JP7430657B2 - Laminated body comprising a polyolefin resin layer and packaging product comprising the same - Google Patents

Description

The present invention relates to a laminate including a polyolefin resin layer containing biomass polyolefin, and more specifically, at least a base material layer and a polyolefin resin layer containing biomass polyolefin, which is a polymer of a monomer containing biomass-derived ethylene. , a laminate including a thermoplastic resin layer. Furthermore, the present invention relates to packaging products and flexible packaging including the laminate.

In recent years, with increasing calls for building a recycling-oriented society, there is a desire to move away from fossil fuels in the materials field as well as energy, and the use of biomass is attracting attention. Biomass is an organic compound that is photosynthesized from carbon dioxide and water, and by using it, it becomes carbon dioxide and water again, so it is a so-called carbon-neutral renewable energy. In recent years, the practical use of biomass plastics made from these biomass raw materials is rapidly progressing, and attempts are also being made to produce various resins from biomass raw materials.

Commercial production of biomass-derived resins began first with polylactic acid (PLA), which is produced through lactic acid fermentation, but its performance as a plastic, including its biodegradability, is superior to that of today's general-purpose plastics. Because it is very different from the conventional method, there are limits to product applications and product manufacturing methods, and it has not become widely used. In addition, life cycle assessment (LCA) evaluations are being conducted on PLA, and discussions are taking place regarding the energy consumption during PLA production and the equivalency when replacing general-purpose plastics.

Here, various types of general-purpose plastics are used, such as polyethylene, polypropylene, polyvinyl chloride, and polystyrene. In particular, polyethylene is formed into films, sheets, bottles, etc., and is used for various purposes such as packaging materials, and is used in large quantities around the world. Therefore, using conventional polyethylene derived from fossil fuels has a large environmental impact.

Therefore, it is desired to reduce the amount of fossil fuel used by using biomass-derived raw materials in the production of polyethylene. For example, to date, research has been conducted on producing ethylene and butylene, which are raw materials for polyolefin resins, from renewable natural raw materials (see, for example, Patent Document 1).

Special Publication No. 2011-506628

The present inventors focused on ethylene, which is a raw material for polyolefin resin, and instead of ethylene obtained from conventional fossil fuels, we developed low-density polyethylene (hereinafter simply "biomass-derived low-density polyethylene") using biomass-derived ethylene as a raw material. A laminate comprising a polyolefin resin layer containing polyolefin resin layer (sometimes referred to as "density polyethylene") is a laminate comprising a polyolefin resin layer containing low-density polyethylene (hereinafter simply referred to as "fossil fuel-derived low-density polyethylene") manufactured using ethylene obtained from conventional fossil fuels. It has been found that a laminate having a polyolefin resin layer made of (sometimes) can be obtained in terms of physical properties such as mechanical properties. The present invention is based on this knowledge.

Therefore, an object of the present invention is to provide a polyolefin resin layer containing biomass-derived low-density polyethylene that is comparable in physical properties such as mechanical properties to conventional laminates containing polyolefin resin layers made of fossil fuel-derived low-density polyethylene. An object of the present invention is to provide a laminate comprising:

In an aspect of the invention,
A laminate comprising at least a base material layer, a polyolefin resin layer, a plastic film having a barrier layer, and a thermoplastic resin layer in this order,
the base layer contains polypropylene,
The polyolefin resin layer includes biomass-derived low density polyethylene,
The degree of biomass in the polyolefin resin layer is 5% or more,
The base layer constitutes the outermost layer,
A laminate is provided, in which the thermoplastic resin layer constitutes an innermost layer.
In an aspect of the present invention, the laminate preferably includes an adhesive resin layer between the plastic film having the barrier layer and the thermoplastic resin layer.
In another aspect of the present invention, there is provided a method for manufacturing the laminate, comprising:
A method for producing a laminate is provided, in which the base layer and the plastic layer having the barrier layer are bonded together via the melt-extruded polyolefin resin layer.
In another aspect of the present invention, a packaging product comprising the laminate is provided.
In another aspect of the present invention, a flexible packaging including the laminate is provided.
In another aspect of the present invention, a packaging bag including the laminate is provided.

The laminate according to the present invention includes at least a base material layer, a polyolefin resin layer containing biomass-derived low-density polyethylene, a plastic film having a barrier layer, and a thermoplastic resin layer. The amount of fossil fuel used can be reduced, and the environmental impact can be reduced. Furthermore, the laminate according to the present invention is comparable in mechanical properties and other physical properties to a laminate comprising a polyolefin resin layer containing conventional fossil fuel-derived low-density polyethylene. A polyolefin resin layer containing density polyethylene can be substituted.

FIG. 1 is a schematic cross-sectional view showing an example of a laminate according to the present invention. FIG. 1 is a schematic cross-sectional view showing an example of a laminate according to the present invention. FIG. 1 is a schematic cross-sectional view showing an example of a laminate according to the present invention. It is a simplified diagram showing an example of the structure of a standing pouch. It is a simplified diagram showing an example of the structure of a laminate tube.

In the present invention, "biomass polyolefin" and "polyolefin resin layer containing biomass polyolefin" are those that use biomass-derived raw materials at least in part as raw materials, and all of the raw materials are biomass-derived. does not mean.

<Laminated body>
The laminate according to the present invention includes a base material layer, a polyolefin resin layer containing biomass polyolefin, and a thermoplastic resin layer in this order. Hereinafter, when expressed as a thermoplastic resin layer, it refers to the first thermoplastic resin layer. By providing the laminate with a polyolefin resin layer containing biomass polyolefin, the amount of fossil fuel used can be reduced compared to conventional methods, and the environmental load can be reduced. Furthermore, the laminate according to the present invention is comparable to the conventional laminate of polyolefin resin manufactured from raw materials obtained from fossil fuels in terms of physical properties such as mechanical properties. can be substituted.

The laminate according to the present invention may further include at least one other layer such as a printing layer, a barrier layer, a plastic film, an adhesive layer, a second thermoplastic resin layer, etc. in addition to the above-mentioned layers. When having two or more other layers, they may have the same composition or different compositions.

The laminate according to the present invention will be explained with reference to the drawings. Examples of schematic cross-sectional views of the laminate according to the present invention are shown in FIGS. 1 to 3.
The laminate 10 shown in FIG. 1 includes a base material layer 11, a polyolefin resin layer 12 formed on the base material layer 11, and a thermoplastic resin layer 13 formed directly on the polyolefin resin layer 12. It is. In the case of a flexible packaging including the laminate 10, the thermoplastic resin layer 13 is located inside the flexible packaging. Here, the polyolefin resin layer 12 is a polyolefin resin layer containing biomass polyolefin.
The laminate 20 shown in FIG. 2 includes a base layer 11 and, on one surface of the base layer 11, a polyolefin resin layer 12, a barrier layer 14, and a thermoplastic resin layer 13 in this order. In the case of a flexible packaging including the laminate 20, the thermoplastic resin layer 13 is located inside the flexible packaging.
The laminate 30 shown in FIG. 3 includes a base layer 11, a polyolefin resin layer 12, a plastic film 15, an adhesive layer 16, and a thermoplastic resin layer 13 on one surface of the base layer 11. Prepare in this order. In the case of a flexible packaging including the laminate 30, the thermoplastic resin layer 13 is located inside the flexible packaging.
Note that any of the laminates may further include a printed layer or a second thermoplastic resin layer. When laminating the printed layer and the second thermoplastic resin layer, they may be laminated so that the second thermoplastic resin layer is the outermost surface.
Each layer constituting the laminate will be described below.

