WO2020067426A1

WO2020067426A1 - Laminate, packaging material, packaging bag, and stand pouch

Info

Publication number: WO2020067426A1
Application number: PCT/JP2019/038156
Authority: WO
Inventors: 山田　憲一; 智裕米本
Original assignee: 大日本印刷株式会社
Priority date: 2018-09-28
Filing date: 2019-09-27
Publication date: 2020-04-02

Abstract

[Problem] To provide a laminate that comprises sufficient strength and heat resistance to serve as a packaging material and makes it possible to realize a packaging material having exceptional recyclability. [Solution] This laminate is characterized in comprising a base material and a heat seal layer, the base material and the heat seal layer being configured from the same material, said material being polyethylene, and the base material being a stretched resin film.

Description

Laminates, packaging materials, packaging bags and stand pouches

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 have been manufactured using a resin film composed 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, resin films composed of polyethylene cannot be used as a base material or an intermediate layer provided for improving strength because resin films having poor strength and heat resistance are used, and resin films composed of polyester, polyamide, etc. For this reason, a usual packaging material is composed of a laminated film made of a resin material different from a base material or an intermediate layer and a heat seal layer (for example, see Patent Document 1). ).

In recent years, with the increasing demand for building a recycling-based society, packaging materials with 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 have made it possible to use polyethylene, which has been conventionally used as a heat seal layer, as a stretched resin film so that it can be used as a base material or an intermediate layer. It has been found that by using a laminate with a seal layer, a recyclable packaging material having sufficient strength and heat resistance 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.

In the first aspect, the laminate of the present invention includes a substrate and a heat seal layer,
The base material and the heat seal layer are made of the same material,
The same material is polyethylene,
The base material is a stretched resin film.

において In one embodiment, the laminate of the present invention includes an adhesive layer between the base material and the heat seal layer.

In one embodiment, in the laminate of the present invention, the heat seal layer includes a vapor-deposited film on a surface on the base material side.

In one embodiment, 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 and an isocyanate compound.

In one embodiment, the laminate of the present invention includes an intermediate layer between the base material and the heat seal layer,
The intermediate layer includes a deposited film and an intermediate layer substrate.

In one embodiment, at least one of the base material and the heat seal layer contains biomass-derived polyethylene as polyethylene.

In one embodiment, the base material is 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, It comprises a five-layer co-stretched film of a polyethylene layer.

In the second aspect, the laminate of the present invention includes a base material, an intermediate layer, and a heat seal layer,
The substrate is composed of polyester,
The intermediate layer and the heat seal layer are made of the same material,
The same material is polyethylene,
The intermediate layer is a stretched resin film,
The thickness of the substrate is smaller than the sum of the thickness of the intermediate layer and the thickness of the heat seal layer.

In one embodiment, at least one of the intermediate layer and the heat seal layer contains biomass-derived polyethylene as polyethylene.

において In one embodiment of the present invention, the laminate is used for packaging materials.

包装 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.

According to the present invention, it is possible to provide a laminate capable of realizing a packaging material having strength and heat resistance as a packaging material and excellent recyclability.

FIG. 1 is a schematic cross-sectional view showing one embodiment of a laminate of the present invention in a first aspect. FIG. 1 is a schematic cross-sectional view showing one embodiment of a laminate of the present invention in a first aspect. FIG. 1 is a schematic cross-sectional view showing one embodiment of a laminate of the present invention in a first aspect. FIG. 1 is a schematic cross-sectional view showing one embodiment of a laminate of the present invention in a first aspect. FIG. 1 is a schematic cross-sectional view showing one embodiment of a laminate of the present invention in a first aspect. It is a cross section schematic diagram showing one embodiment of a layered product of the present invention in a 2nd mode. It is a cross section schematic diagram showing one embodiment of a layered product of the present invention in a 2nd mode. It is a cross section schematic diagram showing one embodiment of a layered product of the present invention in a 2nd mode. 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 in First Embodiment>
The 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.

In addition, in one embodiment of the present invention, as shown in FIG. 2, the laminate 10 can include a deposition film 13 between the base material 11 and the heat seal layer 12.

In one embodiment of the present invention, as shown in FIG. 3, the laminate 10 may include an adhesive layer 14 between the base material 11 and the heat seal layer 12 or the vapor-deposited film 13.

Further, in one embodiment of the present invention, as shown in FIG. 4, the laminate 10 includes an intermediate layer 17 including a deposition film 15 and an intermediate layer substrate 16 between the substrate 11 and the heat seal layer 12. Can be prepared.

Further, in one embodiment of the present invention, as shown in FIG. 5, the laminate 10 includes an adhesive layer 18 between the base material 11 and the intermediate layer 17 and between the intermediate layer 17 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 resin film composed 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 resin film may be a uniaxially stretched resin film or a biaxially stretched resin film.

The stretch ratio in the machine direction (MD) of the stretched resin film is preferably 2 times or more and 10 times or less, and more preferably 3 times or more and 7 times or less.
By setting the stretching ratio in the longitudinal direction (MD) of the stretched resin film to 2 times or more, the strength and heat resistance of the laminate 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 resin film is not particularly limited, but is preferably 10 times or less from the viewpoint of the breaking limit of the stretched resin film.

The stretching ratio in the transverse direction (TD) of the stretched resin film is preferably 2 times or more and 10 times or less, and more preferably 3 times or more and 7 times or less.
By setting the stretching ratio in the transverse direction (TD) of the stretched resin film to 2 times or more, the strength 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 resin film is not particularly limited, but is preferably 10 times or less from the viewpoint of the breaking limit of the stretched resin film.

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

As the polyethylene contained in the base material, high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and very low density polyethylene (VLDPE) are used. be able to.
Here, 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, the density of 0.925 g / cm ³ or more and less than 0.945 g / cm ³ can be used. Polyethylene 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. A 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 ultra-low density polyethylene, a polyethylene having a density of less than 0.900 g / cm ³ can be used.
Among these, high-density polyethylene and medium-density polyethylene are preferred from the viewpoint of printability, strength and heat resistance of the laminate of the present invention, and stretchability of the film, and medium-density polyethylene is more preferred from the viewpoint of stretchability.

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

For example, it has a configuration of a co-pressed film of a high-density polyethylene layer and a medium-density polyethylene layer from the outside.
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.
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 further improved. Further, by setting the ratio of the thickness of the high-density polyethylene layer to the thickness of the medium-density polyethylene layer to 1/1 or less, the stretchability of the resin film can be further improved.

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

Also, for example, from the outside, a high-density polyethylene layer, a medium-density polyethylene layer, and a low-density polyethylene layer, a linear low-density polyethylene layer, or an ultra-low-density polyethylene layer (in this paragraph, for simplicity of description, It is also possible to form a five-layer co-pressed film of a high-density polyethylene layer and a medium-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 base material.
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 the thickness of the low-density polyethylene layer or greater than the thickness of the low-density polyethylene.
The ratio of the thickness of the high-density polyethylene layer to the thickness of the low-density polyethylene 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 low-density polyethylene layer to 1 / 0.25 or more. By setting the ratio of the thickness of the high-density polyethylene layer to the thickness of the low-density polyethylene layer to 1/1 or less, the adhesion between the medium-density polyethylene layers can be 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.

ポリエチレン 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.

遷移 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 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 cocatalyst refers to a cocatalyst capable of effectively using the above-mentioned transition metal compound of Group IV of the periodic table as a polymerization catalyst, or capable of balancing 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.

共 Also, a copolymer of ethylene and another monomer can 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.

Further, in the present invention, it is preferable to use biomass-derived ethylene instead of ethylene obtained from fossil fuel as a raw material for obtaining the high-density polyethylene or the like. 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 as described in JP-A-2013-177531. Alternatively, commercially available biomass-derived polyethylene (for example, Green PE commercially available from Braskem) may be used.

ポリエチレン 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.

The base material may be provided with the following deposited film on its surface.

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 produced by forming a film of polyethylene by a T-die method or an inflation method, producing a film, and then stretching the film.

When the substrate is produced by the T-die method, the MFR of the polyethylene 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 substrate is produced by the inflation method, the MFR of the polyethylene 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.

Note that the substrate is not limited to 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 or the like having sufficient strength and heat resistance can be manufactured.
However, the polyethylene resin layer 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.

(4) The heat seal layer may 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.

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 where a packaging bag 30 as shown in FIG. 9 is 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 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 40 as shown in FIG. 10 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. 9 and 10 are the heat seal 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.

には 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 thermochemical vapor phase growth method, and a photochemical vapor phase growth 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 in 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.

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

<Adhesive layer>
In one embodiment, the laminate of the present invention may include an adhesive layer between the substrate and the heat seal layer or the vapor-deposited film. Thereby, the adhesion between these layers can be improved.
In one embodiment, the laminate may include an adhesive layer between the base material and the intermediate layer described below, and between the intermediate layer and the heat seal layer.

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 an aluminum vapor-deposited film, it is preferable that the adhesive layer be formed of a cured product of a resin composition containing a polyester polyol and an isocyanate 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 and an isocyanate 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.
In particular, 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 Polycarboxylic acids, such as the acidic derivatives, 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.

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).

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

In the general formula (2), 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 Represents an alkylene group having 2 to 6 carbon atoms such as a group and 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 anhydride in which the carboxylic acid is substituted at the ortho position include orthophthalic acid or anhydride, naphthalene 2,3-dicarboxylic acid or anhydride, naphthalene 1,2-dicarboxylic acid or 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. Examples of the substituent include chloro, bromo, methyl, ethyl, i-propyl, hydroxyl, methoxy, ethoxy, phenoxy, methylthio, phenylthio, cyano, nitro, amino, Examples include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group and a naphthyl group.

Also, 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.

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 the 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 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).

において 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.

において 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. Examples of the substituent include chloro, bromo, methyl, ethyl, i-propyl, hydroxyl, methoxy, ethoxy, phenoxy, methylthio, phenylthio, cyano, nitro, amino, Examples include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group and a naphthyl group.
X is preferably a hydroxyl group, a cyano group, a nitro group, an amino group, a phthalimido 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 phthalimido group and A phenyl group is most preferred.

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

において 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.

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

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

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

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

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

The resin composition constituting the cured product can contain a phosphoric acid-modified compound, and 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 (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 -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 , Isopropylisostearoyl diacryl titanate, diisostearoyl ester Renchitaneto, 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 composed of six glucose units, β-cyclodextrin composed of seven glucose units, and γ-cyclodextrin composed 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.

から 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, 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.

Examples of the acetylated cyclodextrin 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.

Examples of the hydroxyalkylated cyclodextrin include, for example, hydroxypropyl-α-cyclodextrin, hydroxypropyl-β-cyclodextrin, hydroxypropyl-γ-cyclodextrin, and the like. 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 including a vapor-deposited film and an intermediate layer substrate between the substrate 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.

