JP2020158191A - Base material, laminate, packaging material, packaging bag, and stand pouch - Google Patents

Abstract

To provide a base material which enables manufacturing of a packaging material having sufficient strength and barrier property for a packaging material while being excellent in recyclability.SOLUTION: A base material is made from a film which is constituted of polyethylene, with the film having been subjected to stretching treatment and at least one surface of the film having been subjected to electron beam irradiation treatment. The polyethylene contains biomass-derived polyethylene.SELECTED DRAWING: Figure 1

Description

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

Conventionally, a resin film composed of a resin material has been used as a material constituting a packaging material. For example, a resin film composed of polyolefin is widely used as a packaging material because it has appropriate flexibility and transparency and is excellent in heat-sealing property.

Normally, a resin film made of polyolefin is inferior in strength and heat resistance, so it cannot be used as a base material for making packaging materials, etc., and is attached to a resin film made of polyester, polyamide, etc. Therefore, the usual packaging material is composed of a laminate in which the base material and the heat-sealing layer are made of different kinds of resin materials (for example, Patent Document 1).

In recent years, with the growing demand for the construction of a recycling-oriented society, packaging materials and the like are required to be highly recyclable. However, the conventional packaging material is composed of different types of resin materials as described above, and it is difficult to separate each resin material, so that the packaging material is not recycled at present.

Japanese Unexamined Patent Publication No. 2009-202519

The present inventors significantly improve the strength and heat resistance of a polyolefin film, specifically a polyethylene film, which has been conventionally used as a heat seal layer, by subjecting it to a stretching treatment and an electron beam irradiation treatment. It was found that it can be used as a base material for packaging materials.
Further, by laminating the base material with a heat seal layer made of polyethylene to form a laminate, a laminate having high strength and heat resistance and capable of producing a recyclable packaging material or the like can be obtained. I got the finding that it can be done.

The present invention has been made in view of the above findings, and the problem to be solved is to produce a packaging material having sufficient strength and barrier properties as a base material for a packaging material and also having excellent recyclability. It is to provide a substrate that makes it possible.

Another problem to be solved by the present invention is to provide a laminate provided with the base material.

Furthermore, an object to be solved by the present invention is to provide a packaging material, a packaging bag and a stand pouch composed of the laminate.

The substrate of the present invention comprises a film composed of polyethylene.
The film has been stretched and has been stretched.
At least one surface of the film is subjected to electron beam irradiation treatment.
The polyethylene is characterized by containing biomass-derived polyethylene.

In one embodiment, the thickness of the substrate of the present invention is 10 μm or more and 50 μm or less.

In one embodiment, the stretching ratio of the substrate of the present invention in the longitudinal direction and / or the lateral direction is 2 times or more and 10 times or less.

The laminate of the present invention comprises the above-mentioned base material and a heat-sealing layer.
The base material is provided so that the electron beam irradiation surface of the base material is the outermost surface.
The heat-sealing layer is made of polyethylene.

In one embodiment, the heat seal layer comprises polyethylene derived from biomass.

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

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

The packaging bag of the present invention is composed of the above laminated body.
The heat seal layer is characterized in that the thickness is 20 μm or more and 60 μm or less.

The stand pouch of the present invention is composed of the above laminated body.
The heat seal layer is characterized in that the thickness is 50 μm or more and 200 μm or less.

According to the present invention, it is possible to provide a base material having sufficient strength and barrier properties to be applied as a base material for a packaging material and capable of producing a packaging material having excellent recyclability.

It is sectional drawing which shows one Embodiment of the base material of this invention. It is sectional drawing which shows one Embodiment of the base material of this invention. It is sectional drawing which shows one Embodiment of the laminated body of this invention. It is sectional drawing which shows one Embodiment of the laminated body of this invention. It is a perspective view which shows one Embodiment of the packaging material produced using the laminated body of this invention. It is a perspective view which shows one Embodiment of the packaging material produced using the laminated body of this invention.

(Base material)
The base material of the present invention is a film made of polyethylene, which is characterized by being stretched and at least one surface thereof being subjected to electron beam irradiation treatment.
As described above, the heat resistance and strength of the film can be remarkably improved by stretching the film made of polyethylene and irradiating at least one surface of the film with an electron beam to improve the cross-linked density of the polyethylene. It can satisfy the physical properties required as an outer layer such as a packaging material.

As the polyethylene, high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene and ultra low density polyethylene can be used.
Among these, high-density polyethylene and medium-density polyethylene are preferable from the viewpoint of strength and heat resistance of the base material, and medium-density polyethylene is more preferable from the viewpoint of stretchability.

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

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

The above-mentioned single-site catalyst is a catalyst capable of forming a uniform active species, and is usually prepared by contacting a metallocene-based transition metal compound or a non-metallocene-based transition metal compound with an activation co-catalyst. .. A single-site catalyst is preferable because it has a uniform active site structure as compared with a multi-site catalyst, and thus can polymerize a polymer having a high molecular weight and a high uniformity structure. As the single-site catalyst, it is particularly preferable to use a metallocene-based catalyst. The metallocene-based catalyst is a catalyst containing a transition metal compound of Group IV of the Periodic Table, which contains a ligand having a cyclopentadienyl skeleton, a cocatalyst, an organometallic compound if necessary, and each catalyst component of the carrier. is there.

In the transition metal compound of Group IV of the Periodic Table containing the ligand having the cyclopentadienyl skeleton, the cyclopentadienyl skeleton is a cyclopentadienyl group, a substituted cyclopentadienyl group or the like. .. The substituted cyclopentadienyl group includes 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. 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 an indenyl ring, a fluorenyl ring, an azulenyl ring, a hydrogenator thereof, etc. are formed. It may be formed. Rings formed by bonding substituents to each other may further have substituents 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 preferable. The transition metal compound usually has two ligands having a cyclopentadienyl skeleton, and the ligands having each cyclopentadienyl skeleton are preferably bonded to each other by a cross-linking 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 dialkyl silylene group and a diaryl silylene group, and a substituted gel millene group such as a dialkyl gel millene group and a diaryl gel millene group. It is preferably a substituted silylene group. The above-mentioned transition metal compound of Group IV of the Periodic Table containing a ligand having a cyclopentadienyl skeleton can have one or a mixture of two or more as a catalyst component.

