since such biomass-derived polyethylene is a carb-neutral material, it can be used as a packaging material with even less environmental load. Such biomass-derived polyethylene can be produced, for example, by a method described in JP-A-2013-177531. Alternatively, commercially available biomass-derived polyethylene (for example, Green PE commercially available from Braskem) may be used.

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

  The base material may contain additives within a range that does not impair the properties of the present invention. For example, a crosslinking agent, an antioxidant, an anti-blocking agent, a slip (slip) agent, an ultraviolet absorber, a light stabilizer, a filler Agents, reinforcing agents, antistatic agents, pigments and modifying resins.

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 10 μm or more and 50 μm or less, and more preferably 12 μm or more and 30 μm or less.
By setting the thickness of the 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 prepared by forming a film of polyethylene by a T-die method or an inflation method, forming a film, and then stretching the film.

When a substrate is produced by the T-die method, the MFR of the polyethylene constituting each layer is preferably 3 g / 10 min or more and 20 g / 10 min or less.
By setting the MFR of the 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 base material is manufactured by the inflation method, the MFR of the 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 the 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-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.

<Heat seal layer>
The heat seal layer provided in the laminate of the present invention is characterized in that it is made of polyethylene, similarly to the above-mentioned base material. With such a configuration, a recyclable packaging material having sufficient strength and heat resistance as a packaging material can be obtained.
However, the stretched polyethylene film is formed by an unstretched polyethylene resin film or by melt extrusion of polyethylene.

The polyethylene constituting the heat seal layer is preferably a low density polyethylene (LDPE), a linear low density polyethylene (LLDPE) and a super density polyethylene (VLDPE) from the viewpoint of heat sealability.
A copolymer of ethylene and another monomer can be used as long as the properties of the present invention are not impaired.
In addition, from the viewpoint of environmental load, biomass-derived polyethylene or recycled polyethylene is preferable.

  The heat seal 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 multilayer structure, and includes, 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 / a layer containing at least one of medium-density polyethylene and high-density polyethylene / low-density polyethylene, linear It can be constituted by a layer containing at least one of a low-density polyethylene and an ultra-low-density polyethylene.
By adopting such a configuration, it is possible to further improve the suitability and strength of the laminate of the present invention while maintaining the heat sealing property.

In another embodiment, the heat sealing layer is a layer containing at least one of low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene / a layer containing biomass-derived polyethylene / low-density polyethylene, It can be configured to include a layer containing at least one of chain low-density polyethylene and ultra-low-density polyethylene.
With such a configuration, the environmental load of a packaging material or the like manufactured 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 by the laminate of the present invention.
For example, in the case of manufacturing a packaging bag 20 as shown in FIG. 6 in which contents of 1 g or more and 200 g or less are filled, 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 contents from leaking due to breakage of the heat seal layer. Further, by setting the heat seal layer to 60 μm or less, the processability of the laminate of the present invention can be improved.

Further, for example, in the case of manufacturing a stand pouch 30 as shown in FIG. 7 that fills a content 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 contents 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 processability of the laminate of the present invention can be improved.
The hatched portions in FIGS. 6 and 7 are heat-sealed portions.

<Evaporated film>
The laminate of the present invention can include a deposited film between the base material 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.

  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.
When the thickness of the deposited film is 1 nm or more, the oxygen barrier property and the water vapor barrier property of the laminate 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 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 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 vapor 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>
In one embodiment, the laminate of the present invention can include an adhesive layer between any layers. Thereby, the adhesion between these layers can be improved.

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.

In the case where the adhesive layer is provided so as to be adjacent to the vapor-deposited film that is the aluminum vapor-deposited film, the adhesive layer is preferably made of a cured product of a resin composition containing a polyester polyol, an isocyanate compound, and a phosphoric acid-modified compound. .
With the adhesive layer having such a configuration, the oxygen barrier property and the water vapor barrier property of the laminate of the present invention can be further improved.
In addition, when a laminate provided with 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 the resin composition 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、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 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), R1, R2 and R3 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 R1, R2 and R3 represents a group represented by the general formula (2).

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

  Further, a compound in which any one of R1, R2, and R3 is a group represented by the general formula (2), and a compound in which any two of R1, R2, and R3 are a group represented by the general formula (2) And a compound in which all of R1, R2, and R3 are groups represented by the general formula (2) may be a mixture of two or more compounds.

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、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 the general formula (3), R1, R2, and R3 each independently represent "-(CH2) n1-OH (where n1 represents an integer of 2 to 4)" or a structure of the general formula (4). Represent.

  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 R1, R2 and R3 is a group represented by the general formula (4).

  In the general formula (3), the alkylene group represented by-(CH2) n1- may be linear or branched. 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 R1, R2, and R3 is a group represented by the general formula (4). Among them, it is preferable that all of R1, R2, and R3 are groups represented by the 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 a group represented by general formula (4) And a compound in which all of R1, R2, and R3 are groups represented by the general formula (4) may be a mixture of two or more of them.