The deposited film can be formed by the above method.

(Intermediate layer substrate)
The intermediate layer substrate is made of polyethylene. With such a configuration, a recyclable packaging material having higher strength and heat resistance can be obtained.

延伸 For the intermediate layer base material, use a stretched resin film made of polyethylene to further improve the strength and heat resistance as a packaging material. The stretched resin film may be a uniaxially stretched resin film or a biaxially stretched resin film.

The stretch ratio in the machine direction (MD) of the stretched resin film is preferably 2 times or more and 10 times or less, and more preferably 3 times or more and 7 times or less.
By setting the stretching ratio in the longitudinal direction (MD) of the stretched resin film to 2 times or more, the strength and heat resistance of the laminate 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 resin film is not particularly limited, but is preferably 10 times or less from the viewpoint of the breaking limit of the stretched resin film.

The stretching ratio in the transverse direction (TD) of the stretched resin film is preferably 2 times or more and 10 times or less, and more preferably 3 times or more and 7 times or less.
By setting the stretching ratio in the transverse direction (TD) of the stretched resin film to 2 times or more, the strength 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 resin film is not particularly limited, but is preferably 10 times or less from the viewpoint of the breaking limit of the stretched resin film.

As the polyethylene contained in the intermediate layer base material, 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 proper stretching. .
Further, the intermediate layer base material may have the above-mentioned multilayer structure similarly to the base material.

The intermediate layer base material can contain the above-mentioned additives as long as the properties of the present invention are not impaired.

The thickness of the intermediate layer base material 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 intermediate layer base material 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 intermediate layer substrate to 50 μm or less, the processability of the laminate of the present invention can be improved.

As the intermediate layer substrate, a substrate produced by the T-die method or the inflation method described above or a commercially available substrate may be used.

<Laminate in Second Embodiment>
A laminate according to the present invention will be described with reference to the drawings.
As shown in FIG. 6, the laminate 20 includes a base material 21, an intermediate layer 22, and a heat seal layer 23.

In addition, in one embodiment of the present invention, as shown in FIG. 7, the stacked body 20 may further include a deposition film 24 between the base material 21 and the intermediate layer 22.

Further, in one embodiment of the present invention, as shown in FIG. 8, the laminate 20 is formed between the base 21 or the deposited film 24 and the intermediate layer 22 and between the intermediate layer 22 and the heat seal layer 23. May further include an adhesive layer 25 on at least one of them.

Further, the laminate of the present invention is characterized in that the thickness of the substrate is smaller than the sum of the thickness of the intermediate layer and the thickness of the heat seal layer. This makes it possible to improve the recyclability of packaging materials and the like produced using the laminate of the present invention.
The difference between the thickness of the base material and the sum of the thickness of the intermediate layer and the thickness of the heat seal layer is preferably 40 μm or more, and more preferably 100 μm or more.

In the laminate of the present invention, the content of polyethylene is preferably 80% by mass or more.
By setting the polyethylene content in the entire laminate of the present invention to 80% 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.

<Substrate>
The substrate provided in the laminate of the present invention is characterized in that it is made of polyester. Thereby, the strength and heat resistance of the laminate of the present invention can be improved.

Examples of the polyester include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene isophthalate, polybutylene naphthalate (PBN), polypropylene terephthalate (PPT), and polybutylene naphthalate (PBN). . Among these, polyethylene terephthalate (PET) is preferred from the viewpoint of the strength and heat resistance of the laminate.

A stretched resin film composed of polyester can be used for the substrate, and thereby the heat resistance and strength of the laminate can be improved. In addition, the suitability for printing on the polyethylene resin layer can be improved.
The stretched resin film may be a uniaxially stretched resin film or a biaxially stretched resin film.

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 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 base material to 10 μm or more, the strength and heat resistance 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 recyclability of the laminate of the present invention can be improved.

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

<Intermediate layer>
The intermediate layer included in 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.

For the intermediate layer, a stretched resin 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 intermediate layer can be improved.
The stretched resin film may be a uniaxially stretched resin film or a biaxially stretched resin film.

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

The intermediate layer may have an image formed on its surface. The method of forming an image is as described above.

As the polyethylene contained in the middle, high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE) and very low-density polyethylene (VLDPE) Can be used.
Among these, high-density polyethylene and medium-density polyethylene are preferable from the viewpoint of the strength and heat resistance of the laminate of the present invention and proper stretching of the film, and medium-density polyethylene is more preferable from the viewpoint of proper stretching.

In one embodiment, the intermediate layer includes a layer composed of high-density polyethylene (hereinafter, referred to as a high-density polyethylene layer) and a layer composed of medium-density polyethylene (hereinafter, referred to as a medium-density polyethylene layer). Can be used.
By providing the high-density polyethylene layer outside the intermediate layer, the strength and heat resistance of the laminate of the present invention can be further improved. Further, by providing the medium density polyethylene layer, the stretchability of the resin film constituting the intermediate layer can be further improved.

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

In addition, for example, a configuration including a high-density polyethylene layer / a medium-density polyethylene layer / a high-density polyethylene layer from the outside may be employed.
With such a configuration, the stretchability of the resin film can be further improved. Further, the strength and heat resistance of the laminate of the present invention can be further improved. Further, curling of the intermediate layer can be prevented.
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 further improved. Further, by setting the ratio of the thickness of the high-density polyethylene layer to the thickness of the medium-density polyethylene layer to 1/1 or less, the stretchability of the resin film can be further improved.

Also, for example, from the outside, 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 (in this paragraph, for simplicity of description, low It is also possible to adopt a configuration consisting of a density polyethylene layer) / medium density polyethylene layer / high density polyethylene layer.
With such a configuration, the stretchability of the resin film can be improved.
Further, the strength and heat resistance of the laminate of the present invention can be improved. Further, curling of the intermediate layer can be prevented.
Further, the production efficiency of the resin film 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 resin film can be improved.
Further, the thickness of the high-density polyethylene layer is preferably the same as the thickness of the low-density polyethylene layer or greater than the thickness of the low-density polyethylene.
The ratio of the thickness of the high-density polyethylene layer to the thickness of the low-density polyethylene 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 low-density polyethylene layer to 1 / 0.25 or more. By setting the ratio of the thickness of the high-density polyethylene layer to the thickness of the low-density polyethylene layer to 1/1 or less, the adhesion between the medium-density polyethylene layers can be improved.
In one embodiment, the intermediate layer having such a configuration can be manufactured 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.

共 Also, a copolymer of ethylene and the other monomer described above may be used as long as the properties of the present invention are not impaired.

In the present invention, biomass-derived ethylene may be used in place of ethylene obtained from fossil fuel as a raw material for obtaining the high-density polyethylene or the like. Since such biomass-derived polyethylene is a carb-neutral material, it can be used as a packaging material with even less environmental load.

ポリエチレン Also, polyethylene recycled by mechanical recycling can be used.

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

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

The thickness of the intermediate layer is preferably from 9 μm to 50 μm, more preferably from 12 μm to 30 μm.
By setting the thickness of the intermediate layer to 9 μm or more, the strength of the laminate of the present invention can be improved. Further, by setting the thickness of the intermediate layer to 50 μm or less, the workability of the laminate of the present invention can be improved.

The intermediate layer can be formed by forming a film of polyethylene by a T-die method or an inflation method, forming a film, and then stretching the film.

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

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

<Evaporated film>
In one embodiment, the layered product of the present invention is provided with a vapor deposition film between a substrate and an intermediate layer. Thereby, the gas barrier properties, particularly the oxygen barrier properties and the water vapor barrier properties of the laminate of the present invention can be improved.
The details of the deposited film are as described in the first embodiment.

<Adhesive layer>
In one embodiment, the laminate of the present invention may include an adhesive layer at least between the substrate or the deposited film and the intermediate layer, and at least one between the intermediate layer and the heat seal layer. Thereby, the adhesion between these layers can be improved.
The details of the adhesive film are as described in the first embodiment.

<Application>
The laminate of the present invention can be particularly suitably used for packaging materials.
The shape of the packaging material is not particularly limited, and may be a packaging bag 30 as shown in FIG. 9 or a stand pouch 40 having a body 41 and a bottom 42 as shown in FIG. Good. 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>
Medium-density polyethylene (density: 0.941 g / cm ³ , melting point: 129 ° C., MFR: 1.3 g / 10 min, manufactured by Dow Chemical Company, trade name: Elite5538G) is formed into a film by an inflation molding method, and a polyethylene film having a thickness of 100 μm. I got
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 20 μm. When the haze value of the substrate A was measured in accordance with JIS K 7105, the haze value was 6.5%.

(4) An image was formed on one surface of the substrate A by a flexographic printing method using an aqueous flexographic ink (trade name: Aquariona, manufactured by Toyo Ink Co., Ltd.).

As a heat seal layer, an unstretched linear low-density polyethylene film having a thickness of 120 μm (Mitsui Kagaku Tosello Co., Ltd., trade name: TUX-TCS) was prepared. Lamination was performed via a liquid-curable urethane-based adhesive (trade name: RU-77T / H-7, manufactured by Rock Paint Co., Ltd.) 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 97% by mass.

<Example 1-2>
A high-density polyethylene (density: 0.961 g / cm ³ , melting point 135 ° C., MFR: 0.7 g / 10 min, manufactured by ExxonMobil, trade name: HTA108) and the above-described medium-density polyethylene were formed into a film by an inflation molding method. A polyethylene film consisting of a high-density polyethylene layer / medium-density polyethylene layer / high-density polyethylene layer was produced. The thickness of each of the high-density polyethylene layers was 20 μm, and the thickness of the medium-density polyethylene layer was 60 μm.
This polyethylene film is stretched in the longitudinal direction (MD) at a draw ratio of 5 times, and a high-density polyethylene layer having a thickness of 4 μm and a medium-density polyethylene layer having a thickness of 12 μm has a total thickness of 20 μm. B was obtained. When the haze value of the base material B was measured, the haze value was 8.9%.

(4) An image was formed on one surface of the base material B by the flexographic printing method using the aqueous flexographic ink.

As the heat seal layer, the unstretched linear low-density polyethylene film having a thickness of 120 μm was prepared and laminated on the image forming surface of the base material B via the two-part curable urethane-based adhesive. Was obtained.
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.

<Example 1-3>
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.
The polyethylene film was stretched in the longitudinal direction (MD) and the width direction (TD) at a stretch ratio of 2.24 times to obtain a base material C having a thickness of 20 μm. When the haze value of the substrate C was measured, the haze value was 5.1%.

画像 An image was formed on one surface of the base material C by the flexographic printing method using the above-mentioned aqueous flexographic ink.