(Base material layer)
In the present invention, the base material layer functions as a base material layer that holds the polyolefin resin layer, and is preferably one that can impart strength to the laminate as a packaging product. As the base material layer, a resin base material, preferably a plastic film of a resin material such as polyester such as polyethylene terephthalate, polyolefin such as polyethylene or polypropylene, or polyamide such as nylon, can be used, and it may be used alone, You may use two or more types in combination. Furthermore, when two or more types are combined, they may be laminated using a dry lamination method or a melt extrusion method. The thickness of the base material layer can be 5 μm or more and 38 μm or less, preferably 5 μm or more and 25 μm or less, and more preferably 8 μm or more and 16 μm or less.

The base material layer may contain a biomass-derived material or a fossil fuel-derived material.

The base material layer may include a biomass polyester having biomass-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit. The base material layer may further include a fossil fuel-derived polyester having fossil fuel-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit.

The "biomass degree" (biomass-derived carbon concentration) in the base material layer is a value obtained by measuring the biomass-derived carbon content by radiocarbon (C14) measurement. Since carbon dioxide in the atmosphere contains C14 at a certain rate (105.5 pMC), the C14 content in plants that grow by taking in atmospheric carbon dioxide, such as corn, is also around 105.5 pMC. It is known. It is also known that fossil fuels contain almost no C14. Therefore, by measuring the proportion of C14 contained in all carbon atoms in polyester, the proportion of carbon derived from biomass can be calculated. In the present invention, the biomass-derived carbon content Pbio, where the C14 content in the polyester is PC14, can be determined as follows.
Pbio (%) = PC14/105.5×100

Taking polyethylene terephthalate as an example, polyethylene terephthalate is a polymerization of ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms in a molar ratio of 1:1, so only biomass-derived ethylene glycol can be used. When Pbio is used, the biomass-derived carbon content Pbio in the polyester is 20%. In the present invention, the content of biomass-derived carbon determined by radiocarbon (C14) measurement is preferably 10% or more and 20% or less, and 10% or more and 19% or less, based on the total carbon in the biomass polyester. There may be. If the content of biomass-derived carbon in the biomass polyester is 10% or more, it is suitable as a carbon offset material. In addition, the content of biomass-derived carbon in fossil fuel-derived polyester produced using fossil fuel-derived ethylene glycol and fossil fuel-derived dicarboxylic acid is 0%, and the biomass content of fossil fuel-derived polyester is 0%. becomes 0%.

The degree of biomass in the base material layer is 5% or more, preferably 10% or more, and more preferably 15% or more. If the biomass content in the base material layer is 5% or more, the amount of polyester derived from fossil fuels can be reduced compared to the conventional method, and the environmental load can be reduced.

The base material layer can be formed by forming a film using a T-die method, for example, using a resin composition of biomass polyester or a resin composition containing biomass polyester and fossil fuel-derived polyester.

(biomass polyester)
Biomass polyester consists of a diol unit and a dicarboxylic acid unit, and is obtained by a polycondensation reaction using biomass-derived ethylene glycol as the diol unit and fossil fuel-derived dicarboxylic acid as the dicarboxylic acid unit.

Biomass-derived ethylene glycol is made from ethanol produced from biomass (biomass ethanol). For example, biomass-derived ethylene glycol can be obtained by converting biomass ethanol into ethylene glycol via ethylene oxide using a conventionally known method. Moreover, commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycol Corporation can be suitably used.

The dicarboxylic acid unit of the biomass polyester uses dicarboxylic acid derived from fossil fuels. As the dicarboxylic acid, aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and derivatives thereof can be used without limitation. Examples of aromatic dicarboxylic acids include terephthalic acid and isophthalic acid, and examples of derivatives of aromatic dicarboxylic acids include lower alkyl esters of aromatic dicarboxylic acids, specifically methyl esters, ethyl esters, propyl esters, and butyl esters. Examples include esters. Among these, terephthalic acid is preferred, and as the aromatic dicarboxylic acid derivative, dimethyl terephthalate is preferred.

(Polyolefin resin layer)
In the present invention, the polyolefin resin layer contains biomass polyolefin, which is a polymer of monomers containing biomass-derived ethylene, and may further contain a fossil fuel-derived polyolefin. The polyolefin resin layer may contain 5% by mass or more and 100% by mass or less of biomass polyolefin and 0% by mass or more and 95% by mass or less of fossil fuel-derived polyolefin, based on the entire polyolefin resin layer. It may contain less than 0% by mass of biomass polyolefin and more than 0% by mass and not more than 95% by mass of fossil fuel-derived polyolefin, and 25% by mass or more and 75% by mass or less of biomass polyolefin and 25% by mass or more and not more than 75% by mass of fossil fuel. It may also contain polyolefins derived from It is sufficient if the polyolefin resin layer as a whole can achieve the following biomass degree. In the present invention, since the polyolefin resin layer contains biomass polyolefin, the amount of polyolefin derived from fossil fuels can be reduced compared to the conventional method, and the environmental load can be reduced.

In the present invention, the "biomass degree" (biomass-derived carbon concentration in the biomass polyolefin) in the polyolefin resin layer is a value obtained by measuring the biomass-derived carbon content by radiocarbon (C14) measurement. Since carbon dioxide in the atmosphere contains C14 at a certain rate (105.5 pMC), the C14 content in plants that grow by taking in atmospheric carbon dioxide, such as corn, is also around 105.5 pMC. It is known. It is also known that fossil fuels contain almost no C14. Therefore, by measuring the proportion of C14 contained in all carbon atoms in the polyolefin, the proportion of carbon derived from biomass can be calculated. In the present invention, the biomass-derived carbon content P _bio can be determined as follows, where the C14 content in the polyolefin is P _C14 .
P _bio (%) = P _C14 /105.5×100

In the present invention, theoretically, if ethylene derived entirely from biomass is used as a raw material for polyolefin, the biomass degree is 100%, and the biomass degree of the biomass-derived polyolefin is 100%. Further, the biomass-derived carbon concentration in the fossil fuel-derived polyolefin produced only from fossil fuel-derived raw materials is 0%, and the biomass degree of the fossil fuel-derived polyolefin is 0%.

In the present invention, the degree of biomass in the polyolefin resin layer is 5% or more, preferably 10% or more, more preferably 15% or more, and even more preferably 20% or more. Note that the degree of biomass in the polyolefin resin layer does not need to be 100%. This is because if biomass-derived raw materials are used in even a part of the laminate, the purpose of the present invention is to reduce the amount of fossil fuel used compared to the conventional method. If the biomass content in the polyolefin resin layer is 5% or more, the amount of fossil fuel-derived polyolefin can be reduced compared to the conventional method, and the environmental load can be reduced.

The polyolefin resin layer is preferably 0.91 g/cm ³ or more and 0.93 g/cm ³ or less, more preferably 0.911 g/cm ³ or more and 0.928 g/cm ³ or less, and even more preferably 0.915 g/cm ³ or more. It has a density of 0.925 g/cm ³ or less. The density of the polyolefin resin layer is a value measured according to the method specified in Method A of JIS K7112-1980 after performing annealing as described in JIS K6760-1995. If the density of the polyolefin resin layer is 0.91 g/cm ³ or more and 0.93 g/cm ³ or less, processing and molding can be facilitated.