The co-catalyst is one in which the transition metal compound of Group IV of the periodic table can be effectively used as a polymerization catalyst, or the ionic charge in a catalytically activated state can be equalized. As co-catalysts, benzene-soluble organoxane of organoaluminum oxy compounds, benzene-insoluble organoaluminum oxy compounds, ion-exchange layered silicates, boron compounds, cations containing or not containing active hydrogen groups and non-coordinating anions are used. Examples thereof include ionic compounds, lanthanoid salts such as lanthanum oxide, tin oxide, and phenoxy compounds containing a fluoro group.

The transition metal compound of Group IV of the Periodic Table, which contains a ligand having a cyclopentadienyl skeleton, may be used by supporting it on a carrier of an inorganic or organic compound. The carrier is preferably an inorganic or organic compound porous oxide, and specifically, an ion-exchangeable 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, etc. or a mixture thereof can be mentioned. Further, examples of the organometallic compound used as necessary include organoaluminum compounds, organomagnesium compounds, and organozinc compounds. Of these, organoaluminum is preferably used.

Further, a copolymer of ethylene and another monomer can be used as long as the characteristics 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, and examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene and 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. Further, as long as the object of the present invention is not impaired, it may be a copolymer with vinyl acetate, acrylic acid ester or the like.

Further, in the present invention, the base material contains polyethylene derived from biomass.
Biomass-derived polyethylene uses biomass-derived ethylene as a raw material for obtaining the above-mentioned polyethylene, instead of ethylene obtained from fossil fuels.

In one embodiment, plant-derived ethylene is produced by fermenting sugar solution or starch obtained from plants such as sugar cane, corn, and sweet potato with a microorganism such as yeast to produce bioethanol, which is heated in the presence of a catalyst. Can be obtained by doing.
Further, as the biomass-derived polyethylene, commercially available polyethylene (for example, green PE commercially available from Braskem) may be used.

The content of biomass-derived polyethylene in the base material is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably 70% by mass or more.

It is also possible to use polyethylene recycled by mechanical recycling. Here, mechanical recycling generally refers to crushing a recovered polyethylene film or the like, alkaline cleaning to remove stains and foreign substances on the film surface, and then drying the film under high temperature and reduced pressure for a certain period of time to stay inside the film. This is a method of diffusing pollutants, decontaminating, removing stains on a film made of polyethylene, and returning the film to polyethylene.

The base material can contain additives as long as the properties of the present invention are not impaired, and for example, a cross-linking agent, an antioxidant, an anti-blocking agent, a slip agent, an ultraviolet absorber, a light stabilizer, and a filling. Examples include agents, reinforcing agents, antistatic agents, pigments and modifying resins.

In one embodiment, the substrate of the present invention has a multi-layer structure.
In one embodiment, the substrate of the present invention comprises a layer composed of high-density polyethylene (hereinafter referred to as high-density polyethylene layer), a layer composed of medium-density polyethylene (hereinafter referred to as medium-density polyethylene layer), and the like. It includes a layer made of high-density polyethylene (hereinafter referred to as a high-density polyethylene layer).
With such a configuration, the strength and heat resistance of the base material can be further improved while maintaining the stretchability of the base material.
At this time, the thickness of the high-density polyethylene layer is preferably thinner than the thickness of the medium-density polyethylene layer.
The ratio of the thickness of the high-density polyethylene layer to the thickness of the medium-density polyethylene layer is preferably 1/10 or more and 1/1, and more preferably 1/5 or more and 1/2 or less.
By setting the ratio of the thickness of the high-density polyethylene layer to the thickness of the medium-density polyethylene layer to 1/10 or more, the strength and heat resistance of the base material 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 base material can be further improved.

In one embodiment, the substrate is a high density polyethylene layer, a medium density polyethylene layer, a low density polyethylene layer, a linear low density polyethylene layer or an ultralow density polyethylene layer (in this paragraph, for simplification of description). , Collectively referred to as a low-density polyethylene layer), a medium-density polyethylene layer, and a high-density polyethylene layer.
With such a configuration, the stretchability of the base material can be improved. In addition, the strength and heat resistance of the base material can be improved. In addition, it is possible to prevent the occurrence of curl on the base material. Further, the production efficiency of the base material can be improved.
At this time, the thickness of the high-density polyethylene layer is preferably thinner than the thickness of the medium-density polyethylene layer.
The ratio of the thickness of the high-density polyethylene layer to the thickness of the medium-density polyethylene layer is preferably 1/10 or more and 1/1, and more preferably 1/5 or more and 1/2 or less.
By setting the ratio of the thickness of the high-density polyethylene layer to the thickness of the medium-density polyethylene layer to 1/10 or more, the strength and heat resistance of the base material 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 base material 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 thicker 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, and more preferably 1 / 0.5 or more and 1/1 or less. preferable.
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, the heat resistance of the base material can be improved. Further, 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, a substrate having such a configuration can be produced, for example, by an inflation method.
Specifically, from the outside, the high-density polyethylene, the medium-density polyethylene layer, and the low-density polyethylene layer, the linear low-density polyethylene layer, or the ultra-low-density polyethylene layer are co-extruded in a tubular shape and then opposed to each other. It can be produced by crimping a low-density polyethylene layer, a linear low-density polyethylene layer, or an ultra-low-density polyethylene layer with each other with a rubber roll or the like.
By manufacturing by such a method, the number of defective products in manufacturing can be remarkably reduced, and finally, the production efficiency can be improved.
Further, in the inflation film forming machine, stretching can also be performed, whereby the production efficiency can be further improved.

The base material may be a uniaxially stretched film or a biaxially stretched film.
The stretching ratio in the longitudinal direction (MD) of the base material is preferably 2 times or more and 10 times or less, and preferably 3 times or more and 7 times or less.
By setting the draw ratio in the longitudinal direction (MD) of the base material to 2 times or more, the strength and heat resistance of the base material of the present invention can be improved. Further, the printability on the base material can be improved. In addition, the transparency of the base material can be improved. On the other hand, the upper limit of the draw ratio in the longitudinal direction (MD) of the base material is not particularly limited, but is preferably 10 times or less from the viewpoint of the breaking limit of the base material.
Further, the stretching ratio in the lateral direction (TD) of the base material is preferably 2 times or more and 10 times or less, and preferably 3 times or more and 7 times or less.
By setting the stretching ratio of the base material in the lateral direction (TD) to 2 times or more, the strength and heat resistance of the base material of the present invention can be improved. Further, the printability on the base material can be improved. In addition, the transparency of the base material can be improved. On the other hand, the upper limit of the stretching ratio in the lateral direction (TD) of the base material is not particularly limited, but is preferably 10 times or less from the viewpoint of the breaking limit of the base material.