As the heat seal layer, the unstretched linear low-density polyethylene film having a thickness of 120 μm was prepared and laminated on the image forming surface of the base material C via the two-component curable urethane-based adhesive. Was obtained.
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 1-1>
The medium-density polyethylene was formed into a film by an inflation molding method to obtain a base material a having a thickness of 20 μm. When the haze value of the substrate a was measured, the haze value was 23.5%.

画像 An image was formed on one surface of the substrate a by the flexographic printing method using the above-mentioned aqueous flexographic ink.

As the heat seal layer, the unstretched linear low-density polyethylene film having a thickness of 120 μm was prepared, and was laminated on the image forming surface of the substrate a via the two-component curable urethane-based adhesive. 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 1-2>
The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare a base material b composed of a high-density polyethylene layer / medium-density polyethylene layer / high-density polyethylene layer. The thickness of the high-density polyethylene layer was 4 μm, and the thickness of the medium-density polyethylene layer was 12 μm. When the haze value of the substrate b was measured, the haze value was 28.8%.

As the heat seal layer, the unstretched linear low-density polyethylene film having a thickness of 120 μm is prepared, and is laminated on the image forming surface of the base material b via the two-part curable urethane-based adhesive. 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 1-3>
A laminate was obtained in the same manner as in Example 1-1, except that the base material A was a biaxially stretched polyester film having a thickness of 12 μm (trade name: Toyobo Co., Ltd .: E5100). The proportion of polyethylene in the laminate thus obtained was 88% by mass.

<Example 2-1>
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.
This polyethylene film was stretched in the longitudinal direction (MD) at a stretch ratio of 5 times to obtain a base material D having a thickness of 20 μm. When the haze value of the substrate D was measured, the haze value was 6.5%.

画像 An image was formed on one surface of the substrate D by the flexographic printing method using the above-mentioned aqueous flexographic ink.

As a heat seal layer, an unstretched linear low-density polyethylene film having a thickness of 40 μm (trade name: TUX-TCS, manufactured by Mitsui Chemicals Tosello Co., Ltd.) was prepared. Lamination was performed via a 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 ratio of polyethylene in the laminate thus obtained was 94% by mass.

<Example 2-2>
The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare a polyethylene film composed of a high-density polyethylene layer / a medium-density polyethylene layer / a high-density polyethylene layer. The thickness of each of the high-density polyethylene layers was 20 μm, and the thickness of the medium-density polyethylene layer was 60 μm.
This polyethylene film is stretched in the longitudinal direction (MD) at a draw ratio of 5 times, and a high-density polyethylene layer having a thickness of 4 μm and a medium-density polyethylene layer having a thickness of 12 μm has a total thickness of 20 μm. E was obtained. When the haze value of the substrate E was measured, the haze value was 8.9%.

画像 An image was formed on one surface of the substrate E by the flexographic printing method using the aqueous flexographic ink.

As the heat seal layer, the unstretched linear low-density polyethylene film having a thickness of 40 μm was prepared and laminated on the image forming surface of the base material E via the two-component curable urethane-based adhesive. Was 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 94% by mass.

<Example 2-3>
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.
This polyethylene film was stretched in the longitudinal direction (MD) and the width direction (TD) at a stretch ratio of 2.24 times to obtain a base material F having a thickness of 20 μm. When the haze value of the substrate F was measured, the haze value was 5.1%.

(4) An image was formed on one surface of the substrate F by the flexographic printing method using the aqueous flexographic ink.

As the heat seal layer, the unstretched linear low-density polyethylene film having a thickness of 40 μm was prepared and laminated on the image forming surface of the base material F via the two-part curable urethane-based adhesive. Was 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 94% by mass.

<Comparative Example 2-1>
The medium-density polyethylene was formed into a film by an inflation molding method to obtain a base material c having a thickness of 20 μm. When the haze value of the substrate c was measured, the haze value was 23.5%.

(4) An image was formed on one surface of the base material c by the flexographic printing method using the aqueous flexographic ink.

As the heat seal layer, the unstretched linear low-density polyethylene film having a thickness of 40 μm is prepared, and is laminated on the image forming surface of the substrate c via the two-component curable urethane-based adhesive. I got
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 94% by mass.

<Comparative Example 2-2>
The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare a substrate d composed of a high-density polyethylene layer / medium-density polyethylene layer / high-density polyethylene layer. The thickness of the high-density polyethylene layer was 4 μm, and the thickness of the medium-density polyethylene layer was 12 μm. When the haze value of the substrate d was measured, the haze value was 28.8%.

(4) An image was formed on one surface of the substrate d by the flexographic printing method using the aqueous flexographic ink.

As the heat seal layer, the unstretched linear low-density polyethylene film having a thickness of 40 μm is prepared, and is laminated on the image forming surface of the substrate d via the two-component curable urethane-based adhesive. I got
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 94% by mass.

<Comparative Example 2-3>
A laminate was obtained in the same manner as in Example 2-1 except that the base material D was a biaxially stretched polyester film having a thickness of 12 μm (trade name: E5100, manufactured by Toyobo Co., Ltd.). The proportion of polyethylene in the laminate thus obtained was 71% by mass.

<Example 3-1>
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.
This polyethylene film was stretched in the longitudinal direction (MD) at a stretch ratio of 5 times to obtain a base material G having a thickness of 20 µm. When the haze value of the substrate G was measured, the haze value was 6.5%.

画像 An image was formed on one surface of the substrate G by the flexographic printing method using the above-mentioned aqueous flexographic ink.

(4) The unstretched linear low-density polyethylene film having a thickness of 40 μm was prepared as a heat seal layer, and a 20 nm-thick aluminum vapor-deposited film was formed on one surface of the film by a PVD method.

The image forming surface of the base material G and the vapor-deposited surface of the heat seal layer 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 ratio of polyethylene in the laminate thus obtained was 94% by mass.

<Example 3-2>
The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare a polyethylene film composed of a high-density polyethylene layer / a medium-density polyethylene layer / a high-density polyethylene layer. The thickness of each of the high-density polyethylene layers was 20 μm, and the thickness of the medium-density polyethylene layer was 60 μm.
This polyethylene film is stretched in the longitudinal direction (MD) at a stretch ratio of 5 times, and a substrate having a total thickness of 20 μm, wherein the thickness of the high density polyethylene layer is 4 μm and the thickness of the medium density polyethylene layer is 12 μm, respectively. H was obtained. When the haze value of the substrate H was measured, the haze value was 8.9%.

(4) An image was formed on one surface of the base material H by the flexographic printing method using the aqueous flexographic ink.

The image forming surface of the base material H and the vapor-deposited surface of the heat seal layer 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 ratio of polyethylene in the laminate thus obtained was 94% by mass.

<Example 3-3>
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.
This polyethylene film was stretched in the longitudinal direction (MD) and the width direction (TD) at a stretch ratio of 2.24 times to obtain a base material I having a thickness of 20 μm. When the haze value of the substrate I was measured, the haze value was 5.1%.

(4) An image was formed on one surface of the base material I by the flexographic printing method using the aqueous flexographic ink.

The image forming surface of the base material I and the vapor-deposited film of the heat seal layer 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 ratio of polyethylene in the laminate thus obtained was 94% by mass.

<Example 3-4>
In Example 3-1, the adhesion between the image forming surface of the base material G and the vapor-deposited surface of the heat seal layer was determined by using a two-part curable adhesive containing a polyester polyol and an isocyanate compound (PASLIM VM001 / manufactured by DIC Corporation). VM102CP), and a laminate of the present invention was produced in the same manner as in Example 3-1.

<Comparative Example 3-1>
The medium-density polyethylene was formed into a film by an inflation molding method to obtain a base material e having a thickness of 20 μm. When the haze value of the substrate e was measured, the haze value was 23.5%.

(4) An image was formed on one surface of the substrate e by a flexographic printing method using the aqueous flexographic ink.

The image forming surface of the base material e and the vapor-deposited surface of the heat seal layer 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 ratio of polyethylene in the laminate thus obtained was 94% by mass.

<Comparative Example 3-2>
The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare a substrate f composed of a high-density polyethylene layer / a medium-density polyethylene layer / a high-density polyethylene layer. The thickness of the high-density polyethylene layer was 4 μm, and the thickness of the medium-density polyethylene layer was 12 μm. When the haze value of the substrate f was measured, the haze value was 28.8%.

画像 An image was formed on one surface of the substrate f by the flexographic printing method using the above-mentioned aqueous flexographic ink.

The image forming surface of the base material f and the vapor-deposited surface of the heat seal layer 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 3-3>
A laminate was obtained in the same manner as in Example 3-1 except that the base material G was a biaxially stretched polyester film having a thickness of 12 μm (trade name: Toyobo Co., Ltd .: E5100). The proportion of polyethylene in the thus obtained laminate was 71% by mass.

<Example 4-1>
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.
This polyethylene film was stretched in the longitudinal direction (MD) at a stretch ratio of 5 times to obtain a base material J having a thickness of 20 μm. When the haze value of the substrate J was measured, the haze value was 6.5%.

(4) An image was formed on one surface of the base material J by the flexographic printing method using the aqueous flexographic ink.

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

(4) The image forming surface of the base material J was laminated on the 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.

As the heat seal layer, the unstretched linear low-density polyethylene film having a thickness of 40 μm was prepared and laminated on the non-deposited surface of the intermediate layer A via the two-component curable urethane-based adhesive. Was obtained.
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 92% by mass.

<Example 4-2>
The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare a polyethylene film composed of a high-density polyethylene layer / a medium-density polyethylene layer / a high-density polyethylene layer. The thickness of each of the high-density polyethylene layers was 20 μm, and the thickness of the medium-density polyethylene layer was 60 μm.
This polyethylene film is stretched in the longitudinal direction (MD) at a stretch ratio of 5 times, and the thickness of the high-density polyethylene layer is 4 μm, the thickness of the medium-density polyethylene layer is 12 μm, and the total thickness is 20 μm. A substrate K was obtained. When the haze value of the substrate K was measured, the haze value was 8.9%.

(4) An image was formed on one surface of the base material K by the flexographic printing method using the above aqueous flexographic ink.

The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare a polyethylene film composed of a high-density polyethylene layer / a medium-density polyethylene layer / a high-density polyethylene layer. The thickness of each of the high-density polyethylene layers was 20 μm, and the thickness of the medium-density polyethylene layer was 60 μm.
This polyethylene film is stretched in the longitudinal direction (MD) at a stretch ratio of 5 times, and the thickness of the high-density polyethylene layer is 4 μm, the thickness of the medium-density polyethylene layer is 12 μm, and the total thickness is 20 μm. A polyethylene resin layer B was obtained. Next, a 20-nm-thick aluminum vapor-deposited film was formed on one surface of the polyethylene resin layer B by a PVD method to obtain an intermediate layer B.