The polyolefin resin layer has a thickness of 5 μm or more and 100 μm or less, preferably 10 μm or more and 60 μm or less, and more preferably 15 μm or more and 40 μm or less. If the thickness of the polyolefin resin layer is within the above range, it can sufficiently perform the function of bonding the two layers together.

(biomass polyolefin)
In the present invention, the biomass polyolefin is a polymer of monomers containing ethylene derived from biomass. As the biomass-derived ethylene, it is preferable to use one obtained by the production method described below. Since biomass-derived ethylene is used as the raw material monomer, the polymerized polyolefin is biomass-derived. Note that the raw material monomer of the polyolefin does not have to contain 100% by mass of ethylene derived from biomass.

The monomer that is the raw material for the biomass polyolefin may further contain a fossil fuel-derived ethylene monomer and/or a fossil fuel-derived α-olefin monomer, or may further contain a biomass-derived α-olefin monomer.

The number of carbon atoms of the above α-olefin is not particularly limited, but those having 3 to 20 carbon atoms can be used, and butylene, hexene, or octene is preferable. This is because butylene, hexene, or octene can be produced by polymerizing ethylene, which is a raw material derived from biomass. Further, by including such an α-olefin, the polymerized polyolefin has an alkyl group as a branched structure, and therefore can be made more flexible than a simple linear one.

As the biomass polyolefin, polyethylene or a copolymer of ethylene and α-olefin may be used alone, or two or more types may be used as a mixture. In particular, the biomass polyolefin is preferably polyethylene. This is because by using ethylene, which is a raw material derived from biomass, it is theoretically possible to manufacture with 100% biomass-derived components.

The biomass polyolefin may contain two or more kinds of biomass polyolefins having different biomass degrees, and the biomass degree of the entire polyolefin resin layer may be within the above range.

The biomass polyolefin is preferably 0.91 g/cm ³ or more and 0.93 g/cm ³ or less, more preferably 0.912 g/cm ³ or more and 0.928 g/cm ³ or less, and even more preferably 0.915 g/cm 3 or more and 0.928 g/cm ³ or less. It has a density of .925 g/cm ³ or less.
The density of the biomass polyolefin is a value measured according to the method specified in Method A of JIS K7112-1980 after performing annealing as described in JIS K6760-1995. If the density of the biomass polyolefin is 0.91 g/cm ³ or more, the rigidity of the polyolefin resin layer containing the biomass polyolefin can be increased, and it can be suitably used as an inner layer of a packaged product. Further, if the density of the biomass polyolefin is 0.93 g/cm ³ or less, the transparency and mechanical strength of the polyolefin resin layer containing the biomass polyolefin can be improved, and it can be suitably used as an inner layer of a packaged product.

The biomass polyolefin has a melt flow of 0.1 g/10 minutes or more and 10 g/10 minutes or less, preferably 0.2 g/10 minutes or more and 9 g/10 minutes or less, and more preferably 1 g/10 minutes or more and 8.5 g/10 minutes or less. rate (MFR). The melt flow rate is a value measured by method A under conditions of a temperature of 190° C. and a load of 21.18 N in the method specified in JIS K7210-1995. If the MFR of the biomass polyolefin is 0.1 g/10 minutes or more, the extrusion load during molding can be reduced. Moreover, if the MFR of the biomass polyolefin is 10 g/10 minutes or less, the mechanical strength of the polyolefin resin layer containing the biomass polyolefin can be increased.

In the present invention, the biomass polyolefin preferably used is biomass-derived low-density polyethylene manufactured by Braskem (trade name: SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 min, biomass degree 95%), biomass-derived low-density polyethylene manufactured by Braskem (trade name: SPB681, density: 0.922 g/cm ³ , MFR: 3.8 g/10 min, biomass degree 95%), and the like.

(Method for producing ethylene derived from biomass)
In the present invention, the method for producing biomass-derived ethylene, which is a raw material for biomass polyolefin, is not particularly limited, and it can be obtained by conventionally known methods. An example of a method for producing ethylene derived from biomass will be described below.

Biomass-derived ethylene can be produced using biomass-derived ethanol as a raw material. In particular, it is preferable to use fermented ethanol derived from biomass obtained from plant materials. The plant material is not particularly limited, and conventionally known plants can be used. For example, corn, sugar cane, beets and manioc may be mentioned.

In the present invention, fermented ethanol derived from biomass refers to ethanol produced by contacting a culture solution containing a carbon source obtained from a plant material with a product derived from an ethanol-producing microorganism or its crushed product, and then purified. Conventionally known methods such as distillation, membrane separation, and extraction can be applied to purify ethanol from the culture solution. For example, methods include adding benzene, cyclohexane, etc. and azeotropically distilling the mixture, or removing water by membrane separation or the like.

In order to obtain the ethylene of the present invention, at this stage, high-level purification such as reducing the total amount of impurities in ethanol to 1 ppm or less may be further performed.

A catalyst is usually used to obtain ethylene through the dehydration reaction of ethanol, but this catalyst is not particularly limited, and any conventionally known catalyst can be used. A fixed bed flow reaction is advantageous in terms of process because it allows easy separation of the catalyst and the product, and for example, γ-alumina is preferred.

Since this dehydration reaction is an endothermic reaction, it is usually carried out under heating conditions. The heating temperature is not limited as long as the reaction proceeds at a commercially useful reaction rate, but a temperature of preferably 100°C or higher, more preferably 250°C or higher, and still more preferably 300°C or higher is suitable. The upper limit is also not particularly limited, but from the viewpoint of energy balance and equipment, it is preferably 500°C or less, more preferably 400°C or less.

The reaction pressure is also not particularly limited, but a pressure higher than normal pressure is preferred in order to facilitate subsequent gas-liquid separation. Industrially, a fixed bed flow reaction is preferred because it allows easy separation of the catalyst, but a liquid phase suspension bed, a fluidized bed, etc. may also be used.

In the dehydration reaction of ethanol, the yield of the reaction is influenced by the amount of water contained in the ethanol supplied as a raw material. In general, when performing a dehydration reaction, it is preferable to have no water in consideration of water removal efficiency. However, it has been found that in the case of ethanol dehydration using a solid catalyst, the amount of other olefins, especially butene, tends to increase in the absence of water. This is probably because ethylene dimerization after dehydration cannot be suppressed unless a small amount of water is present. The lower limit of the allowable water content is 0.1% or more, preferably 0.5% or more. The upper limit is not particularly limited, but from the viewpoint of material balance and heat balance, it is preferably 50% by mass or less, more preferably 30% or less, and still more preferably 20% or less.

By performing the dehydration reaction of ethanol in this way, a mixed portion of ethylene, water, and a small amount of unreacted ethanol is obtained, but since ethylene is a gas at room temperature and below about 5 MPa, gas-liquid separation is performed from this mixed portion. Ethylene can be obtained by excluding water and ethanol. This method may be performed by a known method.

The ethylene obtained by gas-liquid separation is further distilled, and there are no particular restrictions on the distillation method, operating temperature, residence time, etc., except that the operating pressure at this time is equal to or higher than normal pressure.

When the raw material is biomass-derived ethanol, the obtained ethylene contains carbonyl compounds such as ketones, aldehydes, and esters, which are impurities mixed in during the ethanol fermentation process, as well as carbon dioxide gas, which is the decomposition product thereof, and enzyme decomposition products. Contains extremely small amounts of impurities such as nitrogen-containing compounds such as amines and amino acids, as well as ammonia, which is a decomposition product thereof. Depending on the use of ethylene, these minute amounts of impurities may pose a problem, so they may be removed by purification. The purification method is not particularly limited, and can be performed by a conventionally known method. As a suitable purification operation, for example, an adsorption purification method can be mentioned. The adsorbent used is not particularly limited, and conventionally known adsorbents can be used. For example, a material with a high surface area is preferable, and the type of adsorbent is selected depending on the type and amount of impurities in ethylene obtained by the dehydration reaction of biomass-derived ethanol.