As shown in FIG. 1, the base material 10 may have polyethylene on one surface whose cross-linking density has been improved by electron beam irradiation, and as shown in FIG. 2, the cross-linked polyethylene in the entire base material 10 may be cross-linked. There may be one with improved density.
Further, when the base material has a multilayer structure, it is sufficient that the crosslink density of polyethylene in the outermost layer is at least improved by electron beam irradiation.
From the viewpoint of strength and heat resistance, it is preferable that the cross-linked density of polyethylene as a whole is improved by electron beam irradiation.

As a device that can be used for irradiating the base material with an electron beam, a conventionally known device can be used, for example, a curtain type electron irradiating device (LB1023, manufactured by iElectron Beam Co., Ltd.), a line irradiation type low energy. An electron beam irradiator (EB-ENGINE, manufactured by Hamamatsu Photonics Co., Ltd.) and a drum roll type electron beam irradiator (EZ-CURE, manufactured by Eye Electron Beam Co., Ltd.) can be preferably used.

The dose of the electron beam irradiated to the base material is preferably in the range of 10 kGy or more and 2000 kGy or less, and more preferably in the range of 20 kGy or more and 1000 kGy or less.
The accelerating voltage of the electron beam is preferably in the range of 30 kV or more and 300 kV or less, more preferably in the range of 50 kV or more and 300 kV or less, and further preferably in the range of 50 kV or more and 250 kV or less.
The irradiation energy of the electron beam is preferably in the range of 20 keV or more and 750 keV or less, more preferably in the range of 25 keV or more and 500 keV or less, further preferably in the range of 30 keV or more and 400 keV or less, and more preferably 20 keV or more and 200 keV or less. The following range is particularly preferable.

The oxygen concentration in the electron beam irradiator is preferably 500 ppm or less, more preferably 100 ppm or less. By performing electron beam irradiation under such conditions, it is possible to suppress the generation of ozone and suppress the radicals generated by electron beam irradiation from being inactivated by oxygen in the atmosphere. it can. Such conditions can be achieved, for example, by creating an atmosphere of an inert gas (nitrogen, argon, etc.) in the apparatus.

In one embodiment, the electron beam irradiation can be performed at the same time as cooling by using a cooling drum or the like.

Further, the base material may be surface-treated. As a result, the adhesion to the adjacent layer can be improved when the following laminated body is formed.
The surface treatment method is not particularly limited, and 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. Examples include chemical treatment such as treatment.
Further, an anchor coat layer may be formed on the surface of the base material by using a conventionally known anchor coat agent.

An image may be formed on the surface of the base material of the present invention, and the formed image is not particularly limited, and characters, patterns, symbols, combinations thereof, and the like are represented.
The image formation on the base material is preferably performed using an ink derived from biomass, whereby a packaging material or the like having a lower environmental load can be produced using the base material of the present invention.
The method for forming an image is not particularly limited, and examples thereof include conventionally known printing methods 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.

In one embodiment, the substrate of the present invention may have a vapor deposition film on its surface. Thereby, the gas barrier property of the base material, specifically, the oxygen barrier property and the water vapor barrier property can be improved.

The vapor-deposited film includes a metal such as aluminum and an inorganic oxide such as aluminum oxide, silicon oxide, magsium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, and barium oxide. Can be mentioned.

The thickness of the thin-film deposition film is preferably 1 nm or more and 150 nm or less, more preferably 5 nm or more and 60 nm or less, and further preferably 10 nm or more and 40 nm or less.
By setting the thickness of the thin-film deposition film to 1 nm or more, the oxygen barrier property and the water vapor barrier property of the base material can be further improved. Further, by setting the thickness of the thin-film deposition film to 150 nm or less, it is possible to prevent the occurrence of cracks in the thin-film deposition film. Further, when the base material of the present invention is applied to the following laminate, its recyclability can be maintained.

In one embodiment, the substrate of the present invention comprises a barrier coat layer, which can improve the oxygen barrier property and the water vapor barrier property of the substrate.
When the base material includes a thin-film deposition film, the barrier coat layer may be provided on the vapor-deposited film or below the thin-film deposition film.

In one embodiment, the barrier coat layer is a polyamide, polyester, such as ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol, polyacrylonitrile, nylon 6, nylon 6,6 and polymethoxylylen adipamide (MXD6). Includes polyurethane and gas barrier resins such as (meth) acrylic resins. Among these, polyvinyl alcohol is preferable from the viewpoint of oxygen barrier property and water vapor barrier property.
Further, when the vapor-deposited film is composed of an inorganic oxide, the occurrence of cracks in the vapor-deposited film can be effectively prevented by containing polyvinyl alcohol in the barrier coat layer.

The content of the gas barrier resin in the barrier coat layer is preferably 50% by mass or more and 95% by mass or less, and more preferably 75% by mass or more and 90% by mass or less. By setting the content of the gas barrier resin in the barrier coat layer to 50% by mass or more, the oxygen barrier property and the water vapor barrier property of the base material of the present invention can be further improved.

The barrier coat layer can contain the above additives as long as the characteristics of the present invention are not impaired.

The thickness of the barrier coat layer is preferably 0.01 μm or more and 10 μm or less, and more preferably 0.1 μm or more and 5 μm or less.
By setting the thickness of the barrier coat layer to 0.01 μm or more, the oxygen barrier property and the water vapor barrier property of the base material of the present invention can be further improved. By setting the thickness of the barrier coat layer to 10 μm or less, the recyclability can be maintained when the base material of the present invention is applied to the following laminate.

The barrier coat layer can be formed by dissolving or dispersing the above-mentioned material in water or a suitable solvent, applying the material, and drying the material. The barrier coat layer can also be formed by applying a commercially available barrier coat agent and drying it.