(4) The image forming surface of the base material K was laminated on the vapor deposition surface of the intermediate layer B 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.

As the heat seal layer, the unstretched linear low-density polyethylene film having a thickness of 40 μm was prepared and laminated on the non-deposited surface of the intermediate layer B via the two-component curable urethane-based adhesive. Was obtained.
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 92% by mass.

<Example 4-3>
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.
This polyethylene film was stretched in the longitudinal direction (MD) and the width direction (TD) at a stretch ratio of 2.24 times to obtain a base material L having a thickness of 20 μm. When the haze value of the substrate L was measured, the haze value was 5.1%.

(4) An image was formed on one surface of the base material L by the flexographic printing method using the aqueous flexographic ink.

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.
This polyethylene film was stretched in the longitudinal direction (MD) and the width direction (TD) at a stretch ratio of 2.24 times to obtain a polyethylene resin layer C having a thickness of 20 μm. Next, a 20 nm-thick aluminum vapor-deposited film was formed on one surface of the polyethylene resin layer C by a PVD method to obtain an intermediate layer C.

(4) The image forming surface of the base material L was laminated on the vapor deposition surface of the intermediate layer C 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.

As the heat seal layer, the unstretched linear low-density polyethylene film having a thickness of 40 μm was prepared and laminated on the non-deposited surface of the intermediate layer C via the two-component curable urethane-based adhesive. Was obtained.
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 92% by mass.

<Example 4-4>
In Example 4-1, the adhesion between the image forming surface of the base material J and the deposition surface of the intermediate layer A was determined by using a two-part curable adhesive containing a polyester polyol and an isocyanate compound (PASLIM VM001 / manufactured by DIC Corporation). VM102CP), and a laminate of the present invention was produced in the same manner as in Example 4-1 except that the process was performed using VM102CP).

<Comparative Example 4-1>
The medium-density polyethylene was formed into a film by an inflation molding method to obtain a base material g having a thickness of 20 μm. When the haze value of the substrate g was measured, the haze value was 23.5%.

(4) An image was formed on one surface of the substrate g by the flexographic printing method using the aqueous flexographic ink.

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

{Circle around (2)} The image forming surface of the base material g was laminated on the 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.

As the heat seal layer, the unstretched linear low-density polyethylene film having a thickness of 40 μm was prepared, and was laminated on the non-deposited surface of the intermediate layer a via the two-component curable urethane-based adhesive. 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 92% by mass.

<Comparative Example 4-2>
The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare a substrate h consisting of a high-density polyethylene layer / medium-density polyethylene layer / high-density polyethylene layer. The thickness of the high-density polyethylene layer was 4 μm, and the thickness of the medium-density polyethylene layer was 12 μm. When the haze value of the substrate h was measured, the haze value was 23.5%.

(4) An image was formed on one surface of the substrate h by a flexographic printing method using the aqueous flexographic ink.

The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare a polyethylene resin layer b composed of a high-density polyethylene layer / a medium-density polyethylene layer / a high-density polyethylene layer. The thickness of the high-density polyethylene layer was 4 μm, and the thickness of the medium-density polyethylene layer was 12 μm.
Next, a 20 nm-thick aluminum vapor-deposited film was formed on one surface of the polyethylene resin layer b by a PVD method to obtain an intermediate layer b.

{Circle around (2)} The image forming surface of the base material h was laminated on the vapor deposition surface of the intermediate layer b 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.

As the heat seal layer, the unstretched linear low-density polyethylene film having a thickness of 40 μm was prepared, and was laminated on the non-deposited surface of the intermediate layer b via the two-component curable urethane-based adhesive. 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 92% by mass.

<Comparative Example 4-3>
A laminate was obtained in the same manner as in Example 4-1 except that the base material and the polyethylene resin layer of the intermediate layer were changed to a biaxially stretched polyester film having a thickness of 12 μm (trade name: E5100, Toyobo Co., Ltd.). . The proportion of polyethylene in the laminate thus obtained was 56% 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 Tables 1 to 4.
(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>
From the laminates obtained in Examples 1-1 to 1-3 and Comparative Examples 1-1 and 1-2, 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 laminates obtained in Examples 1-1 to 1-3 and Comparative examples 1-1 and 1-2, and this was used as a heat seal layer. It was folded into a V-shape so as to be on the outside, and was heat-sealed at 140 ° C. with the cylindrical body to form a bottom and a stand pouch.
Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-2, Examples 3-1 to 3-4, Comparative Examples 3-1 to 3-2, and Examples 4-1 to 4-4 From the laminates obtained in Comparative Examples 4-1 to 4-3, 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.
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>
Using the tensile tester (trade name: RTC-1310A, manufactured by Orientec Co., Ltd.), the laminates prepared in the above Examples and Comparative Examples were measured for the strength when a needle having a diameter of 0.5 mm was pierced. 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 laminates obtained in Examples 3-1 to 3-4 and Comparative examples 3-1 to 3-2, and Examples 4-1 to 4-4 and Comparative examples 4-1 to 4-3 were obtained. 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.
Further, the laminates obtained in Examples 3-1 to 3-4 and Comparative examples 3-1 to 3-2, and Examples 4-1 to 4-4 and Comparative examples 4-1 to 4-3 were: 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.

<Example 5-1>
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.
This polyethylene film was stretched in the machine direction (MD) at a stretch ratio of 5 times to obtain a substrate having a thickness of 20 μm. When the haze value of the substrate was measured in accordance with JIS K 7105, the haze value was 6.5%.

(4) An image was formed on one surface of the substrate by a flexographic printing method using an aqueous flexographic ink (trade name: Aquariona, manufactured by Toyo Ink Co., Ltd.).

As a heat seal layer, an unstretched linear low-density polyethylene film having a thickness of 120 μm (Mitsui Kagaku Tosello Co., Ltd., trade name: TUX-TCS) was prepared. An aluminum deposition film was formed.

{Circle around (2)} The image forming surface of the base material and the surface on which the vapor-deposited film of the heat seal layer was formed 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.

<Example 5-2>
The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare a polyethylene film composed of a high-density polyethylene layer / a medium-density polyethylene layer / a high-density polyethylene layer. The thickness of each of the high-density polyethylene layers was 20 μm, and the thickness of the medium-density polyethylene layer was 60 μm.
This polyethylene film is stretched in the longitudinal direction (MD) at a draw ratio of 5 times, and a high-density polyethylene layer having a thickness of 4 μm and a medium-density polyethylene layer having a thickness of 12 μm has a total thickness of 20 μm. I got When the haze value of the substrate was measured, the haze value was 8.9%.

(4) An image was formed on one surface of the substrate by the flexographic printing method using the aqueous flexographic ink.

(4) The unstretched linear low-density polyethylene film having a thickness of 120 μm was prepared as a heat seal layer, and a 20 nm-thick aluminum vapor-deposited film was formed on one surface of the film by a PVD method.

<Example 5-3>
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.
This polyethylene film was stretched in the longitudinal direction (MD) and the width direction (TD) at a stretch ratio of 2.24 times to obtain a substrate having a thickness of 20 μm. When the haze value of the substrate was measured, the haze value was 5.1%.

<Example 5-4>
In Example 5-1, the adhesion between the image forming surface of the base material and the surface on which the heat-sealing layer was formed was determined by using a two-part curable adhesive containing a polyester polyol and an isocyanate compound (PASLIM VM001, manufactured by DIC Corporation). / VM102CP), to produce a laminate in the same manner as in Example 5-1.

<Comparative Example 5-1>
The medium-density polyethylene was formed into a film by an inflation molding method to obtain a base material having a thickness of 20 μm. When the haze value of the substrate was measured, the haze value was 23.5%.

{Circle around (2)} The image forming surface of the base material and the vapor-deposited film forming surface of the heat seal layer 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.

<Comparative Example 5-2>
The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare a base material composed of a high-density polyethylene layer / a medium-density polyethylene layer / a high-density polyethylene layer. The thickness of the high-density polyethylene layer was 4 μm, and the thickness of the medium-density polyethylene layer was 12 μm. When the haze value of the substrate was measured, the haze value was 28.8%.

<Comparative Example 5-3>
A laminate was obtained in the same manner as in Example 5-1 except that the base material was a biaxially stretched polyester film having a thickness of 12 μm (trade name: E5100, Toyobo Co., Ltd.).

<Heat resistance evaluation>
From the laminates obtained in Examples 5-1 to 5-4 and Comparative Examples 5-1 and 5-2, 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 Examples 5-1 to 5-4 and Comparative examples 5-1 to 5-2, and this was used as a heat seal layer. It was folded into a V-shape so as to be on the outside, and was heat-sealed at 140 ° C. with the cylindrical body to form a bottom and a stand pouch.
The prepared packaging material was visually observed and evaluated based on the following evaluation criteria. Table 5 summarizes the evaluation results.
(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>
An image formed on the base material included in the laminate prepared in the above Examples and Comparative Examples was visually observed, and its printability was evaluated based on the following evaluation criteria. The evaluation results are summarized in Tables 1 and 5.
(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. Table 5 summarizes the measurement results.

<Strength test>
Using the tensile tester (trade name: RTC-1310A, manufactured by Orientec Co., Ltd.), the laminates prepared in the above Examples and Comparative Examples were measured for the strength when a needle having a diameter of 0.5 mm was pierced. The piercing speed was 50 mm / min. Table 5 summarizes the measurement results.

<Bending load resistance test>
First, the oxygen permeability and the water vapor permeability of the laminate obtained above 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, a bending load (stroke: 155 mm, bending operation: 440 °) was applied to the laminate obtained above using a gelbo flex tester (manufactured by Tester Sangyo Co., Ltd., trade name: BE1006BE) in accordance with ASTM F392. ) Was given 5 times.
After the bending load, the oxygen permeability and the water vapor permeability of the laminate were measured.
Table 5 summarizes the oxygen permeability and the water vapor permeability of the laminate before and after the bending load test.

<Example 6-1>
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.
This polyethylene film was stretched in the machine direction (MD) at a stretch ratio of 5 times to obtain a substrate having a thickness of 20 μm. When the haze value of the substrate was measured, the haze value was 6.5%.

The medium-density polyethylene is 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 times to obtain an intermediate layer base material having a thickness of 20 μm. Was. Next, a 20 nm-thick aluminum vapor-deposited film was formed on one surface of the intermediate layer base material by a PVD method to obtain an intermediate layer.

(4) The image forming surface of the base material was laminated on the deposition surface of the intermediate layer 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 non-stretched linear low-density polyethylene (LLDPE) film having a thickness of 120 μm (LLDPE) as a heat seal layer on the non-evaporated surface of the intermediate layer via the two-liquid curable urethane-based adhesive (Mitsui Chemicals East Sero Corporation, (Trade name: TUX-TCS) 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 96% by mass.