Note that caustic water treatment may be used in combination as a method for purifying impurities in ethylene. If caustic water treatment is to be performed, it is desirable to perform it before adsorption purification. In that case, it is necessary to perform water removal treatment after caustic treatment and before adsorption purification.

(Method for producing biomass polyolefin)
In the present invention, the method for polymerizing a monomer containing biomass-derived ethylene is not particularly limited, and can be performed by a conventionally known method. The polymerization temperature and polymerization pressure are preferably adjusted as appropriate depending on the polymerization method and polymerization apparatus. The polymerization device is not particularly limited either, and conventionally known devices can be used. An example of a method for polymerizing a monomer containing ethylene will be described below.

Polymerization methods for polyolefins, particularly ethylene polymers and copolymers of ethylene and α-olefins, are based on the desired type of polyethylene, such as high-density polyethylene (HDPE), medium-density polyethylene (MDPE), and low-density polyethylene (LDPE). ), linear low-density polyethylene (LLDPE), and the like, depending on the density and branching.
For example, using a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst as a polymerization catalyst, by any of gas phase polymerization, slurry polymerization, solution polymerization, and high-pressure ionic polymerization, It is preferable to perform the reaction in one stage or in multiple stages of two or more stages.

The above-mentioned single-site catalyst is a catalyst that can form a uniform active species, and is usually prepared by bringing a metallocene transition metal compound or a non-metallocene transition metal compound into contact with an activation cocatalyst. . Single-site catalysts are preferable compared to multi-site catalysts because they have a more uniform active site structure and can polymerize a polymer with a high molecular weight and a highly uniform structure. As the single site catalyst, it is particularly preferable to use a metallocene catalyst. The metallocene catalyst is a catalyst containing a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, a cocatalyst, an organometallic compound if necessary, and each catalyst component of a support. be.

In the above 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, etc. . 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. The substituted cyclopentadienyl group may have two or more substituents, and the substituents may combine with each other to form a ring, such as an indenyl ring, a fluorenyl ring, an azulenyl ring, or a hydrogenated product thereof. may be formed. The ring formed by bonding the substituents to each other may further have a substituent.

In a 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, hafnium, etc., and zirconium and hafnium are particularly preferred. The transition metal compound usually has two cyclopentadienyl skeleton-containing ligands, and each of the cyclopentadienyl skeleton-containing ligands is preferably bonded to each other via a crosslinking group. Examples of the crosslinking group include alkylene groups having 1 to 4 carbon atoms, substituted silylene groups such as silylene groups, dialkylsilylene groups, and diarylsilylene groups, and substituted germylene groups such as dialkylgermylene groups and diarylgermylene groups. Preferably, it is a substituted silylene group.

In transition metal compounds of Group IV of the periodic table, typical ligands other than those having a cyclopentadienyl skeleton include hydrogen, a hydrocarbon group having 1 to 20 carbon atoms (alkyl group), , alkenyl group, aryl group, alkylaryl group, aralkyl group, polyenyl group, etc.), halogen, metaalkyl group, metaaryl group, etc.

One or a mixture of two or more of the transition metal compounds of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton can be used as a catalyst component.

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

A transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton may be used by being supported on an inorganic or organic compound carrier. The carrier is preferably a porous oxide of an inorganic or organic compound, and specifically, ion exchange layered silicates such as montmorillonite, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, _ThO2 , etc., or a mixture thereof.

Furthermore, examples of organometallic compounds that may be used as necessary include organoaluminum compounds, organomagnesium compounds, organozinc compounds, and the like. Among these, organic aluminum is preferably used.

In addition to the polyolefin that is the main component, various additives may be added to the biomass polyolefin as long as its properties are not impaired. Examples of additives include plasticizers, ultraviolet stabilizers, anti-coloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, yarn friction reducers, slip agents, mold release agents, and antislip agents. Oxidizing agents, ion exchange agents, color pigments, etc. can be added. These additives are preferably added in an amount of 1% by mass or more and 20% by mass or less, preferably 1% by mass or more and 10% by mass or less, based on the entire biomass polyolefin.

(Thermoplastic resin layer)
The thermoplastic resin layer can be formed using a conventionally known thermoplastic resin. The laminate further includes a thermoplastic resin layer, thereby imparting heat resistance, pressure resistance, water resistance, heat sealability, pinhole resistance, puncture resistance, and other physical properties similar to conventional laminates. be able to.

Examples of thermoplastic resins include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, propylene-ethylene copolymer, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid copolymer. Coalescence, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ionomer resin, polyester resin, polyvinyl chloride resin, polystyrene resin, nylon, etc. Among them, low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, and ethylene-methacrylic acid copolymer are preferred.

The thermoplastic resin layer may contain a biomass-derived material or a fossil fuel-derived material. When the thermoplastic resin layer contains a material derived from biomass, it may contain biomass polyolefin, which is a polymer of monomers containing ethylene derived from biomass, similarly to the polyolefin resin layer.

Further, as described above, a second thermoplastic resin layer may be provided on the surface of the base material layer opposite to the polyolefin resin layer. The same resin as the thermoplastic resin layer (first thermoplastic resin layer) can be used for the second thermoplastic resin layer.

(Printing layer)
The printing layer contains letters, numbers, pictures, figures, symbols, patterns, etc. for decoration, display of contents, display of expiration date, display of manufacturer, seller, etc., and for giving a sense of beauty. This layer forms any desired printed pattern. The printing layer can be provided as needed, and for example, can be provided on the base material layer. The printing layer may be provided on the entire surface of the base material layer, or may be provided on a part of the base material layer. The printing layer can be formed using conventionally known pigments and dyes, and the forming method is not particularly limited.

(barrier layer)
The barrier layer is made of an inorganic substance and/or an inorganic oxide, and is preferably made of a vapor-deposited film of an inorganic substance or an inorganic oxide, or a metal foil. The deposited film can be formed by a conventionally known method using a conventionally known inorganic substance or inorganic oxide, and its composition and formation method are not particularly limited. When the laminate further includes a barrier layer, gas barrier properties that block the transmission of oxygen gas, water vapor, etc., and light shielding properties that block the transmission of visible light, ultraviolet rays, etc. can be imparted or improved. Note that the laminate may have two or more barrier layers. When there are two or more barrier layers, they may have the same composition or different compositions.

Examples of the deposited film include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), and titanium (Ti). ), lead (Pb), zirconium (Zr), yttrium (Y), or other inorganic substances or evaporated films of inorganic oxides can be used. Particularly suitable for packaging materials (bags) and the like, it is preferable to use vapor-deposited films of aluminum metal, or vapor-deposited films of silicon oxide, aluminum metal, or aluminum oxide.

Inorganic oxides are expressed as, for example, MO _x such as SiO _x , _AlO expressed. The value range of X is 0 to 2 for silicon (Si), 0 to 1.5 for aluminum (Al), 0 to 1 for magnesium (Mg), 0 to 1 for calcium (Ca), Potassium (K) is 0 to 0.5, tin (Sn) is 0 to 2, sodium (Na) is 0 to 0.5, boron (B) is 0 to 1, 5, titanium (Ti) can take a value in the range of 0 to 2, lead (Pb) can take a value in the range of 0 to 1, zirconium (Zr) can take a value in the range of 0 to 2, and yttrium (Y) can take a value in the range of 0 to 1.5. In the above, when X=0, it is a completely inorganic substance (pure substance) and is not transparent, and the upper limit of the range of X is a completely oxidized value. Silicon (Si) and aluminum (Al) are preferably used for the packaging material, with silicon (Si) in the range of 1.0 to 2.0 and aluminum (Al) in the range of 0.5 to 1.5. You can use the value of .