  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 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, 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.

  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 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 low-molecular-weight active hydrogen compounds 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、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。 The phosphoric acid-modified compound is, for example, a compound represented by the following general formula (5) or (6).

In the general formula (5), R1, R2 and R3 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 (meth) acryloyloxy group. It is 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 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 to 4 carbon atoms having a (meth) acryloyloxy group. 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 Examples thereof include ethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, and polyoxyethylene alkyl ether phosphoric acid. 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 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. Further, the bending load resistance of the laminate 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. Further, the bending load resistance of the laminate 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. 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 so as to be adjacent to an aluminum vapor-deposited film, the 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 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.

<Intermediate layer>
In one embodiment, the laminate of the present invention can include an intermediate layer formed of a stretched polyethylene film having a vapor-deposited film on one surface, between the base material and the heat seal layer. Thereby, the strength, the oxygen barrier property and the water vapor barrier property of the laminate can be further improved.

(Evaporated film)
The intermediate layer includes a vapor-deposited film, whereby the gas barrier properties, particularly, the oxygen barrier properties and the water vapor barrier properties can be 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.
When the thickness of the deposited film is 1 nm or more, the oxygen barrier property and the water vapor barrier property of the laminate 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 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 laminate of the present invention. In the present invention, the OD value can be measured according to JIS-K-7361.

  The deposition film can be formed by the above method.

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

(Stretched polyethylene film)
The stretched polyethylene film constituting the intermediate layer is characterized by being composed of polyethylene as in the case of the above-mentioned base material and heat seal layer. With such a configuration, a recyclable packaging material can be obtained while maintaining the strength and heat resistance of the packaging material.

  As the stretched polyethylene film, a stretched film made of polyethylene is used in order to further improve the 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 machine direction (MD) of the stretched 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 film 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 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 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 film 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 is preferably 10 times or less from the viewpoint of the breaking limit of the stretched film.

As the polyethylene contained in the stretched polyethylene film, among the above, high-density polyethylene and medium-density polyethylene are preferable from the viewpoint of strength and heat resistance and proper stretching of the film, and medium-density polyethylene is more preferable from the viewpoint of stretchability.
Further, the intermediate layer may have a multilayer structure as described above, similarly to the base material.

  The stretched polyethylene film may contain the above-mentioned 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. Further, 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.

  As the stretched polyethylene film, a film produced by the above-mentioned T-die method or inflation method may be used, or a commercially available film may be used.

<Application>
The laminate of the present invention can be particularly suitably used 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 41 and a bottom 42 as shown in FIG. In the stand pouch, even if only the trunk is formed of the laminate, only the bottom is formed of the laminate, or both the trunk and the bottom are formed of the laminate. Good.

The packaging bag can be manufactured by folding in two so that the heat-seal layer of the above-mentioned laminated body is inside, and lapping, and heat-sealing the end.
Further, the packaging bag can also be manufactured by stacking two laminates such that the heat seal layers face each other and heat sealing the ends thereof.

  The stand pouch forms a body by heat-sealing the laminate so that the heat-seal layer of the laminate is on the inside, and then forms the body with the heat-seal layer on the inside so that the heat-seal layer is on the inside. It can be manufactured by folding it into a letter shape, sandwiching it from one end of the body, and heat-sealing to form the bottom.

  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.

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.

  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 Dow Chemical Co., trade name: Elite5960), medium-density polyethylene (density: 0.940 g / cm ³ , melting point) 126 ° C., MFR: 0.85 g / 10 min, manufactured by Dow chemical, trade name: Elite5940) and ultra-low density polyethylene (density: 0.870 g / cm ³ , melting point 55 ° C., MFR: 1.0 g / 10 min, Dow chemical) Company, trade name: Affinity EG8100G) 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 inflation molding. After extruding as a tubular film The inner low-density polyethylene layers are pressed together with a rubber roll, and a high-density polyethylene layer (12.5 μm), a medium-density polyethylene layer (43.75 μm), an ultra-low-density polyethylene layer (12.5 μm), and a medium density A 125 μm thick polyethylene film with a polyethylene layer (43.75 μm) and a high density polyethylene layer (12.5 μm) was obtained.
This polyethylene film was stretched in the longitudinal direction (MD) at a stretch ratio of 5 times to obtain a base material A having a thickness of 25 μm.
When the haze value of the substrate A was measured in accordance with JIS K 7105, the haze value was 6.2%.