<Example 6-2>
The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare a polyethylene film composed of a high-density polyethylene layer / a medium-density polyethylene layer / a high-density polyethylene layer. The thickness of each of the high-density polyethylene layers was 20 μm, and the thickness of the medium-density polyethylene layer was 60 μm.
This polyethylene film was stretched in the machine direction (MD) at a stretch ratio of 5 times to obtain a substrate having a thickness of 20 μm. When the haze value of the substrate was measured, the haze value was 8.9%.

The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare a polyethylene film composed of a high-density polyethylene layer / a medium-density polyethylene layer / a high-density polyethylene layer. The thickness of each of the high-density polyethylene layers was 20 μm, and the thickness of the medium-density polyethylene layer was 60 μm.
This polyethylene film was stretched in the longitudinal direction (MD) at a stretch ratio of 5 times to obtain a 20 μm thick intermediate layer base material. Next, a 20 nm-thick aluminum vapor-deposited film was formed on one surface of the intermediate layer base material by a PVD method to obtain an intermediate layer.

The unstretched linear low-density polyethylene (LLDPE) film having a thickness of 120 μm was laminated as a heat seal layer on the non-evaporated surface of the intermediate layer via the two-component curable urethane-based adhesive, according to the present invention. A laminate was obtained.
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 96% by mass.

<Example 6-3>
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.
This polyethylene film was stretched in the longitudinal direction (MD) and the width direction (TD) at a stretch ratio of 2.24 times to obtain a substrate having a thickness of 20 μm. When the haze value of the substrate was measured, the haze value was 5.1%.

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.
This polyethylene film was stretched in the longitudinal direction (MD) and the width direction (TD) at a stretch ratio of 2.24 times to obtain an intermediate layer base material having a thickness of 20 μm. Next, a 20 nm-thick aluminum vapor-deposited film was formed on one surface of the intermediate layer base material by a PVD method to obtain an intermediate layer.

<Example 6-4>
In Example 6-1, the adhesion between the image forming surface of the base material and the deposition surface of the intermediate layer was determined by a two-part curable adhesive containing polyester polyol and an isocyanate compound (PASLIM VM001 / VM102CP, manufactured by DIC Corporation). A laminate was produced in the same manner as in Example 6-1 except that the above procedure was performed.

<Comparative Example 6-1>
The medium-density polyethylene was formed into a film by an inflation molding method to obtain a polyethylene film having a thickness of 20 μm, which was used as a base material. When the haze value of the substrate was measured, the haze value was 23.5%.

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

The unstretched linear low-density polyethylene (LLDPE) film having a thickness of 120 μm is laminated as a heat seal layer on the non-deposited surface of the intermediate layer via the two-liquid curable urethane-based adhesive, and the laminate is formed. Obtained.
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 96% by mass.

<Comparative Example 6-2>
The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare a base material composed of a high-density polyethylene layer / a medium-density polyethylene layer / a high-density polyethylene layer. The thickness of the high-density polyethylene layer was 4 μm, and the thickness of the medium-density polyethylene layer was 12 μm. When the haze value of the substrate was measured, the haze value was 23.5%.

(4) The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare an intermediate layer base material composed of a high-density polyethylene layer / a medium-density polyethylene layer / a high-density polyethylene layer. The thickness of the high-density polyethylene layer was 4 μm, and the thickness of the medium-density polyethylene layer was 12 μm. Next, a 20-nm-thick aluminum vapor-deposited film was formed on one surface of the intermediate layer base material by a PVD method to obtain an intermediate layer.

<Comparative Example 6-3>
A laminate was obtained in the same manner as in Example 6-1 except that the intermediate layer substrate of the intermediate layer and the intermediate layer was changed to a biaxially stretched polyester film having a thickness of 12 μm (trade name: E5100, Toyobo Co., Ltd.). Was. The proportion of polyethylene in the laminate thus obtained was 79% 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 80% by mass or more.
X: The content of polyethylene in the laminate was less than 80% by mass.

<Heat resistance evaluation>
From the laminates obtained in the above Examples 6-1 to 6-4 and Comparative Examples 6-1 to 6-3, 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 each of Examples 6-1 to 6-4 and Comparative examples 6-1 to 6-3. It was folded into a V-shape so as to be on the outside, and was heat-sealed at 140 ° C. with the cylindrical body to form a bottom and a stand pouch.
The prepared packaging material was visually observed and evaluated based on the following evaluation criteria. Table 6 summarizes the evaluation results.
(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. Table 6 summarizes the evaluation results.
(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 test>
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. Table 6 summarizes the measurement results.

<Strength test>
Using the tensile tester (trade name: RTC-1310A, manufactured by Orientec Co., Ltd.), the laminates prepared in the above Examples and Comparative Examples were measured for the strength when a needle having a diameter of 0.5 mm was pierced. The piercing speed was 50 mm / min. Table 6 summarizes the measurement results.

<Bending load resistance test>
First, the oxygen permeability and the water vapor permeability of the laminate obtained above 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, a bending load (stroke: 155 mm, bending operation: 440 °) was applied to the laminate obtained above using a gelbo flex tester (manufactured by Tester Sangyo Co., Ltd., trade name: BE1006BE) in accordance with ASTM F392. ) Was given 5 times.
After the bending load, the oxygen permeability and the water vapor permeability of the laminate were measured.
Table 6 shows the oxygen permeability and the water vapor permeability of the laminate before and after the bending load test.

<Example 7-1>
Medium-density polyethylene (density: 0.941 g / cm ³ , melting point: 129 ° C., MFR: 1.3 g / 10 min, manufactured by Dow Chemical Company, trade name: Elite5538G) is formed into a film by an inflation molding method, and a polyethylene film having a thickness of 100 μm. I got
This polyethylene film was stretched in the machine direction (MD) at a stretch ratio of 5 times to obtain a substrate having a thickness of 20 μm. When the haze value of the substrate was measured in accordance with JIS K 7105, the haze value was 6.5%.

As the heat seal layer, linear low-density polyethylene (density: 0.925, MFR: 1.9 g / 10 min, made of Prime Polymer, trade name: SP2520) and linear low-density polyethylene derived from biomass (density: 0) .916 g / cm ³ , MFR: 1.3 g / 10 min, biomass degree: 87%, manufactured by Braskem, trade name: SLL18), and formed into a film by an inflation molding method. A polyethylene film composed of a chain low-density polyethylene layer / a linear low-density polyethylene layer was produced.
The thickness of each of the linear low-density polyethylene layers was 30 μm, the thickness of the biomass-derived linear low-density polyethylene layer was 60 μm, and the total thickness was 120 μm. This is laminated on the image forming surface of the base material via a two-component curable urethane-based adhesive (trade name: RU-77T / H-7, manufactured by Rock Paint Co., Ltd.), and a 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.

<Example 7-2>
A high-density polyethylene (density: 0.961 g / cm ³ , melting point 135 ° C., MFR: 0.7 g / 10 min, manufactured by ExxonMobil, trade name: HTA108) and the above-described medium-density polyethylene were formed into a film by an inflation molding method. A polyethylene film consisting of a high-density polyethylene layer / medium-density polyethylene layer / high-density polyethylene layer was produced. The thickness of each of the high-density polyethylene layers was 20 μm, and the thickness of the medium-density polyethylene layer was 60 μm.
This polyethylene film is stretched in the longitudinal direction (MD) at a draw ratio of 5 times, and a high-density polyethylene layer having a thickness of 4 μm and a medium-density polyethylene layer having a thickness of 12 μm has a total thickness of 20 μm. I got When the haze value of the substrate was measured, the haze value was 8.9%.

The polyethylene film having a thickness of 120 μm was prepared as a heat seal layer, and laminated on the image forming surface of the substrate via the two-component curable urethane 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 97% by mass.

<Example 7-3>
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.
This polyethylene film was stretched in the longitudinal direction (MD) and the width direction (TD) at a stretch ratio of 2.24 times to obtain a substrate having a thickness of 20 μm. When the haze value of the substrate was measured, the haze value was 5.1%.

<Comparative Example 7-1>
The medium-density polyethylene was formed into a film by an inflation molding method to obtain a base material having a thickness of 20 μm. When the haze value of the substrate was measured, the haze value was 23.5%.

The polyethylene film having a thickness of 120 μm was prepared as a heat seal layer, and laminated on the image forming surface of the substrate 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 7-2>
The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare a base material composed of a high-density polyethylene layer / a medium-density polyethylene layer / a high-density polyethylene layer. The thickness of the high-density polyethylene layer was 4 μm, and the thickness of the medium-density polyethylene layer was 12 μm. When the haze value of the substrate was measured, the haze value was 28.8%.

<Comparative Example 7-3>
A laminate was obtained in the same manner as in Example 7-1 except that the base material was a biaxially stretched polyester film having a thickness of 12 μm (trade name: Toyobo Co., Ltd .: E5100).
The proportion of polyethylene in the laminate thus obtained was 88% by mass.

<Example 8-1>
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.
This polyethylene film was stretched in the machine direction (MD) at a stretch ratio of 5 times to obtain a substrate having a thickness of 20 μm. When the haze value of the substrate was measured, the haze value was 6.5%.

As the heat seal layer, linear low-density polyethylene (density: 0.925, MFR: 1.9 g / 10 min, made of Prime Polymer, trade name: SP2520) and linear low-density polyethylene derived from biomass (density: 0) .916 g / cm ³ , MFR: 1.3 g / 10 min, biomass degree: 87%, manufactured by Braskem, trade name: SLL18), and formed into a film by an inflation molding method. A polyethylene film composed of a chain low-density polyethylene layer / a linear low-density polyethylene layer was produced. The thickness of each of the linear low-density polyethylene layers was 10 μm, the thickness of the biomass-derived linear low-density polyethylene layer was 20 μm, and the total thickness was 40 μm. The laminate was laminated on the image forming surface of the substrate via the above 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 ratio of polyethylene in the laminate thus obtained was 94% by mass.

<Example 8-2>
The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare a polyethylene film composed of a high-density polyethylene layer / a medium-density polyethylene layer / a high-density polyethylene layer. The thickness of each of the high-density polyethylene layers was 20 μm, and the thickness of the medium-density polyethylene layer was 60 μm.
This polyethylene film is stretched in the longitudinal direction (MD) at a draw ratio of 5 times, and a high-density polyethylene layer having a thickness of 4 μm and a medium-density polyethylene layer having a thickness of 12 μm has a total thickness of 20 μm. I got When the haze value of the substrate was measured, the haze value was 8.9%.