In the present invention, the thickness of the vapor-deposited film of the inorganic substance or inorganic oxide as described above varies depending on the type of inorganic substance or inorganic oxide used, but is, for example, 50 Å or more and 2000 Å or less, preferably 100 Å or more and 1000 Å or less. It is desirable to arbitrarily select and form it within the range of . More specifically, in the case of a vapor deposited film of aluminum, the film thickness is desirably 50 Å or more and 600 Å or less, more preferably 100 Å or more and 450 Å or less, and in the case of a vapor deposited film of aluminum oxide or silicon oxide, The film thickness is desirably 50 Å or more and 500 Å or less, more preferably 100 Å or more and 300 Å or less.

The vapor deposition film can be formed on a plastic film such as polyethylene terephthalate or nylon using the following formation method. Examples of methods for forming the deposited film include physical vapor deposition methods (PVD methods) such as vacuum evaporation methods, sputtering methods, and ion plating methods, or plasma chemical vapor deposition methods and thermochemical methods. Examples include a chemical vapor deposition method (CVD method) such as a vapor phase growth method and a photochemical vapor deposition method.

According to another embodiment, the barrier layer may be a metal foil obtained by rolling metal. As the metal foil, a conventionally known metal foil can be used. Aluminum foil is preferable from the viewpoint of gas barrier properties that block the transmission of oxygen gas, water vapor, etc., and light shielding properties that block the transmission of visible light, ultraviolet rays, etc.

(Plastic film)
In the present invention, various plastic films may be used as other layers. For example, any of stretched polyethylene terephthalate film, stretched nylon film, stretched polypropylene film, nylon 6/metaxylylenediamine nylon 6 co-extruded co-stretched film, or polypropylene/ethylene-vinyl alcohol copolymer co-extruded co-stretched film, or A composite film obtained by laminating two or more of these films may also be used. Note that the plastic film may be coated with polyvinyl alcohol or the like.

The plastic film may contain materials derived from biomass or from fossil fuels. When the plastic film contains a biomass-derived material, it may further contain a fossil fuel-derived polyester having fossil fuel-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit.

(Adhesive layer)
The adhesive layer can be an adhesive layer formed by applying an adhesive to the surface of the layer to be laminated and drying it when two layers are adhered by a dry lamination method.
Examples of adhesives include one-component or two-component curing or non-curing vinyl-based, (meth)acrylic-based, polyamide-based, polyester-based, polyether-based, polyurethane-based, epoxy-based, rubber-based, and others. Solvent-based, water-based, or emulsion-based adhesives can be used. Coating methods for the above laminating adhesive include, for example, direct gravure roll coating, gravure roll coating, kiss coating, reverse roll coating, Fontaine method, transfer roll coating, and other methods to form a laminate. It can be applied to the coated side of the layer. The coating amount is preferably 0.1 g/m ² or more and 10 g/m ² or less (dry state), more preferably 1 g/m ² or more and 5 g/m ² or less (dry state).

In addition, when laminating polyolefin resin layers, thermoplastic resin layers, etc. using the melt extrusion lamination method, the adhesive layer is an anchor coating agent that is formed by applying an anchor coating agent to the surface of the layer to be laminated and drying it. It may be a coat layer. Examples of the anchor coating agent include anchor coating agents made of any resin with a heat resistance temperature of 135°C or higher, such as vinyl-modified resin, epoxy resin, urethane resin, polyester resin, etc. An anchor coating agent consisting of a polyacrylic or polymethacrylic resin having a hydroxyl group and an isocyanate compound as a curing agent can be preferably used. Further, a silane coupling agent may be used together as an additive, and nitrified cotton may be used together in order to improve heat resistance.

Further, the adhesive layer may be an adhesive resin layer used for bonding two layers together by a sand lamination method or a melt extrusion lamination method. Thermoplastic resins that can be used for the adhesive resin layer include polyethylene resins, polypropylene resins, cyclic polyolefin resins, copolymer resins, modified resins, and mixtures (including alloys) containing these resins as main components. ) can be used. Examples of polyolefin resins include low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), polypropylene (PP), and metallocene catalysts. Ethylene-α-olefin copolymer polymerized using ethylene-α-olefin copolymer, ethylene-polypropylene random or block copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-α-olefin copolymer Ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-maleic acid copolymer, ionomer resin, and interlayer adhesion In order to improve this, it is possible to use acid-modified polyolefin resins in which the above-mentioned polyolefin resins are modified with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid. can. Further, a resin obtained by graft polymerizing or copolymerizing an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or an ester monomer to the polyolefin resin can be used. These materials can be used alone or in combination of two or more. As the cyclic polyolefin resin, for example, cyclic polyolefins such as ethylene-propylene copolymer, polymethylpentene, polybutene, and polynorbornene can be used. These resins can be used alone or in combination. It goes without saying that as the polyethylene resin mentioned above, one using the above-mentioned biomass-derived ethylene as a monomer unit can be used.

The adhesive resin layer may contain a biomass-derived material or a fossil fuel-derived material. When the adhesive resin layer contains a material derived from biomass, it may contain biomass polyolefin, which is a polymer of monomers containing ethylene derived from biomass, similarly to the polyolefin resin layer.

(Method for manufacturing laminate)
The method for manufacturing the laminate according to the present invention is not particularly limited, and it can be manufactured using conventionally known methods such as dry lamination, melt extrusion lamination, and sand lamination. In the present invention, it is preferable to laminate other layers via the melt-extruded polyolefin resin layer using a sand lamination method. Alternatively, the polyolefin resin layer and other layers may be laminated by coextrusion.

The thickness of the laminate obtained as described above is arbitrary depending on its use, but is usually 5 μm or more and 500 μm or less, preferably 20 μm or more and 300 μm or less.

The laminate according to the present invention can be provided with surface functions such as chemical functions, electrical functions, magnetic functions, mechanical functions, friction/wear/lubrication functions, optical functions, thermal functions, and biocompatibility. It is also possible to perform secondary processing for this purpose. Examples of secondary processing include embossing, painting, adhesion, printing, metallization (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, coating, etc.). Moreover, a molded product can also be manufactured by subjecting the laminate according to the present invention to lamination processing (dry lamination or extrusion lamination), bag making processing, and other post-processing processing.

(Application)
The laminate according to the present invention can be used for packaging products, and as packaging products, it is preferably used for flexible packaging such as packaging bags, laminate tubes, and lidding materials. Examples of packaging bags include standing pouch type, side seal type, two side seal type, three side seal type, four side seal type, envelope sticker type, gasho sticker type (pillow seal type), pleated seal type, and flat bottom seal type. There are various types of packaging bags, such as a type, a square bottom seal type, and a gusset type. The thickness of the laminate in that case can be appropriately determined depending on the application, and is used in the form of a film having a thickness of, for example, 30 μm or more and 300 μm or less, preferably 35 μm or more and 180 μm or less.