Further, in another embodiment, the barrier coat layer is a metal alkoxide obtained by polycondensing a mixture of a metal alkoxide and a water-soluble polymer by a sol-gel method in the presence of a sol-gel method catalyst, water, an organic solvent, or the like. It is a gas barrier coating film containing at least one resin composition such as a hydrolyzate of the above or a hydrolyzed condensate of a metal alkoxide.
When the base material of the present invention includes a thin-film deposition film composed of an inorganic oxide, the barrier coat layer of this form is provided adjacent to the thin-film deposition film to effectively prevent the occurrence of cracks in the thin-film deposition film. can do.

In one embodiment, the metal alkoxide is represented by the following general formula.
R ¹ _n M (OR ² ) _m
(However, in the formula, R ¹ and R ² each represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, and m represents an integer of 1 or more. , N + m represents the valence of M.)

As the metal atom M, for example, silicon, zirconium, titanium, aluminum and the like can be used.
Examples of the organic group represented by R ¹ and R ² include alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group and i-butyl group. Can be done.

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

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

Two or more kinds of the above-mentioned silane coupling agent may be used, and the silane coupling agent is used within the range of about 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the above-mentioned alkoxide. Is preferable.

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

The content of the water-soluble polymer in the gas barrier coating film is preferably 5 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the metal alkoxide.
By setting the content of the water-soluble polymer in the gas barrier coating film to 5 parts by mass or more with respect to 100 parts by mass of the metal alkoxide, the oxygen barrier property and the water vapor barrier property of the base material of the present invention can be further improved. it can. Further, by setting the content of the water-soluble polymer in the gas barrier coating film to 500 parts by mass or less with respect to 100 parts by mass of the metal alkoxide, the film forming property of the gas barrier coating film can be improved.

The thickness of the gas barrier coating film is preferably 0.01 μm or more and 100 μm or less, and more preferably 0.1 μm or more and 50 μm or less. Thereby, the oxygen barrier property and the water vapor barrier property can be further improved while maintaining the recyclability.
By setting the thickness of the gas barrier coating film to 0.01 μm or more, the oxygen barrier property and the water vapor barrier property of the base material of the present invention can be improved. Further, when it is provided adjacent to the thin-film deposition film composed of an inorganic oxide, it is possible to prevent the occurrence of cracks in the thin-film deposition film.

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

The composition may further contain an acid. The acid is used as a catalyst for the sol-gel process, mainly as a catalyst for hydrolysis of alkoxides, silane coupling agents and the like.
As the acid, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid and tartaric acid are used. The amount of the acid used is preferably 0.001 mol or more and 0.05 mol or less with respect to the total molar amount of the alkoxide content (for example, the silicate portion) of the alkoxide and the silane coupling agent.
The catalytic effect can be improved by setting the amount of the acid to be 0.001 mol or more with respect to the total molar amount of the alkoxide content (for example, the silicate portion) of the alkoxide and the silane coupling agent. Further, the thickness of the gas barrier coating film formed can be made uniform by setting the total molar amount of the alkoxide and the silane coupling agent (for example, the silicate portion) to 0.05 mol or less. it can.

Further, the composition may contain water at a ratio of preferably 0.1 mol or more and 100 mol or less, more preferably 0.8 mol or more and 2 mol or less, based on 1 mol of the total molar amount of alkoxide. preferable.
By setting the water content to 0.1 mol or more with respect to 1 mol of the total molar amount of alkoxide, the oxygen barrier property and the water vapor barrier property of the laminate of the present invention can be improved. Further, by setting the water content to 100 mol or more with respect to 1 mol of the total molar amount of alkoxide, the hydrolysis reaction can be carried out rapidly.

Moreover, the said composition may contain an organic solvent. As the organic solvent, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol and the like can be used.

Hereinafter, an embodiment of a method for forming a gas barrier coating film will be described below.
First, a composition is prepared by mixing a metal alkoxide, a water-soluble polymer, a sol-gel method catalyst, water, an organic solvent and, if necessary, a silane coupling agent. The polycondensation reaction gradually proceeds in the composition.
Next, the composition is applied and dried on the polyolefin resin layer by the above-mentioned conventionally known method. By this drying, the polycondensation reaction of the alkoxide and the water-soluble polymer (and the silane coupling agent if the composition contains a silane coupling agent) further proceeds to form a layer of the composite polymer.
Finally, the gas barrier coating film can be formed by heating the composition at a temperature of 20 to 250 ° C., preferably 50 to 220 ° C. for 1 second to 10 minutes.

An image may be formed on the surface of the barrier coat layer. The method of forming the image is as described above.

The thickness of the base material is preferably 10 m 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 required for a base material such as a packaging material can be sufficiently satisfied. Further, by setting the thickness of the base material to 50 μm or less, the processability of the base material can be improved.

The base material can be produced by forming a film of a resin composition containing at least polyethylene by using a T-die method, an inflation method, or the like, forming a resin film, and then stretching and irradiating with an electron beam.
By forming a film by the inflation method, the resin film can be stretched at the same time.
The resin film may be stretched or irradiated with an electron beam first, but it is preferable to stretch the resin film first because of its suitability for stretching.

When the base material is produced by the T-die method, the MFR of the resin composition is preferably 3 g / 10 minutes or more and 20 g / 10 minutes or less.
By setting the MFR of the resin composition to 3 g / 10 minutes or more, the processability of the base material of the present invention can be improved. Further, by setting the MFR of the resin composition to 20 g / 10 minutes or less, it is possible to prevent the base material from breaking.

When the base material is produced by the inflation method, the MFR of the resin composition is preferably 0.5 g / 10 minutes or more and 5 g / 10 minutes or less.
By setting the MFR of the resin composition to 0.5 g / 10 minutes or more, the processability of the base material of the present invention can be improved. Further, by setting the MFR of the resin composition to 5 g / 10 minutes or less, the film-forming property can be improved.

The formation of the vapor deposition film on the substrate can be carried out by using a conventionally known method, for example, a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method and an ion plating method, PVD. (Method), and chemical vapor deposition methods (Chemical Vapor Deposition method, CVD method) such as plasma chemical vapor deposition method, thermochemical vapor deposition method, and photochemical vapor deposition method can be mentioned.