  An image was formed on one surface of the substrate A by a gravure printing method using an oil-based gravure ink (manufactured by DIC Graphics Co., Ltd., 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), and linear low-density polyethylene A 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%, trade name: SLL118, manufactured by Braskem) And low-density linear polyethylene B (density: 0.913 g / cm ³ , melting point: 116 ° C., MFR: 2.0 g / 10 minutes, product name: SP1520, manufactured by Prime Polymer Co., Ltd.) by inflation molding. A layer made of linear low-density polyethylene A having a thickness of 17 μm, a linear low-density polyethylene A having a thickness of 16 μm, and And a layer made of linear low-density polyethylene B having a thickness of 17 μm, and a heat-seal layer A having a thickness of 50 μm was prepared.

A two-part curable urethane adhesive (manufactured by Rock Paint Co., Ltd., trade name: RU- 77T / H-7) to obtain a laminate of the present invention.
The thickness of the adhesive layer formed by the two-component curable urethane-based adhesive was 3.0 μm.
The proportion 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 as a tubular film having a high-density polyethylene layer, a medium-density polyethylene layer and an ultra-low-density polyethylene layer by an inflation molding method. The inner ultra-low-density polyethylene layers are pressed together with a rubber roll, and 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 comprising a layer (8.75 μm) and a high density polyethylene layer (2.5 μm) was obtained.
When the haze value of the substrate a was measured in accordance with JIS K 7105, the haze value was 21.3%.

  An image was formed on one surface of the substrate a by a gravure printing method using the above oil-based gravure ink.

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 A were laminated via the two-component curable urethane-based adhesive to obtain a laminate. .
The thickness of the adhesive layer formed by the two-component curable urethane-based adhesive was 3.0 μm.
The proportion 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 base material A was changed to a 12-μm-thick biaxially stretched PET film (trade name: E5100, manufactured by Toyobo Co., Ltd.).
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 substrate A by a gravure printing method using an oil-based gravure ink (manufactured by DIC Graphics Co., Ltd., trade name: Finart).

  Inflation molding of the linear low-density polyethylene A, a 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 having a thickness of 34 μm, a layer composed of linear low-density polyethylene A having a thickness of 32 μm and polyethylene derived from biomass, and a linear layer having a thickness of 34 μm. A heat seal layer B having a thickness of 100 μm and including a layer made of low density polyethylene B was prepared.

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-based adhesive, and the laminate of the present invention is provided. I got
The thickness of the adhesive layer formed by the two-component curable urethane-based adhesive was 3.0 μm.
The proportion of polyethylene in the laminate thus obtained was 97% by mass.

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

  An image was formed on one surface of the substrate a by a gravure printing method using the above oil-based gravure ink.

The image forming surface of the substrate a and the layer made of the linear low-density polyethylene A of the heat seal layer B were laminated via the two-component curable urethane-based adhesive to obtain a laminate. .
The thickness of the adhesive layer formed by the two-component curable urethane-based adhesive was 3.0 μm.
The proportion 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.
The proportion of polyethylene in the thus obtained laminate was 86% by mass.

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

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

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

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-based adhesive to obtain a laminate of the present invention.
The thickness of the adhesive layer formed by the two-component curable urethane-based adhesive was 3.0 μm.
The proportion of polyethylene in the laminate thus obtained was 95% by mass.

<Example 3-2>
In Example 3-1, the adhesion between the image forming surface of the substrate A and the vapor-deposited surface of the heat seal layer A was determined by using a two-component curable 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 the process was performed using PASLIM VM001 / VM102CP).

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

  An image was formed on one surface of the substrate a by a gravure printing method using the above oil-based gravure ink.

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

The image forming surface of the substrate a and the vapor-deposited surface of the heat seal layer A were laminated via the two-component curable urethane-based adhesive to obtain a laminate.
The thickness of the adhesive layer formed by the two-component curable urethane-based adhesive was 3.0 μm.
The proportion 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.
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 substrate A by a gravure printing method using an oil-based gravure ink (manufactured by DIC Graphics Co., Ltd., 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 stretch ratio of 5 to obtain a stretched polyethylene film A having a thickness of 20 μm. Was. Next, a 20 nm-thick aluminum vapor-deposited film was formed on one surface of the stretched polyethylene film A by a PVD method to obtain an intermediate layer A.

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

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

<Example 4-2>
In Example 4-1, the adhesion between the image forming surface of the substrate A and the deposition surface of the intermediate layer A was determined by using a two-part curable adhesive containing an isocyanate compound and a phosphoric acid-modified compound (PASLIM, manufactured by DIC Corporation). VM001 / VM102CP), and a laminate of the present invention was produced in the same manner as in Example 4-1.

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

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

  The medium-density polyethylene was formed into a film by an inflation molding method to obtain a stretched polyethylene film a having a thickness of 20 μm. Next, a 20 nm-thick aluminum vapor-deposited film was formed on one surface of the stretched polyethylene film a by a PVD method to obtain an intermediate layer a.