The polyethylene film having a thickness of 40 μm was prepared as a heat seal layer, and laminated on the image forming surface of the substrate via the two-component curable urethane 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 ratio of polyethylene in the laminate thus obtained was 94% by mass.

<Example 8-3>
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.
This polyethylene film was stretched in the longitudinal direction (MD) and the width direction (TD) at a stretch ratio of 2.24 times to obtain a substrate having a thickness of 20 μm. When the haze value of the substrate was measured, the haze value was 5.1%.

<Comparative Example 8-1>
The medium-density polyethylene was formed into a film by an inflation molding method to obtain a base material having a thickness of 20 μm. When the haze value of the substrate was measured, the haze value was 23.5%.

The polyethylene film having a thickness of 40 μm was prepared as a heat seal layer, and was laminated on the image forming surface of the substrate 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 ratio of polyethylene in the laminate thus obtained was 94% by mass.

<Comparative Example 8-2>
The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare a base material composed of a high-density polyethylene layer / a medium-density polyethylene layer / a high-density polyethylene layer. The thickness of the high-density polyethylene layer was 4 μm, and the thickness of the medium-density polyethylene layer was 12 μm. When the haze value of the substrate was measured, the haze value was 28.8%.

As the heat seal layer, the unstretched linear low-density polyethylene film having a thickness of 40 μm is prepared, and is laminated on the image forming surface of the substrate via the two-component curable urethane-based adhesive. 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 94% by mass.

<Comparative Example 8-3>
A laminate was obtained in the same manner as in Example 8-1, except that the substrate was a biaxially stretched polyester film having a thickness of 12 μm (trade name: Toyobo Co., Ltd .: E5100).
The proportion of polyethylene in the laminate thus obtained was 71% by mass.

<Example 9-1>
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.
This polyethylene film was stretched in the machine direction (MD) at a stretch ratio of 5 times to obtain a substrate having a thickness of 20 μm. When the haze value of the substrate was measured, the haze value was 6.5%.

(4) The above polyethylene film having a thickness of 40 μm was prepared as a heat seal layer, and a 20 nm-thick aluminum vapor-deposited film was formed on one surface of the polyethylene film by a PVD method.

The image forming surface of the base material and the vapor-deposited surface of the heat seal layer 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 ratio of polyethylene in the laminate thus obtained was 94% by mass.

<Example 9-2>
The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare a polyethylene film composed of a high-density polyethylene layer / a medium-density polyethylene layer / a high-density polyethylene layer. The thickness of each of the high-density polyethylene layers was 20 μm, and the thickness of the medium-density polyethylene layer was 60 μm.
This polyethylene film is stretched in the longitudinal direction (MD) at a draw ratio of 5 times, and a high-density polyethylene layer having a thickness of 4 μm and a medium-density polyethylene layer having a thickness of 12 μm has a total thickness of 20 μm. I got When the haze value of the substrate was measured, the haze value was 8.9%.

<Example 9-3>
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.
This polyethylene film was stretched in the longitudinal direction (MD) and the width direction (TD) at a stretch ratio of 2.24 times to obtain a substrate having a thickness of 20 μm. When the haze value of the substrate was measured, the haze value was 5.1%.

The image forming surface of the substrate and the vapor-deposited film of the heat seal layer were laminated via the above-mentioned 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 ratio of polyethylene in the laminate thus obtained was 94% by mass.

<Example 9-4>
In Example 9-1, the adhesion between the image forming surface of the substrate and the vapor-deposited surface of the heat seal layer was determined by using a two-part curable adhesive containing a polyester polyol and an isocyanate compound (PASLIM VM001 / VM102CP manufactured by DIC Corporation). ), To produce a laminate of the present invention in the same manner as in Example 9-1.

<Comparative Example 9-1>
The medium-density polyethylene was formed into a film by an inflation molding method to obtain a base material having a thickness of 20 μm. When the haze value of the substrate was measured, the haze value was 23.5%.

The image forming surface of the base material and the vapor-deposited surface of the heat seal layer 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 ratio of polyethylene in the laminate thus obtained was 94% by mass.

<Comparative Example 9-2>
The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare a base material composed of a high-density polyethylene layer / a medium-density polyethylene layer / a high-density polyethylene layer. The thickness of the high-density polyethylene layer was 4 μm, and the thickness of the medium-density polyethylene layer was 12 μm. When the haze value of the substrate was measured, the haze value was 28.8%.

The image forming surface of the base material and the vapor-deposited surface of the heat seal layer 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 9-3>
A laminate was obtained in the same manner as in Example 9-1 except that the base material was a biaxially stretched polyester film having a thickness of 12 μm (trade name: E5100, manufactured by Toyobo Co., Ltd.). The proportion of polyethylene in the thus obtained laminate was 71% by mass.

<Example 10-1>
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.
This polyethylene film was stretched in the machine direction (MD) at a stretch ratio of 5 times to obtain a substrate having a thickness of 20 μm. When the haze value of the substrate was measured, the haze value was 6.5%.

The above-mentioned 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 times to obtain a polyethylene resin layer having a thickness of 20 µm. . Next, a 20 nm-thick aluminum vapor-deposited film was formed on one surface of the polyethylene resin layer by a PVD method to obtain an intermediate layer.

(4) The image forming surface of the base material was laminated on the vapor deposition surface of the intermediate layer 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.

The polyethylene film having a thickness of 40 μm was prepared as a heat seal layer, and was laminated on the non-deposited surface of the intermediate layer 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 92% by mass.

<Example 10-2>
The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare a polyethylene film composed of a high-density polyethylene layer / a medium-density polyethylene layer / a high-density polyethylene layer. The thickness of each of the high-density polyethylene layers was 20 μm, and the thickness of the medium-density polyethylene layer was 60 μm.
This polyethylene film is stretched in the longitudinal direction (MD) at a stretch ratio of 5 times, and the thickness of the high-density polyethylene layer is 4 μm, the thickness of the medium-density polyethylene layer is 12 μm, and the total thickness is 20 μm. A substrate was obtained. When the haze value of the substrate was measured, the haze value was 8.9%.

The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare a polyethylene film composed of a high-density polyethylene layer / a medium-density polyethylene layer / a high-density polyethylene layer. The thickness of each of the high-density polyethylene layers was 20 μm, and the thickness of the medium-density polyethylene layer was 60 μm.
This polyethylene film is stretched in the longitudinal direction (MD) at a stretch ratio of 5 times, and the thickness of the high-density polyethylene layer is 4 μm, the thickness of the medium-density polyethylene layer is 12 μm, and the total thickness is 20 μm. A polyethylene resin layer was obtained. Next, a 20 nm-thick aluminum vapor-deposited film was formed on one surface of the polyethylene resin layer by a PVD method to obtain an intermediate layer.

<Example 10-3>
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.
This polyethylene film was stretched in the longitudinal direction (MD) and the width direction (TD) at a stretch ratio of 2.24 times to obtain a substrate having a thickness of 20 μm. When the haze value of the substrate was measured, the haze value was 5.1%.

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.
This polyethylene film was stretched in the longitudinal direction (MD) and the width direction (TD) at a stretch ratio of 2.24 times to obtain a polyethylene resin layer having a thickness of 20 μm. Next, a 20 nm-thick aluminum vapor-deposited film was formed on one surface of the polyethylene resin layer by a PVD method to obtain an intermediate layer.

As the heat seal layer, the unstretched linear low-density polyethylene film having a thickness of 40 μm was prepared, and was laminated on the non-deposited surface of the intermediate layer via the two-part curable urethane-based adhesive. A laminate was obtained.
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 92% by mass.

<Example 10-4>
In Example 10-1, the adhesion between the image forming surface of the substrate and the deposition surface of the intermediate layer was determined by using a two-part curable adhesive containing a polyester polyol and an isocyanate compound (PASLIM VM001 / VM102CP, manufactured by DIC Corporation). A laminate of the present invention was produced in the same manner as in Example 10-1, except that the above procedure was performed.

<Comparative Example 10-1>
The medium-density polyethylene was formed into a film by an inflation molding method to obtain a base material having a thickness of 20 μm. When the haze value of the substrate was measured, the haze value was 23.5%.

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

The polyethylene film having a thickness of 40 μm was prepared as a heat seal layer, and was laminated on the non-deposited surface of the intermediate layer 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 92% by mass.

<Comparative Example 10-2>
The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare a base material composed of a high-density polyethylene layer / a medium-density polyethylene layer / a high-density polyethylene layer. The thickness of the high-density polyethylene layer was 4 μm, and the thickness of the medium-density polyethylene layer was 12 μm. When the haze value of the substrate was measured, the haze value was 23.5%.

The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare a polyethylene resin layer composed of a high-density polyethylene layer / a medium-density polyethylene layer / a high-density polyethylene layer. The thickness of the high-density polyethylene layer was 4 μm, and the thickness of the medium-density polyethylene layer was 12 μm.
Next, a 20 nm-thick aluminum vapor-deposited film was formed on one surface of the polyethylene resin layer by a PVD method to obtain an intermediate layer.

As the heat seal layer, the unstretched linear low-density polyethylene film having a thickness of 40 μm is prepared, and is laminated on the non-deposited surface of the intermediate layer via the two-component curable urethane-based adhesive. Obtained.
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 92% by mass.

<Comparative Example 10-3>
A laminate was obtained in the same manner as in Example 10-1, except that the polyethylene resin layer as the base material and the intermediate layer was changed to a biaxially stretched polyester film having a thickness of 12 μm (trade name: E5100, Toyobo Co., Ltd.). . The proportion of polyethylene in the laminate thus obtained was 56% 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 Tables 7 to 10.
(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>
From the laminates obtained in Examples 7-1 to 7-3 and Comparative Examples 7-1 and 7-2, 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, from the laminates obtained in the above Examples 7-1 to 7-3 and Comparative Examples 7-1 to 7-2, one test piece having a length of 110 mm and a width of 150 mm was prepared. It was folded into a V-shape so as to be on the outside, and was heat-sealed at 140 ° C. with the cylindrical body to form a bottom and a stand pouch.
Examples 8-1 to 8-3 and Comparative Examples 8-1 to 8-2, Examples 9-1 to 9-4, Comparative Examples 9-1 to 9-2, and Examples 10-1 to 10-4 From the laminates obtained in Comparative Examples 10-1 to 10-3, 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.
The prepared packaging material was visually observed and evaluated based on the following evaluation criteria. The evaluation results are summarized in Tables 7 to 10.
(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 7 to 10.
(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 7 to 10.

<Strength test>
Using the tensile tester (trade name: RTC-1310A, manufactured by Orientec Co., Ltd.), the laminates prepared in the above Examples and Comparative Examples were measured for the strength when a needle having a diameter of 0.5 mm was pierced. The piercing speed was 50 mm / min. The measurement results are summarized in Tables 7 to 10.