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

The surface of the vapor-deposited film is preferably subjected to the above surface treatment. Thereby, when applied to the following laminated body, the adhesion with the adjacent layer can be improved.

(Laminated body)
As shown in FIG. 3, the laminate 11 of the present invention includes the base material 10 and the heat seal layer 12.
Further, the heat seal layer included in the laminate of the present invention is made of polyethylene, and by having such a configuration, the recyclability of the laminate can be improved.

In one embodiment, the laminate 11 of the present invention includes an intermediate layer 13 between the base material 10 and the heat seal layer 12, as shown in FIG.

In one embodiment, the laminate of the present invention may include an adhesive layer 14 between any layers, as shown in FIGS. 3 and 4.

The content of polyethylene in the entire laminate of the present invention is preferably 90% by mass or more, and more preferably 90% by mass or more.
By setting the polyethylene content 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.

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

(Base material)
In the laminated body, the base material is provided so that the electron beam irradiation surface is the outermost surface. Since the details of the composition of the base material have been described above, they will be omitted here.

(Heat seal layer)
The heat seal layer is characterized in that it is made of polyethylene. Since the laminate of the present invention is composed of a base material composed of polyethylene and a heat-sealing layer, the recyclability of packaging materials and the like produced by using the laminate can be improved.
However, the heat seal layer is formed by an unstretched polyolefin resin film or by melt extrusion of polyolefin.

From the viewpoint of heat-sealing property, it is preferable to use low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene as the polyethylene.
The heat seal layer preferably contains polyethylene derived from biomass.
It is also possible to use mechanically recycled polyethylene.

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, straight chain. It can be composed of a layer containing at least one of a low density polyethylene and an ultra low density polyethylene.
Further, the intermediate layer may be a layer composed of polyethylene derived from biomass.
With the above configuration, it is possible to further improve the bag-making suitability and strength of the laminate of the present invention while maintaining the heat-sealing property.

The thickness of the heat seal layer is preferably changed as appropriate 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 a packaging bag as shown in FIG. 5 filled with contents of 1 g or more and 200 g or less is produced, 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 damage to 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 a stand pouch as shown in FIG. 6 filled with contents of 50 g or more and 2000 g or less is produced, 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 damage to 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 shaded areas in FIGS. 5 and 6 are heat-sealed parts.

The heat seal layer may be provided with a vapor-deposited film on the surface on the substrate side. By providing the vapor-deposited film, the oxygen barrier property and the water vapor barrier property can be improved.

The vapor-deposited film includes a metal such as aluminum and an inorganic oxide such as aluminum oxide, silicon oxide, magsium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, and barium oxide. Can be mentioned.

The thickness of the thin-film film is preferably 1 nm or more and 150 nm or less, more preferably 5 nm or more and 60 nm or less, and further preferably 10 nm or more and 40 nm or less.

The method for forming the vapor-deposited film is as described above.

The surface of the vapor-deposited film is preferably subjected to the above surface treatment. As a result, the adhesion to the adjacent layer can be improved.

(Mesosphere)
In one embodiment, the intermediate layer comprises a stretched polyethylene film, which can further improve the strength of the laminate of the present invention.
The stretched polyethylene film is composed of polyethylene, and high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene can be used.
The stretched polyethylene film preferably contains polyethylene derived from biomass.
It is also possible to use mechanically recycled polyethylene.

Further, the stretched polyethylene film may have the above-mentioned multilayer structure.

The stretched polyethylene film may be a uniaxially stretched film or a biaxially stretched film, and the preferable stretch ratio is as described above.

The thickness of the stretched polyethylene film 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 stretched polyethylene film 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 stretched polyethylene film to 50 μm or less, the processability of the laminated body can be improved.

In one embodiment, the intermediate layer comprises a gas barrier layer made of a gas barrier resin. By providing such an intermediate layer in the laminate of the present invention, the oxygen barrier property and the water vapor barrier property can be improved.
Examples of the gas barrier resin include polyamides such as ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol, polyacrylonitrile, nylon 6, nylon 6,6 and polymethaxylylene adipamide (MXD6), polyesters and polyurethanes. In addition, (meth) acrylic resin and the like can be mentioned.

The thickness of the gas barrier layer is preferably 0.01 μm or more and 10 μm or less, and more preferably 0.1 μm or more and 5 μm or less.
By setting the thickness of the gas barrier layer to 0.01 μm or more, the oxygen barrier property and the water vapor barrier property of the laminate of the present invention can be further improved. By setting the thickness of the gas barrier layer to 10 μm or less, the recyclability of the laminate of the present invention can be maintained.

In one embodiment, the intermediate layer comprises a thin film. The mode, preferable thickness, forming method and the like of the vapor-deposited film that can be used are as described above.

In one embodiment, the intermediate layer comprises a barrier coat layer. The structure, preferable thickness, forming method and the like of the barrier coat layer are as described above.

(Adhesive layer)
The laminate of the present invention may be provided with an adhesive layer between any layers. Thereby, the adhesion between layers can be improved.

The adhesive layer may be formed by a conventionally known adhesive. The adhesive may be a one-component curable type, a two-component curable type, or a non-curable type.
Further, the adhesive may be a solvent-free adhesive or a solvent-type adhesive, but from the viewpoint of environmental load, a solvent-free adhesive can be preferably used.
Examples of the solvent-free adhesive include polyether adhesives, polyester adhesives, silicone adhesives, epoxy adhesives and urethane adhesives, and among these, two-component curable urethanes. A system adhesive can be preferably used.
Examples of the solvent-based adhesive include rubber-based adhesives, vinyl-based adhesives, silicone-based adhesives, epoxy-based adhesives, phenol-based adhesives, and olefin-based adhesives.

When the adhesive layer is provided adjacent to the aluminum vapor deposition film, the adhesive layer is composed of a cured product of a resin composition containing a polyester polyol, an isocyanate compound, and a phosphoric acid-modified compound. Is preferable.
When molding a laminate having a vapor-deposited film into a packaging material, a bending load is applied to the laminate by a molding machine or the like, so that the aluminum vapor-deposited film may be cracked. By adopting the above-mentioned structure of the adhesive layer, it is possible to suppress deterioration of the oxygen barrier property and the water vapor barrier property even when the aluminum vapor deposition film is cracked (bending load resistance).