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

A heat-sealing layer A is prepared, and a layer made of the linear low-density polyethylene A is laminated on the non-deposited surface of the intermediate layer a via the two-part curable urethane-based adhesive to obtain a laminate. Was.
The thickness of the adhesive layer formed by the two-component curable urethane-based adhesive was 3.0 μm.
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 film of the base material A and the intermediate layer A was changed to a biaxially stretched polyester film having a thickness of 12 μm (trade name: Toyobo Co., Ltd .: E5100). Obtained. The proportion of polyethylene in the thus obtained laminate was 62% by mass.

<Evaluation of recyclability>
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>
Example 1-1 and Comparative Examples 1-1 and 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 From the laminate obtained in -1 to 4-2, 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 140 ° C. to produce a packaging bag.
From the laminates obtained in Example 2-1 and Comparative Examples 2-1 and 2-2, two test pieces each having a length of 110 mm and a width of 150 mm were produced.
The two test pieces were overlapped so that the heat seal layers faced each other, and heat sealed at 140 ° C. on two sides to form a cylindrical body.
Next, one test piece having a length of 110 mm and a width of 150 mm was prepared from the laminate obtained in Example 2-1 and Comparative Examples 2-1 and 2-2, and the heat seal layer was on the outside. Then, it was folded into a V-shape and heat-sealed with the cylindrical body at 140 ° C. to form a bottom and a stand pouch.
The prepared packaging material was visually observed and evaluated based on the following evaluation criteria. The evaluation results are summarized in Tables 1 to 4.
(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.
X: Wrinkles and the like were generated 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 base material of the laminates prepared 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 to 4.
(Evaluation criteria)
：: Good dimensional stability at the time of printing, and a good image free from rubbing, bleeding, etc. could be formed.
X: The film was stretched and shrunk during printing, and the formed image was rubbed and blurred.

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

<Strength test>
The strength when the needle having a diameter of 0.5 mm was pierced by the tensile tester (trade name: RTC-1310A, manufactured by Orientec Co., Ltd.) was measured for the laminates produced in the above Examples and Comparative Examples. The piercing speed was 50 mm / min. The measurement results are summarized in Tables 1 to 4.

<Bending load resistance test>
First, the oxygen of the laminate obtained in the above 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. The permeability and water vapor permeability were measured.
OXTRAN 2/20 manufactured by MOCON is used for the measurement of oxygen permeability, and PERMATRAN 3/31 manufactured by MOCON is used for the measurement of water vapor permeability under the conditions of 23 ° C. and 90% RHn. Under the conditions described above, the measurement was performed.
Furthermore, for 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, A bending load (stroke: 155 mm, bending operation: 440 °) was applied five times according to ASTM F392 using a gelbo flex tester (Tester Sangyo Co., Ltd., trade name: BE1006BE).
After the bending load, the oxygen permeability and the water vapor permeability of the laminate were measured.
Tables 3 and 4 show the oxygen permeability and the water vapor permeability of the laminate before and after the bending load 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: vapor-deposited film, 19: adhesive layer, 20: stretched polyethylene film, 21: intermediate layer, 30: packaging bag, 40: stand pouch, 41: trunk , 42: bottom

Claims (12)

A laminate comprising a base material and a heat seal layer,
Both the base material and the heat seal layer are made of polyethylene,
The substrate,
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,
A medium density polyethylene layer,
A high-density polyethylene layer,
A laminate comprising a five-layer co-stretched film of the above.   The laminate according to claim 1, further comprising a deposition film between the base material and the heat seal layer. The substrate, comprising an adhesive layer between the deposited film,
The deposited film is an aluminum deposited film,
The laminate according to claim 2, wherein 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. Between the base material and the heat seal layer, further comprising an intermediate layer,
The laminate according to any one of claims 1 to 3, wherein the intermediate layer is formed of a stretched polyethylene film having a vapor-deposited film on one surface.   The laminate according to claim 4, further comprising an adhesive layer between the base material and the intermediate layer and between the intermediate layer and the heat seal layer. The deposited film is an aluminum deposited film,
The laminate according to claim 5, wherein the adhesive layer adjacent to the vapor-deposited film is formed of a cured product of a 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 base material is produced by an inflation method.   The laminate according to any one of claims 1 to 7, wherein the content of the polyethylene in the entire laminate is 90% by mass or more.   The laminate according to any one of claims 1 to 8, which is used for packaging materials.   A packaging material produced using the laminate according to any one of claims 1 to 9. A packaging bag,
It is produced using the laminate according to any one of claims 1 to 9,
A packaging bag, wherein the thickness of the heat seal layer is 20 μm or more and 60 μm or less. A stand pouch,
It is produced using the laminate according to any one of claims 1 to 9,
A stand pouch, wherein the thickness of the heat seal layer is 50 μm or more and 200 μm or less.

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