JP2020055177A - Laminate, packaging material, packaging bag and stand pouch - Google Patents

Abstract

To provide a laminate that can achieve a packaging material that has strength and the like as a packaging material and also has excellent recyclability.SOLUTION: A laminate has a base material, an intermediate layer and a heat seal layer. The base material comprises polyester. The heat seal layer comprises polyethylene. The intermediate layer is a stretched film. At least one of the intermediate layer and the heat seal layer has, as polyethylene, biomass-derived polyethylene. A thickness of the base material is smaller than the sum of a thickness of the intermediate layer and a thickness of the heat seal layer.SELECTED DRAWING: Figure 1

Description

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

  BACKGROUND ART Conventionally, a resin film made of a resin material has been used as a constituent material of a packaging material. For example, a resin film composed of polyethylene has moderate flexibility and transparency, and is excellent in heat sealability, and thus is widely used as a packaging material.

  Usually, a resin film composed of polyethylene cannot be used as a base material because it is inferior in strength and heat resistance, and therefore, a usual packaging material is made of a resin material in which the base material and the heat seal layer are different. (For example, Patent Document 1).

  For example, conventionally, a laminated film including a polyester base, a polyamide resin layer, and a heat seal layer has been widely used.

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

JP 2009-202519 A

The present inventors have made it possible to improve the strength and heat resistance by forming a stretched film from polyethylene which has been conventionally used as a heat seal layer, and even if the polyamide resin layer included in the laminate is replaced, It has been found that the strength and heat resistance of the body can be maintained, and further, the recyclability of packaging materials and the like made of the laminate can be significantly improved.
Furthermore, it has been found that the use of biomass-derived polyethylene as the polyethylene can further reduce the environmental burden of the produced packaging material and the like.

The present invention has been made in view of the above findings, and a problem to be solved is to provide a laminate capable of realizing a packaging material having strength and the like as a packaging material and excellent in recyclability. That is.
Another object of the present invention is to provide a packaging material composed of the laminate.

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 heat seal layer is made of polyethylene,
The intermediate layer is a stretched film,
At least one of the intermediate layer and the heat seal layer contains, as polyethylene, polyethylene derived from biomass,
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.

  In one embodiment of the present invention, the intermediate layer and the heat seal layer contain biomass-derived polyethylene as polyethylene.

  In one embodiment of the present invention, the laminate further includes a deposited film between the base material and the intermediate layer.

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

  In one embodiment of the present invention, the 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 40 μm or more.

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

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

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

The packaging bag of the present invention is produced using the above laminate,
The thickness of the heat seal layer is not less than 20 μm and not more than 60 μm.

The stand pouch of the present invention is produced using the above-mentioned laminate,
The thickness of the heat seal layer is not less than 50 μm and not more than 200 μm.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body which can implement | achieve the packaging material which is excellent in recyclability while providing the strength etc. as a packaging material can be provided.

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

<Laminate>
A laminate according to the present invention will be described with reference to the drawings.
As shown in FIG. 1, the laminate 10 includes a base material 11, an intermediate layer 12, and a heat seal layer 13.

  Further, in one embodiment of the present invention, as shown in FIG. 2, the stacked body 10 can further include a vapor deposition film 14 between the base material 11 and the intermediate layer 12.

  Furthermore, in one embodiment of the present invention, as shown in FIG. 3, the laminate 10 is formed between the base material 11 or the deposited film 14 and the intermediate layer 12, and between the intermediate layer 12, The adhesive layer 15 may be further provided on at least one of the layers.

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, and more 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.

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

<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.

  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.

A stretched film made of polyester can be used as the substrate, and thereby 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 film may be a uniaxially stretched film or a biaxially stretched 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 polyester film by a T-die method or an inflation method, producing a film, and then stretching the film.

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

<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.
Furthermore, in the present invention, at least one of the polyethylene constituting the intermediate layer and the polyethylene constituting the heat sealing layer contains, as the polyethylene, polyethylene derived from biomass, whereby the packaging material produced by the laminate of the present invention Can be made less environmentally harmful.

For the intermediate layer, a stretched film made of polyethylene is used, whereby the heat resistance and strength of the laminate can be improved. In addition, the suitability for printing on the intermediate layer can be improved.
The stretched film may be a uniaxially stretched film or a biaxially stretched film.

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

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

  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 intermediate layer, polyethylene includes 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.
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 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 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 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.

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, 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, 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, A five-layer co-pressed film including a high-density polyethylene layer, a medium-density polyethylene layer and a high-density polyethylene layer may be used.
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.

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

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

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

  In the transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, examples of the transition metal include zirconium, titanium, and hafnium, and zirconium and hafnium are particularly preferred. The transition metal compound usually has two ligands each having a cyclopentadienyl skeleton, and it is preferable that each ligand having a cyclopentadienyl skeleton be bonded to each other by a crosslinking group. Examples of the cross-linking group include a substituted silylene group such as an alkylene group having 1 to 4 carbon atoms, a silylene group, a dialkylsilylene group, and a diarylsilylene group, and a substituted germylene group such as a dialkylgermylene group and a diarylgermylene group. Preferably, it is a substituted silylene group. As the transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, one kind or a mixture of two or more kinds can be used as a catalyst component.