<Bending load resistance test>
First, the oxygen of the laminates obtained in the above Examples 9-1 to 9-4 and Comparative Examples 9-1 to 9-2 and Examples 10-1 to 10-4 and Comparative Examples 10-1 to 10-3 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.
Further, the laminates obtained in the above Examples 9-1 to 9-4 and Comparative Examples 9-1 to 9-2, and Examples 10-1 to 10-4 and Comparative Examples 10-1 to 10-3, 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 9 and 10 show the oxygen permeability and the water vapor permeability of the laminate before and after the bending load test.

<Example 11-1>
Medium-density polyethylene (density: 0.941 g / cm ³ , melting point: 129 ° C., MFR: 1.3 g / 10 min, manufactured by Dow Chemical Company, trade name: Elite5538G) is formed into a film by an inflation molding method, and a polyethylene film having a thickness of 100 μm. I got
This polyethylene film was stretched in the longitudinal direction (MD) at a stretch ratio of 5 times to obtain an intermediate layer having a thickness of 20 μm. When the haze value of the intermediate layer was measured, the haze value was 6.5%.

画像 An image was formed on one surface of the intermediate layer by the flexographic printing method using the aqueous flexographic ink.

A polyethylene terephthalate film having a thickness of 12 μm (manufactured by Toyobo Co., Ltd., trade name: E-5100) is prepared as a base material, and the base material and the image forming surface of the intermediate layer are two-part curable urethane-based film. Lamination was carried out using an adhesive (trade name: RU-77T / H-7, manufactured by Rock Paint Co., Ltd.). The thickness of the adhesive layer formed by the two-component curable urethane-based adhesive was 3.0 μm.

As a heat seal layer, an unstretched linear low-density polyethylene film having a thickness of 120 μm (Mitsui Chemicals Tosello Co., Ltd., trade name: TUX-TCS) was prepared. Lamination was performed using a liquid-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 88% by mass.

<Example 11-2>
A high-density polyethylene (density: 0.961 g / cm ³ , melting point 135 ° C., MFR: 0.7 g / 10 min, manufactured by ExxonMobil, trade name: HTA108) and the above-described medium-density polyethylene were formed into a film by an inflation molding method. A polyethylene film consisting of a high-density polyethylene layer / medium-density polyethylene layer / high-density polyethylene layer was produced. The thickness of each of the high-density polyethylene layers was 20 μm, and the thickness of the medium-density polyethylene layer was 60 μm.
This polyethylene film is stretched in the longitudinal direction (MD) at a stretch ratio of 5 times, and a high-density polyethylene layer has a thickness of 4 μm and a medium-density polyethylene layer has a thickness of 12 μm, and has a total thickness of 20 μm. I got When the haze value of the intermediate layer was measured, the haze value was 8.9%.

１２ The polyethylene terephthalate film having a thickness of 12 μm was prepared as a substrate, and the substrate and the image forming surface of the intermediate layer were laminated using 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.

As the heat seal layer, the unstretched linear low-density polyethylene film having a thickness of 120 μm was prepared, and the heat seal layer and the intermediate layer were laminated using the two-part curable urethane-based adhesive. The laminate of the invention was obtained. 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 88% by mass.

<Example 11-3>
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.
This polyethylene film was stretched in the longitudinal direction (MD) and the width direction (TD) at a stretch ratio of 2.24 times to obtain an intermediate layer having a thickness of 20 μm. When the haze value of the intermediate layer was measured, the haze value was 5.1%.

<Example 11-4>
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.
This polyethylene film was stretched in the longitudinal direction (MD) at a stretch ratio of 5 times to obtain an intermediate layer having a thickness of 20 μm. When the haze value of the intermediate layer was measured, the haze value was 6.5%.

(4) A 20 nm-thick aluminum vapor-deposited film was formed on one surface of the substrate by a PVD method.

(4) The above-mentioned polyethylene terephthalate film having a thickness of 12 μm was prepared as a substrate, and the surface on which the vapor-deposited film was formed of the substrate and the above-mentioned intermediate layer were laminated using the above-mentioned 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.

<Example 11-5>
The procedure was carried out except that the adhesion between the surface of the base material on which the vapor-deposited film was formed and the above-mentioned intermediate layer was carried out using a two-part curable adhesive containing a polyester polyol and an isocyanate compound (PASLIM VM001 / VM102CP, manufactured by DIC Corporation). A laminate of the present invention was produced in the same manner as in Example 11-4.
The proportion of polyethylene in the laminate thus obtained was 88% by mass.

<Comparative Example 11-1>
The medium-density polyethylene was formed into a film by an inflation molding method to obtain an intermediate layer having a thickness of 20 μm. When the haze value of the intermediate layer was measured, the haze value was 23.5%.

As the heat seal layer, the unstretched linear low-density polyethylene film having a thickness of 120 μm is prepared, and the heat seal layer and the intermediate layer are laminated using the two-part curable urethane-based adhesive. I got a body. 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 88% by mass.

<Comparative Example 11-2>
The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare an intermediate layer composed of a high-density polyethylene layer / a medium-density polyethylene layer / a high-density polyethylene layer. The thickness of the high-density polyethylene layer was 4 μm, and the thickness of the medium-density polyethylene layer was 12 μm. When the haze value of the intermediate layer was measured, the haze value was 28.8%.

<Comparative Example 11-3>
A laminate was obtained in the same manner as in Example 11-1, except that the intermediate layer was changed to a nylon film having a thickness of 15 μm (trade name: Emblem ONBC, manufactured by Unitika Ltd.).
The proportion of polyethylene in the laminate thus obtained was 78% 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. Table 11 summarizes the evaluation results.
(Evaluation criteria)
：: The content of polyethylene in the laminate was 80% by mass or more.
X: The content of polyethylene in the laminate was less than 80% by mass.

<Heat resistance evaluation>
From the laminates obtained in the above Examples 11-1 to 11-5 and Comparative Examples 11-1 to 11-3, 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 Examples 11-1 to 11-5 and Comparative Examples 11-1 to 11-3, and this was used as a heat seal layer. It was folded into a V-shape so as to be on the outside, and was heat-sealed at 140 ° C. with the cylindrical body to form a bottom and a stand-pouch-shaped packaging material.
The prepared packaging material was visually observed and evaluated based on the following evaluation criteria. Table 11 summarizes the evaluation results.
(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>
Images formed on the polyethylene resin and the nylon film included in the laminates prepared in the above Examples and Comparative Examples were visually observed, and their printability was evaluated based on the following evaluation criteria. Table 11 summarizes the evaluation results.
(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. Table 11 summarizes the measurement results.

<Strength test>
Using the tensile tester (trade name: RTC-1310A, manufactured by Orientec Co., Ltd.), the laminates prepared in the above Examples and Comparative Examples were measured for the strength when a needle having a diameter of 0.5 mm was pierced. The piercing speed was 50 mm / min. Table 11 summarizes the measurement results.

<Bending load resistance test>
First, the oxygen permeability and the water vapor permeability of the laminates obtained in Examples 11-4 and 11-5 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.
Further, for the laminates obtained in Examples 4 and 5, a bending load (stroke: 155 mm, stroke: 155 mm, based on ASTM F392) using a gelbo flex tester (Tester Sangyo Co., Ltd., trade name: BE1006BE). Bending operation: 440 °) five times.
After the bending load, the oxygen permeability and the water vapor permeability of the laminate were measured.
Table 11 shows the oxygen permeability and the water vapor permeability of the laminate before and after the bending load test.

<Example 12-1>
Medium-density polyethylene (density: 0.941 g / cm ³ , melting point: 129 ° C., MFR: 1.3 g / 10 min, manufactured by Dow Chemical Company, trade name: Elite5538G) is formed into a film by an inflation molding method, and a polyethylene film having a thickness of 100 μm. I got
This polyethylene film was stretched in the longitudinal direction (MD) at a stretch ratio of 5 times to obtain an intermediate layer having a thickness of 20 μm. When the haze value of the intermediate layer was measured, the haze value was 6.5%.

A polyethylene terephthalate film having a thickness of 12 μm (manufactured by Toyobo Co., Ltd., trade name: E-5100) was prepared as a base material, and the base and the image forming surface of the intermediate layer A were two-part curable urethane. The layers were laminated using a system adhesive (trade name: RU-77T / H-7, manufactured by Rock Paint Co., Ltd.). The thickness of the adhesive layer formed by the two-component curable urethane-based adhesive was 3.0 μm.

As the heat seal layer, linear low-density polyethylene (density: 0.925, MFR: 1.9 g / 10 min, made of Prime Polymer, trade name: SP2520) and linear low-density polyethylene derived from biomass (density: 0) .916 g / cm ³ , MFR: 1.3 g / 10 min, biomass degree: 87%, manufactured by Braskem, trade name: SLL18), and formed into a film by an inflation molding method. A polyethylene film composed of a chain low-density polyethylene layer / a linear low-density polyethylene layer was produced.
The thickness of each of the linear low-density polyethylene layers was 30 μm, the thickness of the biomass-derived linear low-density polyethylene layer was 60 μm, and the total thickness was 120 μm. This is laminated with an intermediate layer on the image forming surface of the substrate A via a two-component curable urethane adhesive (trade name: RU-77T / H-7, manufactured by Rock Paint Co., Ltd.). The laminate of the invention was obtained. 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 88% by mass.

<Example 12-2>
A high-density polyethylene (density: 0.961 g / cm ³ , melting point 135 ° C., MFR: 0.7 g / 10 min, manufactured by ExxonMobil, trade name: HTA108) and the above-described medium-density polyethylene were formed into a film by an inflation molding method. A polyethylene film consisting of a high-density polyethylene layer / medium-density polyethylene layer / high-density polyethylene layer was produced. The thickness of each of the high-density polyethylene layers was 20 μm, and the thickness of the medium-density polyethylene layer was 60 μm.
This polyethylene film is stretched in the longitudinal direction (MD) at a stretch ratio of 5 times, and a high-density polyethylene layer has a thickness of 4 μm and a medium-density polyethylene layer has a thickness of 12 μm, and has a total thickness of 20 μm. I got When the haze value of the intermediate layer was measured, the haze value was 8.9%.

As the heat seal layer, the above-mentioned polyethylene film having a thickness of 120 μm was prepared, and the heat seal layer and the intermediate layer were laminated using the two-part 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 88% by mass.

<Example 12-3>
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.
This polyethylene film was stretched in the longitudinal direction (MD) and the width direction (TD) at a stretch ratio of 2.24 times to obtain an intermediate layer having a thickness of 20 μm. When the haze value of the intermediate layer was measured, the haze value was 5.1%.