(Flexible packaging)
The laminate according to the present invention can be suitably used for flexible packaging, particularly packaging bags and laminate tubes. A case will be described in which a packaging bag, as an example a standing pouch, is formed using the laminate according to the present invention. FIG. 4 is a simplified diagram showing an example of the configuration of a standing pouch.
As shown in FIG. 4, the standing pouch 40 includes two body parts (side sheets) 41 and a bottom part (bottom sheet) 42. In the standing pouch 40, the side sheet 41 and the bottom sheet 42 may be made of the same member, or may be made of separate members. The side sheet 41 and bottom sheet 42 of the standing pouch 40 can be formed using the laminate according to the present invention.

Next, a case will be described in which a laminate tube is formed using the laminate according to the present invention. FIG. 5 is a simplified diagram showing an example of a laminate tube. As shown in FIG. 5, the laminate tube 50 includes a head portion 51 and a cylindrical body portion 32. As shown in FIG. The head 51 includes a hollow conical shoulder portion 53 and a spout portion 54, which are integrally formed. The cylindrical trunk 52 is connected to the shoulder 53 of the head 51. The cylindrical body portion 52 can be formed using a laminate in which at least a second thermoplastic resin layer, a base material layer, a polyolefin resin layer, and a first thermoplastic resin layer are laminated in this order.

(Another aspect)
The present inventors focused on ethylene, which is a raw material for polyolefin resin, and developed a biomass polyolefin (hereinafter simply referred to as "biomass polyolefin") that uses biomass-derived ethylene as a raw material instead of conventional ethylene obtained from fossil fuels. A laminate including a polyolefin resin layer containing a polyolefin resin layer (hereinafter sometimes simply referred to as "fossil fuel-derived polyolefin") is a polyolefin resin layer made of polyolefin manufactured using ethylene obtained from conventional fossil fuels (hereinafter sometimes simply referred to as "fossil fuel-derived polyolefin"). It was found that it is possible to obtain a laminate that is comparable in terms of physical properties such as mechanical properties to a laminate comprising the following. Another aspect of the present invention is based on this finding.
Therefore, an object of another aspect of the present invention is to provide a laminate comprising a polyolefin resin layer containing a biomass polyolefin, which is comparable in physical properties such as mechanical properties to a conventional laminate comprising a polyolefin resin layer comprising a polyolefin derived from fossil fuels. It's about giving your body.
In another aspect of the invention,
A laminate comprising at least a base material layer, a polyolefin resin layer, and a thermoplastic resin layer in this order,
The polyolefin resin layer includes a biomass polyolefin that is a polymer of a monomer containing ethylene derived from biomass,
A laminate is provided in which the degree of biomass in the polyolefin resin layer is 5% or more.
In another aspect of the present invention, it is preferable that the polyolefin resin layer further contains a fossil fuel-derived polyolefin.
In another aspect of the present invention, the polyolefin resin layer preferably contains the biomass polyolefin at 5% by mass or more and 100% by mass or less, and the fossil fuel-derived polyolefin at 0% by mass or more and 95% by mass or less.
In another aspect of the present invention, the polyolefin resin layer preferably contains polyethylene.
In another aspect of the invention, the thermoplastic resin layer includes a resin material selected from the group consisting of low density polyethylene, linear low density polyethylene, medium density polyethylene, and ethylene-methacrylic acid copolymer. It is preferable.
In another aspect of the invention, it is preferable that the base layer includes a resin material selected from the group consisting of polyester, polyolefin, and polyamide.
In another aspect of the present invention, there is provided a method for manufacturing the laminate, comprising:
A method for manufacturing a laminate is provided, in which the base material layer and the thermoplastic resin layer are bonded together via the melt-extruded polyolefin resin layer.
In another aspect of the present invention, a packaging product comprising the laminate is provided.
In another aspect of the present invention, a flexible packaging including the laminate is provided.
A laminate according to another aspect of the present invention includes at least a base material layer, a polyolefin resin layer containing biomass polyolefin, and a thermoplastic resin layer, thereby reducing the amount of fossil fuel used compared to conventional methods. can reduce environmental impact. In addition, the laminate according to another aspect of the present invention is comparable in physical properties such as mechanical properties to conventional laminates of fossil fuel-derived polyolefin resins, so it is a laminate of conventional fossil fuel-derived polyolefin resins. It is possible to replace the body.

EXAMPLES The present invention will be explained in more detail below with reference to Examples and Comparative Examples, but the present invention should not be construed as limited to the following Examples.

<Measurement/Conditions>
In the following Reference Examples, Reference Comparative Examples, Examples, and Comparative Examples, the biomass degree is the value of biomass-derived carbon concentration determined by radiocarbon (C14) measurement.

The conditions of the extrusion film forming machine used below were as follows.
Screw diameter: 90mm
Screw type: Full flight L/D: 28
T-die: 11S type straight manifold T-die effective opening length: 560mm

[Example 1]
<Preparation of laminate 1>
A fossil fuel-derived polyethylene terephthalate film (manufactured by Toyobo Co., Ltd.: E5100, thickness 12 μm) was prepared as a base material layer, and a two-component curing anchor coating agent (manufactured by Mitsui Chemicals, Inc.: A3210/A3075, polyurethane-based) was prepared on the corona-treated surface. ) to form an anchor coat layer. Subsequently, biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 min, biomass degree: While extruding a fossil fuel-derived linear low-density polyethylene film (manufactured by Mitsui Chemicals Tohcello: T.U.X FC-) through this polyolefin resin layer (biomass degree: 95%, thickness 15 μm). A laminate 1 in which a base material layer, an anchor coat layer, a polyolefin resin layer, and a thermoplastic resin layer were laminated in this order was obtained by bonding the corona-treated surfaces of the laminate (S, thickness: 40 μm).

[Example 2]
<Preparation of laminate 2>
A fossil fuel-derived polyethylene terephthalate film (manufactured by Toyobo Co., Ltd.: E5100, thickness 12 μm) was prepared as the base material layer, and its corona-treated surface was coated with a two-component curing anchor coating agent (manufactured by Mitsui Chemicals, Inc.: A3210/A3075). An anchor coat layer was formed. Subsequently, biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 min, biomass degree: 95%) 50 parts by mass and 50 parts by mass of low-density polyethylene derived from fossil fuel (manufactured by Japan Polyethylene Co., Ltd., LC600A, density: 0.918 g/cm ³ , MFR: 7.0 g/10 min, biomass degree: 0%). While extruding the dry-blended mixed resin, a fossil fuel-derived linear low-density polyethylene film (Mitsui Chemicals Tohcello: T.U. A laminate 2 in which a base material layer, an anchor coat layer, a polyolefin resin layer, and a thermoplastic resin layer were laminated in this order was obtained by laminating the corona-treated surfaces of X FC-S (thickness: 40 μm).

[Comparative example 1]
<Preparation of laminate 3>
A fossil fuel-derived polyethylene terephthalate film (manufactured by Toyobo Co., Ltd.: E5100, thickness 12 μm) was prepared as the base material layer, and its corona-treated surface was coated with a two-component curing anchor coating agent (manufactured by Mitsui Chemicals, Inc.: A3210/A3075). An anchor coat layer was formed. Next, fossil fuel-derived low density polyethylene (manufactured by Japan Polyethylene Co., Ltd., LC600A, density: 0.918 g/cm ³ , MFR: 7.0 g/10 min, biomass) was applied onto the anchor coat layer using a sand lamination method. While extruding a fossil fuel-derived linear low-density polyethylene film (manufactured by Mitsui Chemicals Tohcello: T.U.X. The corona-treated surfaces of FC-S (40 μm thick) were bonded together to obtain a laminate 3 in which a base layer, an anchor coat layer, an adhesive resin layer, and a thermoplastic resin layer were laminated in this order.