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

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

  Further, a copolymer of ethylene and another monomer may be used as long as the properties of the present invention are not impaired. Examples of the ethylene copolymer include a copolymer composed of ethylene and an α-olefin having 3 to 20 carbon atoms. Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 4-methyl-1-pentene and 6-methyl- 1-heptene and the like. In addition, a copolymer with vinyl acetate or an acrylate ester may be used as long as the object of the present invention is not impaired.

In the present invention, the polyethylene constituting the intermediate layer is preferably biomass-derived polyethylene.
The biomass-derived polyethylene means a biomass-derived ethylene used as a raw material instead of ethylene obtained from a fossil fuel.
Since such biomass-derived polyethylene is a carb-neutral material, it can be used as a packaging material with even less environmental load.

In one embodiment, plant-derived ethylene is produced by fermenting a sugar solution or starch obtained from plants such as sugarcane, corn, sweet potato and the like with a microorganism such as yeast to produce bioethanol, and heating the bioethanol in the presence of a catalyst. Can be obtained.
As the polyethylene derived from biomass, commercially available polyethylene (eg, Green PE or the like commercially available from Braskem) may be used.

  Further, in one embodiment, polyethylene that is recycled by mechanical recycling can be used as the polyethylene. 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 intermediate layer may contain the above-mentioned additives as long as the properties of the present invention are not impaired.

  Further, it is preferable that the intermediate layer has been 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.

When the intermediate layer 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 intermediate layer is produced by an 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.

  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 provided in the laminate of the present invention is characterized in that it is made of polyethylene, similarly to the above-mentioned intermediate 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.
In the present invention, from the viewpoint of environmental load, the heat seal layer preferably contains biomass-derived polyethylene as polyethylene.
However, the intermediate 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.
Further, from the viewpoint of environmental load, recycled polyethylene can be used.

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

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

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, when producing a packaging bag 20 as shown in FIG. 4 that fills a content 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, when producing a stand pouch 30 as shown in FIG. 5 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. 4 and 5 are heat seal portions.

<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.

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

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

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

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

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

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

<Adhesive layer>
In one embodiment, the laminate of the present invention 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 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.

Further, in the case where a deposited film is formed between the deposited film and the intermediate layer, and when the deposited film is an aluminum deposited film, the adhesive layer is formed of a polyester polyol, an isocyanate compound, and a phosphoric acid-modified compound. It is preferred to be constituted by a cured product of a resin composition containing the resin composition.
With the adhesive layer having such a configuration, the oxygen barrier property and the water vapor barrier property of the laminate of the present invention can be further improved.
In addition, when a laminate provided with a vapor-deposited film is applied to a packaging material, a bending load is applied to the laminate by a molding machine or the like, so that a crack or the like may occur in the aluminum vapor-deposited film. By using the specific adhesive as described above, it is possible to suppress a decrease in the oxygen barrier property and the water vapor barrier property even when a crack occurs in the aluminum deposited film.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The thickness of the adhesive layer is preferably 0.5 μm or more and 6 μm or less, more preferably 0.8 μm or more and 5 μm or less, and even more preferably 1 μm or more and 4.5 μm or less.
By setting the thickness of the adhesive layer to 0.5 μm or more, the adhesiveness of the adhesive layer can be improved. Further, when an adhesive layer made of a cured product of a resin composition containing a polyester polyol, an isocyanate compound, and a phosphoric acid-modified compound is provided so as to be adjacent to an aluminum vapor-deposited film, the load resistance of the laminate is improved. be able to.
By setting the thickness of the adhesive layer to 6 μm or less, the workability of the laminate can be improved.

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

<Other layers>
The laminate of the present invention can be provided with a heat-resistant coat layer on a substrate.

  The heat-resistant coat layer contains at least one resin material, and examples thereof include polyester, polyolefin, cellulose resin, (meth) acrylic resin, urethane resin, and vinyl resin.

  The ratio of the resin material contained in the heat-resistant coat layer to the sum of the resin materials contained in the laminate is preferably 3% by mass or less, more preferably 1% by mass or less. Thereby, the heat resistance can be improved while maintaining the recyclability of the laminate of the present invention.

  The thickness of the heat-resistant coat layer is preferably 0.1 μm or more and 5 μm or less, more preferably 0.5 μm or more and 3 μm or less. Thereby, the heat resistance can be improved while maintaining the recyclability of the laminate of the present invention.

<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 20 as shown in FIG. 6 or a stand pouch 30 having a body 31 and a bottom 32 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>
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 A having a thickness of 20 µm. When the haze value of the intermediate layer A was measured, the haze value was 6.5%.