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 (adhesive) containing a polyester polyol, an isocyanate compound, and a phosphoric acid-modified compound, a series of PASLIM sold by DIC Corporation can be used.

The resin composition may further contain 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 [1st example] to [3rd example] can be used.
[Example] Polyester polyol obtained by polycondensing an ortho-oriented polyvalent carboxylic acid or its anhydride and a polyhydric alcohol [Example] Polyester polyol having a glycerol skeleton [Example] Having an isocyanul ring Polyester polyols Each polyester polyol will be described below.

The polyester polyol according to the first example is selected from the group consisting of a polyvalent carboxylic acid component containing at least one orthophthalic acid and an anhydride thereof, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol. It is a polycondensate obtained by polycondensing with a polyhydric alcohol component containing at least one of these.
In particular, a polyester polyol having an orthophthalic acid and its anhydride content of 70 to 100% by mass with respect to all the components of the polyvalent carboxylic acid is preferable.

The polyester polyol according to the first example requires orthophthalic acid and its anhydride as the polyvalent carboxylic acid component, but other polyvalent carboxylic acid components are copolymerized as long as the effects of the present embodiment are not impaired. You may.
Specifically, aliphatic polyvalent carboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid and dodecanediocarboxylic acid, unsaturated bond-containing polyvalent carboxylic acids such as maleic anhydride, maleic acid and fumaric acid, 1, Alicyclic polyvalent carboxylic 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. Examples thereof include aromatic polyvalent carboxylic acids such as sex derivatives, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and polybasic acids such as ester-forming derivatives of these dihydroxycarboxylic acids. Among these, succinic acid, 1,3-cyclopentanedicarboxylic acid and isophthalic acid are preferable.
In addition, you may use 2 or more kinds of the above-mentioned 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 mentioned.
In the general formula (1), R ₁ , R ₂ , and R ₃ are 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 is a 1,2-phenylene group, a 1,2-naphthylene group, a 2,3-naphthylene group, 2, which may have a substituent. It represents an arylene group selected from the group consisting of a 3-anthraquinonediyl group and a 2,3-anthracendyl group, and Y represents a group represented by 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). Above all, 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) Any two or more compounds of the compound which is the group to be used and the compound which is the group in which all of R ₁ , R ₂ and R ₃ are represented by the general formula (2) may be a mixture.

X is selected from the group consisting of 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 2,3-anthraquinone diyl group and 2,3-anthracene diyl group, and has a substituent. Represents an allylene group that may be present.
When X is substituted with a substituent, it may be substituted with one or more substituents, the substituent being attached to any carbon atom on X different from the free radical. Examples of the substituent include a chloro group, a bromo group, a methyl group, an ethyl group, an i-propyl group, a hydroxyl group, a methoxy group, an ethoxy group, a phenoxy group, a methylthio group, a phenylthio group, a cyano group, a nitro group and an amino group. Examples thereof 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 is an ethylene group, a propylene group, a butylene group, a neopentylene group, a 1,5-pentylene group, a 3-methyl-1,5-pentylene group, a 1,6-hexylene group, a methylpentylene group. Represents an alkylene group having 2 to 6 carbon atoms such as a group and a dimethylbutylene group. Among Y, a propylene group and an ethylene group are preferable, and an ethylene group is most preferable.

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

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

Further, examples of the polyhydric alcohol component include an alkylene diol 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 isocyanul ring represented by the following general formula (3).
In the general formula (3), R ₁ , R ₂ , and R ₃ are independently "-(CH ₂ ) n1-OH (where n1 represents an integer of 2 to 4)" or the general formula (4). ) Represents the structure.

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, a 1,2-naphthylene group, a 2,3-naphthylene group, It represents an arylene group selected from the group consisting of a 2,3-anthraquinonediyl group and a 2,3-anthracendyl group and 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), the alkylene group represented by − (CH ₂ ) n1- may be linear or branched. Of these, 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 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 2,3-anthraquinonediyl group, and 2,3-anthracenediyl group and has a substituent. Represents an allylene group that may be present.

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

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

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). Above all, 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) Any two or more compounds of the compound which is the group to be used and the compound which is the group in which all of R ₁ , R ₂ and R ₃ are represented by the general formula (4) may be a mixture.

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

Triols having an isocyanuric ring include, for example, 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 so on.

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

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

Further, examples of the polyhydric alcohol component include an alkylene diol 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 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 isocyanul ring, and the carboxylic acid is in the ortho position. A polyester polyol compound having an isocyanul ring using an aromatic polyvalent carboxylic acid substituted with or using orthophthalic anhydride as its anhydride and ethylene glycol as the polyhydric alcohol is particularly excellent in oxygen barrier property and adhesiveness. preferable.

The isocyanul ring is highly polar and trifunctional, and can increase the polarity of the entire system and increase the crosslink density. From this point of view, it is preferable to contain isocyanul 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.
Further, the isocyanate compound may be aromatic, aliphatic, low molecular weight compound, or high molecular weight 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 commonly used appropriate method.
Among them, a polyisocyanate compound having three or more isocyanate groups is preferable from the viewpoint of adhesiveness and retort resistance, and an aromatic compound is preferable from the viewpoint of oxygen barrier property and water vapor barrier property.

Specific examples of the isocyanate compound include tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydride diphenylmethane diisocyanate, metaxylylene diisocyanate, hydride hydride diisocyanate, isophorone diisocyanate, and these isocyanate compounds. Examples thereof include an adduct, a burette, and an allophanate obtained by reacting these isocyanate compounds with a low molecular weight active hydrogen compound or an alkylene oxide adduct thereof, or a high molecular weight active hydrogen compound.
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, and sorbitol. Examples thereof include ethylenediamine, monoethanolamine, diethanolamine, triethanolamine and metaxylylene diamine, and examples of the molecularly active hydrogen compound include various polyester resins, polyether polyols and high molecular weight active hydrogen compounds of polyamide.