[Example 3]
<Preparation of laminate 4>
A fossil fuel-derived polyethylene terephthalate film (manufactured by Toyobo Co., Ltd.: E5100, thickness 12 μm) was prepared as the base material layer, and its corona-treated surface was coated with a two-component curing anchor coating agent (manufactured by Mitsui Chemicals, Inc.: A3210/A3075). An anchor coat layer was formed. Subsequently, biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 min, biomass degree: Aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, thickness 7 μm) was bonded through this polyolefin resin layer (biomass degree: 95%, thickness 15 μm) while extruding the polyolefin resin layer (95%). Subsequently, a two-component curing anchor coating agent (manufactured by Mitsui Chemicals, Inc.: A3210/A3075) was coated on the aluminum foil to form an anchor coating layer. Next, fossil fuel-derived low density polyethylene (manufactured by Japan Polyethylene Co., Ltd., LC600A, density: 0.918 g/cm ³ , MFR: 7.0 g/10 minutes, biomass degree: 0%) was applied to the anchor coat layer at 320°C. Melt extrusion lamination was carried out at a resin temperature of 100 m/min at a line speed of 100 m/min to form a thermoplastic resin layer (biomass degree: 0%, thickness 30 μm), and a base material layer, an anchor coat layer, a polyolefin resin layer, a barrier layer, A laminate 4 was obtained in which an anchor coat layer and a thermoplastic resin layer were laminated in this order.

[Example 4]
<Preparation of laminate 5>
A fossil fuel-derived polyethylene terephthalate film (manufactured by Toyobo Co., Ltd.: E5100, thickness 12 μm) was prepared as the base material layer, and its corona-treated surface was coated with a two-component curing anchor coating agent (manufactured by Mitsui Chemicals, Inc.: A3210/A3075). An anchor coat layer was formed. Subsequently, biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 min, biomass degree: 95%) 50 parts by mass and 50 parts by mass of low-density polyethylene derived from fossil fuel (manufactured by Japan Polyethylene Co., Ltd., LC600A, density: 0.918 g/cm ³ , MFR: 7.0 g/10 min, biomass degree: 0%). While extruding the dry-blended mixed resin, aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, thickness 7 μm) was attached via this polyolefin resin layer (biomass degree: 48%, thickness 15 μm). Subsequently, a two-component curing anchor coating agent (manufactured by Mitsui Chemicals, Inc.: A3210/A3075) was coated on the aluminum foil to form an anchor coating layer. Next, fossil fuel-derived low density polyethylene (manufactured by Japan Polyethylene Co., Ltd., LC600A, density: 0.918 g/cm ³ , MFR: 7.0 g/10 minutes, biomass degree: 0%) was applied to the anchor coat layer at 320°C. Melt extrusion lamination was carried out at a resin temperature of 100 m/min at a line speed of 100 m/min to form a thermoplastic resin layer (biomass degree: 0%, thickness 30 μm), and a base material layer, an anchor coat layer, a polyolefin resin layer, a barrier layer, A laminate 5 was obtained in which an anchor coat layer and a thermoplastic resin layer were laminated in this order.

[Comparative example 2]
<Preparation of laminate 6>
A fossil fuel-derived polyethylene terephthalate film (manufactured by Toyobo Co., Ltd.: E5100, thickness 12 μm) was prepared as the base material layer, and its corona-treated surface was coated with a two-component curing anchor coating agent (manufactured by Mitsui Chemicals, Inc.: A3210/A3075). An anchor coat layer was formed. Next, fossil fuel-derived low density polyethylene (manufactured by Japan Polyethylene Co., Ltd., LC600A, density: 0.918 g/cm ³ , MFR: 7.0 g/10 min, biomass) was applied onto the anchor coat layer using a sand lamination method. Aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, 7 μm thick) was bonded to the adhesive resin layer (biomass concentration: 0%, thickness 15 μm) via this adhesive resin layer (biomass concentration: 0%). Subsequently, a two-component curing anchor coating agent (manufactured by Mitsui Chemicals, Inc.: A3210/A3075) was coated on the aluminum foil to form an anchor coating layer. Next, fossil fuel-derived low density polyethylene (manufactured by Japan Polyethylene Co., Ltd., LC600A, density: 0.918 g/cm ³ , MFR: 7.0 g/10 minutes, biomass degree: 0%) was applied to the anchor coat layer at 320°C. Melt-extrusion lamination was performed at a resin temperature of A laminate 6 was obtained in which an anchor coat layer and a thermoplastic resin layer were laminated in this order.

[Example 5]
<Preparation of laminate 7>
As the aluminum vapor-deposited polyethylene terephthalate film 1, a fossil fuel-derived polyethylene terephthalate film (manufactured by Toray Film Kako Co., Ltd., 1310, thickness 12 μm) on which an aluminum vapor-deposited film was formed was prepared.

A biaxially stretched polypropylene film (manufactured by Toyobo Co., Ltd.: P2161, thickness 20 μm) was prepared as a base material layer, and its corona-treated surface was coated with a two-component curable anchor coating agent (manufactured by Mitsui Chemicals, Inc.: A3210/A3075). , an anchor coat layer was formed. Subsequently, biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 min, biomass degree: The aluminum-deposited surface of the above-mentioned aluminum-deposited polyethylene terephthalate film 1 was bonded to each other via this polyolefin resin layer (biomass degree: 95%, thickness 15 μm) while extruding the polyolefin resin layer (95%). Subsequently, a two-component curing anchor coating agent (manufactured by Mitsui Chemicals, Inc.: A3210/A3075) was coated on the polyethylene terephthalate film surface of the aluminum vapor-deposited polyethylene terephthalate film 1 to form an anchor coat layer. Thereafter, biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 min, biomass degree: 95) was applied onto the anchor coat layer using a sand lamination method. %), a fossil fuel-derived linear low-density polyethylene film (T.U. , 40 μm thick) corona-treated surfaces are laminated together, and a base material layer, anchor coat layer, polyolefin resin layer, barrier layer, plastic film, anchor coat layer, adhesive resin layer, and thermoplastic resin layer are laminated in this order. Obtained body 7.

[Example 6]
<Production of laminate 8>
A biaxially stretched polypropylene film (manufactured by Toyobo Co., Ltd.: P2161, thickness 20 μm) was prepared as a base material layer, and its corona-treated surface was coated with a two-component curable anchor coating agent (manufactured by Mitsui Chemicals, Inc.: A3210/A3075). , an anchor coat layer was formed. Subsequently, biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 min, biomass degree: 95%) 50 parts by mass and 50 parts by mass of low-density polyethylene derived from fossil fuel (manufactured by Japan Polyethylene Co., Ltd., LC600A, density: 0.918 g/cm ³ , MFR: 7.0 g/10 min, biomass degree: 0%). While extruding the dry-blended mixed resin, the aluminum-deposited surface of the aluminum-deposited polyethylene terephthalate film 1 was bonded to the aluminum-deposited polyethylene terephthalate film 1 via this polyolefin resin layer (biomass degree: 48%, thickness 15 μm). Subsequently, a two-component curing anchor coating agent (manufactured by Mitsui Chemicals, Inc.: A3210/A3075) was coated on the polyethylene terephthalate film surface of the aluminum vapor-deposited polyethylene terephthalate film 1 to form an anchor coat layer. Thereafter, biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 min, biomass degree: 95) was applied onto the anchor coat layer using a sand lamination method. %) and 50 parts by mass of fossil fuel-derived low density polyethylene (manufactured by Japan Polyethylene Co., Ltd., LC600A, density: 0.918 g/cm ³ , MFR: 7.0 g/10 min, biomass degree: 0%). While extruding the dry blended mixed resin, a fossil fuel-derived linear low-density polyethylene film (manufactured by Mitsui Chemicals Tohcello: T.U.X. The corona-treated surfaces of FC-S (40 μm thick) are laminated together, and the base layer, anchor coat layer, polyolefin resin layer, barrier layer, plastic film, anchor coat layer, adhesive resin layer, and thermoplastic resin layer are laminated in this order. A laminate 8 was obtained.