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

  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 material and the image forming surface of the intermediate layer A were two-part curable urethane. Lamination was performed using a system adhesive (manufactured by Rock Paint Co., Ltd., trade name: RU-77T / H-7). 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 the intermediate layer A on the image forming surface of the substrate A via a two-component curable urethane-based adhesive (trade name: RU-77T / H-7, manufactured by Rock Paint Co., Ltd.) The laminate of the present 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 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. B was obtained. When the haze value of the intermediate layer B was measured, the haze value was 8.9%.

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

  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 B 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 above-mentioned polyethylene film having a thickness of 120 μm was prepared, and the heat seal layer and the intermediate layer B were laminated using the two-part curable urethane-based adhesive to obtain a laminate of the present invention. 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 88% by mass.

<Example 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 C having a thickness of 20 μm. When the haze value of the intermediate layer C was measured, the haze value was 5.1%.

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

  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 C 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 C were laminated using the two-part curable urethane-based adhesive to obtain a laminate of the present invention. 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 88% by mass.

<Example 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 D having a thickness of 20 μm. When the haze value of the intermediate layer D was measured, the haze value was 6.5%.

  On one surface of the substrate, an aluminum vapor-deposited film having a thickness of 0.02 μm was formed by a PVD method.

  The polyethylene terephthalate film having a thickness of 12 μm was prepared as a substrate, and the surface on which the deposited film was formed of the substrate and the intermediate layer D 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-sealing layer, and the heat-sealing layer and the intermediate layer D were laminated using the above-mentioned two-component 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 5>
Bonding between the surface of the base material on which the vapor-deposited film is formed and the intermediate layer D is performed by using a two-part curable adhesive containing an isocyanate compound and a phosphoric acid-modified compound (PASLIM VM001 / VM102CP manufactured by DIC Corporation). In the same manner as in Example 4, a laminate of the present invention was produced.
The proportion of polyethylene in the laminate thus obtained was 88% by mass.

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

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

  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 a 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 polyethylene film having a thickness of 120 μm was prepared as a heat seal layer, and the heat seal layer and the intermediate layer a 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 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 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. When the haze value of the intermediate layer b was measured, the haze value was 28.8%.

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

  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 b 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 polyethylene film having a thickness of 120 μm was prepared as a heat seal layer, and the heat seal layer and the intermediate layer b 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 3>
A laminate was obtained in the same manner as in Example 1, except that the intermediate layer A 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. 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 Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-3, 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, from the laminates obtained in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-3, one test piece having a length of 110 mm and a width of 150 mm was prepared, 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. The evaluation results are summarized in Table 1.
(Evaluation criteria)
：: No wrinkles or the like were generated on the surface of the packaging material, and no adhesion to the heat seal bar was observed.
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. The evaluation results are summarized in Table 1.
(Evaluation criteria)
：: Good dimensional stability at the time of printing, and a good image free from rubbing, bleeding, etc. could be formed.
X: 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 1 summarizes the measurement results.

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

<Bending load resistance test>
First, the oxygen permeability and the water vapor permeability of the laminates obtained in Examples 4 and 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, using a gelbo flex tester (manufactured by Tester Sangyo Co., Ltd., trade name: BE1006BE)) in accordance with ASTM F392. Bending operation: 440 °) five times.
After the bending load, the oxygen permeability and the water vapor permeability of the laminate were measured.
Table 1 shows the oxygen permeability and the water vapor permeability of the laminate before and after the bending load test.

10: laminated body, 11: base material, 12: intermediate layer, 13: heat seal layer, 14: deposited film, 15: adhesive layer, 20: packaging bag, 30: stand pouch, 31: trunk, 32: bottom

Claims (10)

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 polyethylene,
The intermediate layer is a stretched film,
At least one of the polyethylene constituting the intermediate layer and the heat sealing layer contains biomass-derived polyethylene,
A laminate, wherein 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.   2. The laminate according to claim 1, wherein each of the polyethylene constituting the intermediate layer and the heat seal layer contains biomass-derived polyethylene. 3.   The laminate according to claim 1, further comprising a vapor-deposited film between the base material and the intermediate layer. Further comprising an adhesive layer between the deposited film and the intermediate layer,
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, an isocyanate compound, and a phosphoric acid-modified compound.   The laminate according to any one of claims 1 to 4, wherein a difference between a thickness of the base material and a sum of a thickness of the intermediate layer and a thickness of the heat seal layer is 40 µm or more.   The laminate according to any one of claims 1 to 5, wherein the content of the polyethylene in the entire laminate is 80% by mass or more.   The laminate according to any one of claims 1 to 6, which is used for packaging materials.   A packaging material produced using the laminate according to any one of claims 1 to 7. A packaging bag,
It is produced using the laminate according to any one of claims 1 to 7,
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 7,
A stand pouch, wherein the thickness of the heat seal layer is 50 μm or more and 200 μm or less.

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