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 are hydrogen atoms, alkyl groups having 1 to 30 carbon atoms, (meth) acryloyl groups, phenyl groups which may have substituents, and (meth) acryloyl. It is a group selected from alkyl groups having 1 to 4 carbon atoms having an oxy group, but at least one is a hydrogen atom, and n represents an integer of 1 to 4.
In the formula, R ₄ and R ₅ have 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 of ~ 4, n represents an integer of 1 to 4, x represents an integer of 0 to 30, y represents an integer of 0 to 30, except when x and y are both 0. ..

More specifically, phosphoric acid, pyrophosphate, triphosphate, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis (2-ethylhexyl) phosphate, isododecyl acid phosphate, butoxy. Ethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, polyoxyethylene alkyl ether phosphoric acid and the like can be mentioned, and one or more of these can be used.

The content of the phosphoric acid-modified compound in the resin composition is preferably 0.005% by mass or more and 10% by mass or less, and more preferably 0.01% by mass or more and 1% by mass or less.
By setting the content of the phosphoric acid-modified compound to 0.005% by mass or more, the 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. In addition, the bending load resistance of the laminated body of the present invention can be improved.
Plate-like inorganic compounds include, for example, kaolinite-serpentinite clay minerals (haloisite, kaolinite, enderite, dicite, nacrite, antigolite, chrysotile, etc.) and pyrophyllite-talc (pyrophilite, talc, etc.). Kerorai, etc.).

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

Examples of the silane coupling agent include vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ. -Glysidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxytrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxy Propylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino) Ethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyl Examples thereof include trimethoxysilane, 3-isocyanuspropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane and 3-triethoxysilyl-N- (1,3-dimethyl-butylidene).

Examples of titanium-based coupling agents include isopropyltriisostearoyl titanate, isopropyltri (N-aminoethyl-aminoethyl) titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, and tetraoctylbis. (Didodecylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctainoltitanate, isopropyldimethacrylisostearoyl titanate , Isostatearoyl diacrylic titanate, diisostearoyl ethylene titanate, isopropyltri (dioctyl phosphate) titanate, isopropyltricylphenyl titanate and dicumylphenyloxyacetate titanate and the like.

Specific examples of the aluminum-based coupling agent include acetalkoxyaluminum diisopropyrate, diisopropoxyaluminum ethylacetate, diisopropoxyaluminum monomethacrylate, isopropoxyaluminum alkylacetate monomethacrylate, and aluminum. Examples thereof include -2-ethylhexanoate oxide trimmer, aluminum stearate oxide trimmer and alkylacetate aluminum oxide trimmer.

The resin composition can contain cyclodextrin and / or its derivatives, which can improve the adhesiveness of the adhesive layer. In addition, the bending load resistance of the laminated body 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 the hydrogen atom of the hydroxyl group of the glucose unit is replaced with another functional group is used. Can be done. A branched cyclic dextrin can also be used.
The cyclodextrin skeleton of cyclodextrin and cyclodextrin derivatives is α-cyclodextrin consisting of 6 glucose units, β-cyclodextrin consisting of 7 glucose units, and γ-cyclodextrin consisting of 8 glucose units. It may be either.
These compounds may be used alone or in combination of two or more. In addition, these cyclodextrins and / or derivatives thereof may be collectively referred to as dextrin compounds hereafter.

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 and methyl-γ-cyclodextrin. These compounds may be used alone or in combination of two or more.

Examples of the acetylated cyclodextrin include 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 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 further 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 the adhesive layer is composed of a cured product of a resin composition containing a polyester polyol, an isocyanate compound and a phosphoric acid-modified compound, the bending load resistance of the laminate can be improved.
By setting the thickness of the adhesive layer to 6 μm or less, the processability of the laminated body can be improved.

The adhesive layer is 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. It can be formed by.

The laminate of the present invention can be particularly preferably used for the following packaging material applications.

(Packaging material)
The packaging material of the present invention is characterized by being composed of the above-mentioned laminate.
The shape of the packaging material is not particularly limited, and may be a bag-like shape as shown in FIG.
In the figure, the shaded area represents the heat-sealed part.

In one embodiment, the bag-shaped packaging material can be produced by folding and stacking the laminates of the present invention in half so that the heat-sealing layer is on the inside, and heat-sealing the ends thereof. ..
In another embodiment, the bag-shaped packaging material can also be produced by stacking two laminates so that the heat-sealing layers face each other and heat-sealing the ends thereof.

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

Also, in one embodiment, the packaging material has a stand pouch-like shape with a body and bottom, as shown in FIG.

The stand pouch-shaped packaging material is heat-sealed in a tubular shape so that the heat-seal layer of the laminate is on the inside to form a body, and then another laminate is heat-sealed. The bottom can be formed and manufactured by folding it in a V shape so that the layer is on the inside, sandwiching it from one end of the body, and heat-sealing it.

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

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

Example 1
Biomass-derived linear low-density polyethylene (density: 0.916 g / cm ³ , MFR: 1.3 g / 10 minutes, biomass degree: 87%, manufactured by Braskem, trade name: SLL18) is formed into a film by an inflation molding method. , A polyethylene film having a thickness of 100 μm was obtained.
This polyethylene film was stretched in the longitudinal direction (MD) at a stretching ratio of 5 times to obtain a film having a thickness of 20 μm.

Next, an electron beam is irradiated from one surface of the film using an electron beam irradiation device (line irradiation type irradiation device EZ-CURE, manufactured by Iwasaki Electric Co., Ltd.) under the following conditions to obtain the substrate of the present invention. It was.
Voltage: 100kV
Irradiation dose: 280 kGy
Oxygen concentration in the device: 100 ppm or less Line speed: 25 m / min

An image was formed by a gravure printing method using an oil-based gravure ink (manufactured by DIC Graphics Co., Ltd., trade name: Finato) on the surface of the base material opposite to the surface irradiated with the electron beam.