[Comparative example 3]
<Preparation of laminate 9>
A biaxially stretched polypropylene film (manufactured by Toyobo Co., Ltd.: P2161, thickness 20 μm) was prepared as a base material layer, and its corona-treated surface was coated with a two-component curable anchor coating agent (manufactured by Mitsui Chemicals, Inc.: A3210/A3075). , an anchor coat layer was formed. Next, fossil fuel-derived low density polyethylene (manufactured by Japan Polyethylene Co., Ltd., LC600A, density: 0.918 g/cm ³ , MFR: 7.0 g/10 min, biomass) was applied onto the anchor coat layer using a sand lamination method. The aluminum-deposited surface of the above-mentioned aluminum-deposited polyethylene terephthalate film 1 was bonded together via this adhesive resin layer (biomass degree: 0%, thickness: 15 μm) while extruding the aluminum-deposited polyethylene terephthalate film 1. Subsequently, a two-component curing anchor coating agent (manufactured by Mitsui Chemicals, Inc.: A3210/A3075) was coated on the polyethylene terephthalate film surface of the aluminum vapor-deposited polyethylene terephthalate film 1 to form an anchor coat layer. Then, on the anchor coat layer, using a sand lamination method, low density polyethylene derived from fossil fuel (manufactured by Japan Polyethylene Co., Ltd., LC600A, density: 0.918 g/cm ³ , MFR: 7.0 g/10 minutes, biomass degree : 0%) through this adhesive resin layer (biomass content: 0%, thickness 15 μm). -S, 40 μm thick) corona-treated surfaces are laminated together, and the base material layer, anchor coat layer, adhesive resin layer, barrier layer, plastic film, anchor coat layer, adhesive resin layer, and thermoplastic resin layer are laminated in this order. A laminate 9 was obtained.

[Example 7]
<Production of laminate 10>
Biaxially stretched polyester film 1 (biomass degree: 20%, manufactured by Toyobo Co., Ltd., DE024, thickness 12 μm) was prepared. Next, the corona-treated surface of the polyester film 1 was coated with a two-component curable anchor coating agent (manufactured by Mitsui Chemicals: A3210/A3075, polyurethane type) to form an anchor coat layer. Subsequently, biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 min, biomass degree: While extruding the polyolefin resin layer (biomass content: 95%, thickness 15 μm), a linear low-density polyethylene film derived from fossil fuels (manufactured by Mitsui Chemicals Tohcello: T.U.X FC-) is extruded. A laminate 10 in which a base material layer, an anchor coat layer, a polyolefin resin layer, and a thermoplastic resin layer were laminated in this order was obtained by bonding the corona-treated surfaces of the laminate (S, thickness: 40 μm).

[Example 8]
<Production of laminate 11>
Biaxially stretched polyester film 1 (biomass degree: 20%, manufactured by Toyobo Co., Ltd., DE024, thickness 12 μm) was prepared. Next, a two-part curable anchor coating agent (manufactured by Mitsui Chemicals, Inc.: A3210/A3075) was coated on the corona-treated surface of the polyester film 1 to form an anchor coat layer. Subsequently, biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 min, biomass degree: 95%) 50 parts by mass and 50 parts by mass of low-density polyethylene derived from fossil fuel (manufactured by Japan Polyethylene Co., Ltd., LC600A, density: 0.918 g/cm ³ , MFR: 7.0 g/10 min, biomass degree: 0%). While extruding the dry-blended mixed resin, a fossil fuel-derived linear low-density polyethylene film (Mitsui Chemicals Tohcello: T.U. A laminate 11 in which a base material layer, an anchor coat layer, a polyolefin resin layer, and a thermoplastic resin layer were laminated in this order was obtained by bonding together the corona-treated surfaces of X FC-S (40 μm thick).

[Production Examples 1 to 11]
<Preparation of packaging bag>
A standing pouch was formed by combining the body member laminate (side sheet) and the bottom member laminate (bottom sheet) shown in Table 1 below through the following steps. Specifically, two side sheets are overlapped with the side sheets facing each other so that the thermoplastic resin layer is the innermost layer, and a bottom sheet is inserted between the two side sheets. The bottom sheets were then heat-sealed to produce standing pouches 1 to 11 in the form shown in FIG.

(liquid leak test)
The standing pouches 1 to 11 prepared above were filled with the test liquid (Ageless Seal Check (manufactured by Mitsubishi Gas Chemical)) and stored at room temperature and humidity for 1 hour, and then visually evaluated for liquid leakage according to the evaluation criteria below. did. The evaluation results are shown in Table 1.
(Evaluation criteria)
○: There was no liquid leakage from the heat-sealed part, and the performance as a standing pouch was good.
×: There was liquid leakage from the heat-sealed part, and the performance as a standing pouch was poor.

10, 20, 30 Laminated body 11 Base material layer 12 Polyolefin resin layer 13 Thermoplastic resin layer 14 Barrier layer 15 Plastic film 16 Adhesive layer 40 Standing pouch 41 Body 42 Bottom 50 Laminated tube 51 Head 52 Cylindrical body 53 Shoulder Part 54 Spout part

Claims (6)

A plastic film having at least a base material layer (excluding the biomass polyester resin layer A below), a polyolefin resin layer (excluding those containing biomass-derived linear low-density polyethylene), and a barrier layer. A laminate comprising, in this order, a thermoplastic resin layer, and a thermoplastic resin layer,
the base layer contains polypropylene,
The polyolefin resin layer is composed only of biomass-derived low-density polyethylene, or is composed of a mixed resin of biomass-derived low-density polyethylene and fossil fuel-derived low-density polyethylene,
The degree of biomass in the polyolefin resin layer is 5% or more,
The barrier layer is made of a vapor-deposited film of an inorganic substance or an inorganic oxide,
the barrier layer is in contact with the plastic film,
The thermoplastic resin constituting the thermoplastic resin layer is polypropylene,
The base material layer constitutes the outermost layer,
A laminate, wherein the thermoplastic resin layer constitutes an innermost layer.
Biomass polyester resin layer A:
A biomass polyester resin layer consisting of a biomass polyester resin composition comprising a polyester consisting of a diol unit and a dicarboxylic acid unit as a main component, and wherein the diol unit is ethylene glycol derived from biomass. The laminate according to claim 1, further comprising an adhesive resin layer between the plastic film having the barrier layer and the thermoplastic resin layer. A method for manufacturing a laminate according to claim 1 or 2, comprising:
A method for manufacturing a laminate, in which the base material layer and the plastic layer having the barrier layer are bonded together via the melt-extruded polyolefin resin layer. A packaging product comprising the laminate according to claim 1 or 2. A flexible packaging comprising the laminate according to claim 1 or 2. A packaging bag comprising the laminate according to claim 1 or 2.

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