<Example 12-4>
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.
This polyethylene film was stretched in the longitudinal direction (MD) at a stretch ratio of 5 times to obtain an intermediate layer having a thickness of 20 μm. When the haze value of the intermediate layer was measured, the haze value was 6.5%.

(4) The above polyethylene terephthalate film having a thickness of 12 μm was prepared as a base material, and an aluminum vapor-deposited film having a thickness of 0.02 μm was formed on one surface of the base material by a PVD method. The surface of the substrate on which the deposited film was formed and the intermediate layer were laminated using 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.

The above-mentioned polyethylene film having a thickness of 120 μm was prepared as a heat seal layer, and the heat seal layer and the intermediate layer were laminated using the two-liquid type 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 88% by mass.

<Example 12-5>
Except that the adhesion between the vapor-deposited film forming surface of the base material and the intermediate layer D was performed using a two-part curable adhesive containing a polyester polyol and an isocyanate compound (DIC Corporation, PASLIM VM001 / VM102CP). A laminate of the present invention was produced in the same manner as in Example 12-4.
The proportion of polyethylene in the laminate thus obtained was 88% by mass.

<Comparative Example 12-1>
The medium-density polyethylene was formed into a film by an inflation molding method to obtain an intermediate layer having a thickness of 20 μm. When the haze value of the intermediate layer was measured, the haze value was 23.5%.

The polyethylene film having a thickness of 120 μm was prepared as a heat seal layer, and the heat seal layer and the intermediate layer were laminated using the two-part 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 88% by mass.

<Comparative Example 12-2>
The high-density polyethylene and the medium-density polyethylene were formed into a film by an inflation molding method to prepare an intermediate layer composed of a high-density polyethylene layer / a medium-density polyethylene layer / a high-density polyethylene layer. The thickness of the high-density polyethylene layer was 4 μm, and the thickness of the medium-density polyethylene layer was 12 μm. When the haze value of the intermediate layer was measured, the haze value was 28.8%.

<Comparative Example 12-3>
A laminate was obtained in the same manner as in Example 12-1, except that the intermediate layer was changed to a nylon film having a thickness of 15 μm (trade name: Emblem ONBC, manufactured by Unitika Ltd.).
The proportion of polyethylene in the laminate thus obtained was 78% 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. Table 12 summarizes the evaluation results.
(Evaluation criteria)
：: The content of polyethylene in the laminate was 80% by mass or more.
X: The content of polyethylene in the laminate was less than 80% by mass.

<Heat resistance evaluation>
From the laminates obtained in the above Examples 12-1 to 12-5 and Comparative Examples 12-1 to 12-3, 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 laminates obtained in Examples 12-1 to 12-5 and Comparative examples 12-1 to 12-3, and this was used as a heat seal layer. It was folded into a V-shape so as to be on the outside, and was heat-sealed at 140 ° C. with the cylindrical body to form a bottom and a stand-pouch-shaped packaging material.
The prepared packaging material was visually observed and evaluated based on the following evaluation criteria. Table 12 summarizes the evaluation results.
(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>
Images formed on the polyethylene resin and the nylon film included in the laminates prepared in the above Examples and Comparative Examples were visually observed, and their printability was evaluated based on the following evaluation criteria. Table 12 summarizes the evaluation results.
(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. Table 12 summarizes the measurement results.

<Strength test>
Using the tensile tester (trade name: RTC-1310A, manufactured by Orientec Co., Ltd.), the laminates prepared in the above Examples and Comparative Examples were measured for the strength when a needle having a diameter of 0.5 mm was pierced. The piercing speed was 50 mm / min. Table 12 summarizes the measurement results.

<Bending load resistance test>
First, the oxygen permeability and the water vapor permeability of the laminates obtained in Examples 12-4 and 12-5 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.
Further, for the laminates obtained in Examples 4 and 5, a bending load (stroke: 155 mm, stroke: 155 mm, based on ASTM F392) using a gelbo flex tester (Tester Sangyo Co., Ltd., trade name: BE1006BE). Bending operation: 440 °) five times.
After the bending load, the oxygen permeability and the water vapor permeability of the laminate were measured.
Table 12 shows the oxygen permeability and the water vapor permeability of the laminate before and after the bending load test.

<Example 13-1>
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 multilayer substrate A having a thickness of 25 μm.
When the haze value of the multilayer substrate A was measured according to JIS K 7105, the haze value was 6.2%.

(4) An image was formed on one surface of the multilayer 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 polyethylene derived from biomass. 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-based adhesive (manufactured by Rock Paint Co., Ltd., trade name: RU) is used to form the image forming surface of the multilayer base material A and the layer of the linear low-density polyethylene A of the heat seal layer A. -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 13-1>
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 multilayer substrate a having a thickness of 25 μm comprising a layer (8.75 μm) and a high-density polyethylene layer (2.5 μm) was obtained.
When the haze value of the multilayer substrate a was measured in accordance with JIS K 7105, the haze value was 21.3%.

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

The image forming surface of the multilayer base material a and the layer made of the linear low-density polyethylene A of the heat seal layer A are laminated via the two-component 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 proportion of polyethylene in the laminate thus obtained was 95% by mass.

<Comparative Example 13-2>
A laminate was produced in the same manner as in Example 13-1, except that the multilayer base material A was changed to a biaxially stretched PET film having a thickness of 12 μm (trade name: E5100, manufactured by Toyobo Co., Ltd.).
The ratio of polyethylene in the laminate thus obtained was 75% by mass.

<Example 14-1>
The multilayer base material A was prepared.

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 multilayer 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 laminated. I got a body.
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 14-1>
The multilayer substrate a was prepared.

The image forming surface of the multilayer substrate 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 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 proportion of polyethylene in the laminate thus obtained was 97% by mass.

<Comparative Example 14-2>
A laminate was produced in the same manner as in Example 14-1, except that the multilayer base material A was changed to the above biaxially stretched PET film having a thickness of 12 μm.
The proportion of polyethylene in the thus obtained laminate was 86% by mass.

<Example 15-1>
The multilayer base material A was prepared.

(4) 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 multilayer 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 15-2>
In Example 15-1, the adhesion between the image forming surface of the multilayer base material A and the deposition surface of the heat seal layer A was determined by using a two-part curable adhesive containing a polyester polyol and an isocyanate compound (PASLIM, manufactured by DIC Corporation). VM15 / VM102CP), and a laminate of the invention was produced in the same manner as in Example 15-1.

<Comparative Example 15-1>
The multilayer substrate a was prepared.

The image forming surface of the multilayer 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.
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 15-2>
A laminate was produced in the same manner as in Example 15-1, except that the multilayer 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 16-1>
The multilayer base material A was prepared.

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 times 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.

{Circle around (2)} The image forming surface of the multilayer 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 16-2>
In Example 16-1, the adhesion between the image forming surface of the multilayer base material A and the deposition surface of the intermediate layer A was determined by a two-part curable adhesive containing a polyester polyol and an isocyanate compound (PASLIM VM001, manufactured by DIC Corporation). / VM102CP), and a laminate of the present invention was produced in the same manner as in Example 16-1.

<Comparative Example 16-1>
The multilayer substrate a was prepared.

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

膜 The above-mentioned 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.

{Circle around (2)} The image forming surface of the multilayer substrate 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.

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 16-2>
The laminated body was produced in the same manner as in Example 4-1 except that the stretched polyethylene film of the multilayer base material A and the intermediate layer A was changed to a biaxially stretched polyester film having a thickness of 12 μm (trade name: E5100, Toyobo Co., Ltd.). I got 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 13-1 and Comparative Examples 13-1 and 13-2, Examples 15-1 and 15-2 and Comparative Examples 15-1 and 15-2, and Examples 16-1 and 16-2 and Comparative Example 16 From the laminates obtained in -1 to 16-2, two test pieces each having a length of 80 mm and a width of 80 mm were prepared.
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 14-1 and Comparative Examples 14-1 and 14-2, 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 laminates obtained in Example 14-1 and Comparative Examples 14-1 and 14-2 so that 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 13 to 16.
(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 13 to 16.
(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 13 to 16.

<Strength test>
Using the tensile tester (trade name: RTC-1310A, manufactured by Orientec Co., Ltd.), the laminates prepared in the above Examples and Comparative Examples were measured for the strength when a needle having a diameter of 0.5 mm was pierced. The piercing speed was 50 mm / min. The measurement results are summarized in Tables 13 to 16.

<Bending load resistance test>
First, the oxygen of the laminates obtained in the above Examples 15-1 to 15-2, Comparative Examples 15-1 to 15-2, Examples 16-1 to 16-2 and Comparative Examples 16-1 to 16-2 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.
Further, the laminates obtained in Examples 15-1 and 15-2 and Comparative Examples 15-1 and 15-2, and Examples 16-1 and 16-2 and Comparative Examples 16-1 and 16-2, 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 15 and 16 show the oxygen permeability and water vapor permeability of the laminate before and after the bending load test.

10: laminated body, 11: base material, 12: heat seal layer, 13: evaporated film, 14: adhesive layer, 15: evaporated film, 16: intermediate layer substrate, 17: intermediate layer, 18: adhesive layer, 20: Laminate, 21: base material, 22: intermediate layer, 23: heat seal layer, 24: evaporated film, 25: adhesive layer, 30: packaging bag, 40: stand pouch, 41: trunk, 42: bottom

Claims

Comprising a base material and a heat seal layer,
The base material and the heat seal layer are made of the same material,
The same material is polyethylene,
The laminate, wherein the base material is a stretched resin film.
積層 The laminate according to claim 1, further comprising an adhesive layer between the substrate and the heat seal layer.
3. The laminate according to claim 1, wherein the heat seal layer includes a deposition film on a surface on the base material side. 4.
The deposited film is an aluminum deposited film,
The laminate according to claim 3, wherein the adhesive layer is formed of a cured product of a resin composition containing a polyester polyol and an isocyanate compound.
Provided with an intermediate layer between the base material and the heat seal layer,
The laminate according to any one of claims 1 to 4, wherein the intermediate layer includes a deposited film and an intermediate layer base material.
The laminate according to any one of claims 1 to 5, wherein at least one of the base material and the heat seal layer contains biomass-derived polyethylene as 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,
The laminate according to any one of claims 1 to 6, comprising a five-layer co-stretched stretched film.
With a base material, an intermediate layer, and a heat seal layer,
The substrate is composed of polyester,
The intermediate layer and the heat seal layer are made of the same material,
The same material is polyethylene,
The intermediate layer is a stretched resin film,
A laminate, wherein the thickness of the base material is smaller than the sum of the thickness of the intermediate layer and the thickness of the heat seal layer.
The laminate according to claim 8, wherein at least one of the intermediate layer and the heat seal layer contains biomass-derived polyethylene as polyethylene.
The laminate according to any one of claims 1 to 9, which is used for packaging materials.
包装 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.