As the heat seal layer, linear low density polyethylene 1 (density: 0.925, MFR: 1.9 g / 10 minutes, made of prime polymer, trade name: SP2520) and biomass-derived linear low density polyethylene (density:: 0.916 g / cm ³ , MFR: 1.3 g / 10 minutes, degree of biomass: 87%, manufactured by Braskem, trade name: SLL18) and linear low-density polyethylene 2 (density: 0.903, MFR: 1.2 g) / 10 minutes, made of prime polymer, trade name: SP0510) is formed by the inflation molding method, and the linear low-density polyethylene layer 1 / the linear low-density polyethylene layer derived from biomass / the linear low-density polyethylene layer A polyethylene film composed of 2 was produced. The thickness of the linear low-density polyethylene layer 1 is 10 μm, the thickness of the biomass-derived linear low-density polyethylene layer is 20 μm, the thickness of the linear low-density polyethylene layer 2 is 10 μm, and the total thickness is 40 μm. there were.
The laminate of the present invention was obtained by laminating on the image-forming surface of the base material via the above-mentioned two-component curable urethane adhesive (manufactured by Rock Paint Co., Ltd., trade name: RU-77T / H-7). It was.
The thickness of the adhesive layer formed by the two-component curable urethane adhesive was 3.0 μm.

Example 2
A laminate was produced in the same manner as in Example 1 except that an aluminum vapor-deposited film having a thickness of 20 nm was formed on the substrate laminated surface of the LLDPE film by the PVD method.

Example 3
Medium density polyethylene (density: 0.941 g / cm3, melting point 129 ° C., MFR: 1.3 g / 10 minutes, manufactured by Dowchemical, trade name: Elite5538G) is formed by an inflation molding method to obtain a polyethylene film having a thickness of 100 μm. Obtained.
This polyethylene film was stretched in the longitudinal direction (MD) at a stretching ratio of 5 times to obtain a film having a thickness of 20 μm.

An aluminum vapor-deposited film having a thickness of 20 nm was formed on one surface of the polyethylene film thus obtained by the PVD method to prepare an intermediate layer.

The above adhesive was applied to the vapor-deposited film-forming surface of the intermediate layer, and the image-forming surface of the base material produced in Example 1 was laminated.

The adhesive was applied to the non-deposited film-formed surface of the intermediate layer, and the LLDPE film having a thickness of 40 μm was laminated to obtain the laminate of the present invention.

Comparative Example 1
The above-mentioned linear low-density polyethylene derived from biomass was formed into a film by an inflation molding method to obtain a polyethylene film having a thickness of 20 μm.
A laminate was produced in the same manner as in Example 1 except that the base material was changed to the polyethylene film.

Comparative Example 2
A laminate was prepared in the same manner as in Comparative Example 1 except that one surface of the polyethylene film prepared in Comparative Example 1 was irradiated with an electron beam in the same manner as in Example 1.

Comparative Example 3
The above-mentioned linear low-density polyethylene derived from biomass 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 stretching ratio of 5 times to obtain a polyethylene film having a thickness of 20 μm.
A laminate was produced in the same manner as in Example 1 except that the base material was changed to the polyethylene film.

Comparative Example 4
A laminate was obtained in the same manner as in Example 1 except that the base material was a biaxially stretched polyester film having a thickness of 12 μm (manufactured by Toyobo Co., Ltd., trade name: E5100).

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

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

<< Heat resistance evaluation >>
From the laminates obtained in the above Examples and Comparative Examples, two test pieces each having a length of 80 mm and a width of 80 mm were prepared.
The two test pieces were superposed so that the heat-sealing layers faced each other, and the three sides were heat-sealed at 150 ° C. to prepare a pouch-shaped packaging material.
The prepared packaging material was visually observed, and the heat resistance of the laminate was evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 1.
(Evaluation criteria)
⊚: No wrinkles were generated on the surface of the packaging material, and no adhesion to the heat seal bar was observed.
◯: Some wrinkles were generated on the surface of the packaging material, and some adhesion to the heat seal bar was observed, but there was no problem in practical use.
X: Wrinkles were generated on the surface of the packaging material, and adhesion to the heat seal bar was observed, so that the bag could not be made.

<< Oxygen barrier evaluation >>
The laminates obtained in the above Examples and Comparative Examples were cut into A4 size, and using OXTRAN 2/20 manufactured by MOCON of the United States, oxygen permeability (cc / m ^{2) in} an environment of 23 ° C. and 90% relative humidity. / Day / atm) was measured. The measurement results are summarized in Table 1.
Those exceeding the measurement upper limit of 200 cc / m ² / day / atm are described as "-".

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

<< Heat sealability test >>
The laminates obtained in the above Examples and Comparative Examples were cut into 10 cm × 10 cm to prepare sample pieces. This sample piece was folded in half so that the heat seal layer was on the inside, and a region of 1 cm × 10 cm was heat-sealed under the conditions of a temperature of 140 ° C., a pressure of 1 kgf / cm ² , and 1 second.
Cut the sample piece after heat sealing into strips with a width of 15 mm, grasp both ends that were not heat-sealed with a tensile tester, and determine the peel strength (N / 15 mm) under the conditions of a speed of 300 mm / min and a load range of 50 N. It was measured. The measurement results are summarized in Table 1.
The laminate obtained in Comparative Example 1 adhered to the heat seal bar, and the peel strength could not be measured, so the value was set to "-".

10: Substrate, 11: Laminate, 12: Heat seal layer, 13: Intermediate layer, 14: Adhesive layer

Claims (9)

It is a base material
The base material is made of a film made of polyethylene.
The film has been stretched and has been stretched.
At least one surface of the film has been subjected to electron beam irradiation treatment.
A base material containing polyethylene derived from biomass as the polyethylene. The base material according to claim 1, wherein the thickness is 10 μm or more and 50 μm or less. The base material according to claim 1 or 2, wherein the stretching ratio in the longitudinal direction and / or the lateral direction is 2 times or more and 10 times or less. The base material according to any one of claims 1 to 3,
Equipped with a heat seal layer,
The base material is provided so that the electron beam irradiation surface of the base material is the outermost surface.
A laminate, wherein the heat seal layer is made of polyethylene. The laminate according to claim 4, wherein the heat-sealing layer contains polyethylene derived from biomass. The laminate according to claim 4 or 5, which is used for packaging material applications. A packaging material, which comprises the laminate according to any one of claims 4 to 6. It ’s a packaging bag,
A packaging bag comprising the laminate according to any one of claims 4 to 6, wherein the heat seal layer has a thickness of 20 μm or more and 60 μm or less. It ’s a stand pouch,
It is composed of the laminate according to any one of claims 4 to 6.
A stand pouch characterized in that the thickness of the heat seal layer is 50 μm or more and 200 μm or less.