JP2021062632A - Laminate equipped with polyolefin resin layer and packing product equipped with the same - Google Patents

Abstract

To provide a laminate equipped with a polyolefin resin layer including a polyolefin derived from a conventional fossil fuel and a laminate equipped with a polyolefin resin layer including a biomass polyolefin by no means inferior with regard to physical properties such as mechanical characteristics.SOLUTION: A laminate at least includes a substrate layer, a polyolefin resin layer and a thermoplastic resin layer in this order. The polyolefin resin layer includes a biomass polyolefin being a polymer of a monomer including ethylene derived from biomass. A biomass degree in the polyolefin resin layer is 5% or more.SELECTED DRAWING: Figure 1

Description

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

In recent years, with the growing demand for the construction of a recycling-oriented society, it is desired to break away from fossil fuels in the material field as well as energy, and the use of biomass is drawing attention. Biomass is an organic compound photosynthesized from carbon dioxide and water, and by utilizing it, it becomes carbon dioxide and water again, 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 being made to produce various resins from the biomass raw materials.

As a biomass-derived resin, polylactic acid (PLA), which is produced via lactic acid fermentation, began commercial production in advance, but its biodegradable performance and current general-purpose plastics have performance as plastics. Because it is very different from the above, there are limits to the product applications and product manufacturing methods, and it has not been widely used. In addition, life cycle assessment (LCA) evaluation is being conducted for PLA, and discussions are being held on energy consumption during PLA manufacturing and equivalence when replacing general-purpose plastics.

Here, as the general-purpose plastic, various types such as polyethylene, polypropylene, polyvinyl chloride, and polystyrene are used. In particular, polyethylene is molded into films, sheets, bottles and the like, and is used for various purposes such as packaging materials, and is widely used all over the world. Therefore, the use of conventional fossil fuel-derived polyethylene has a large environmental load.

Therefore, it is desired to reduce the amount of fossil fuel used by using a raw material derived from biomass 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).

Japanese Patent Application Laid-Open No. 2011-506628

The present inventors have focused on ethylene, which is a raw material for polyolefin resins, and instead of ethylene obtained from conventional fossil fuels, low-density polyethylene using ethylene derived from biomass as a raw material (hereinafter, simply "low density derived from biomass"). The laminate provided with the polyolefin resin layer containing (sometimes referred to as "density polyethylene") is a low-density polyethylene produced using ethylene obtained from a conventional fossil fuel (hereinafter, simply referred to as "low-density polyethylene derived from fossil fuel"). It was found that a laminate having a polyolefin resin layer made of (may be) and a laminate having physical properties such as mechanical properties that are comparable to each other can be obtained. The present invention is based on such findings.

Therefore, an object of the present invention is to provide a polyolefin resin layer containing low-density polyethylene derived from biomass, which is comparable in physical properties such as mechanical properties to a laminate having a conventional polyolefin resin layer made of low-density polyethylene derived from fossil fuel. It is to provide a laminate to be provided.

In aspects of the invention
A laminate including 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 material layer contains polypropylene and contains
The polyolefin resin layer contains low density polyethylene derived from biomass and contains
The degree of biomass in the polyolefin resin layer is 5% or more, and the degree of biomass is 5% or more.
The base material layer constitutes the outermost layer, and
Provided is a laminate in which the thermoplastic resin layer constitutes the innermost layer.
In the aspect of the present invention, it is preferable that the laminate 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 a method for producing the laminate.
Provided is a method for producing a laminate in which the base material layer and the plastic layer having the barrier layer are bonded to each other via the polyolefin resin layer that has been melt-extruded.
In another aspect of the invention, a packaged product comprising the laminate is provided.
In another aspect of the invention, flexible packaging with said laminate is provided.
In another aspect of the present invention, a packaging bag comprising the laminate is provided.

The laminate according to the present invention is provided with at least a base material layer, a polyolefin resin layer containing low-density polyethylene derived from biomass, a plastic film having a barrier layer, and a thermoplastic resin layer, as compared with the conventional one. The amount of fossil fuel used can be reduced, and the environmental load can be reduced. Further, the laminate according to the present invention is not inferior to the laminate having a polyolefin resin layer containing low-density polyethylene derived from the conventional fossil fuel in terms of physical properties such as mechanical properties, so that the laminate derived from the conventional fossil fuel is low. A polyolefin resin layer containing density polyethylene can be substituted.

It is a schematic cross-sectional view which shows an example of the laminated body by this invention. It is a schematic cross-sectional view which shows an example of the laminated body by this invention. It is a schematic cross-sectional view which shows an example of the laminated body by this invention. It is a simplified diagram which shows an example of the structure of a standing pouch. It is a simplified figure which shows an example of the structure of a laminated tube.

In the present invention, the "biomass polyolefin" and the "polyolefin resin layer containing biomass polyolefin" are those using at least a part of the raw material derived from biomass as the raw material, and all of the raw materials are derived from biomass. 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 the term "thermoplastic resin layer" is used, it means 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 as compared with the conventional one, and the environmental load can be reduced. Further, the laminate according to the present invention is comparable to the laminate of polyolefin resin produced from the raw material obtained from the conventional fossil fuel in terms of physical properties such as mechanical properties, and therefore the laminate of conventional polyolefin resin. Can be substituted.

In addition to the above layers, the laminate according to the present invention may further have at least one other layer such as a printing layer, a barrier layer, a plastic film, an adhesive layer, and a second thermoplastic resin layer. When two or more other layers are provided, they may have the same composition or different compositions.

The laminate according to the present invention will be described with reference to the drawings. Examples of schematic cross-sectional views of the laminated body according to the present invention are shown in FIGS.
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 directly formed on the polyolefin resin layer 12. Is. In the case of the 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 polyolefin resin layer 12, a barrier layer 14, and a thermoplastic resin layer 13 in this order on one surface of the base material layer 11 and the base material layer 11. In the case of the flexible packaging including the laminate 20, the thermoplastic resin layer 13 is located inside the flexible packaging.
The laminate 30 shown in FIG. 3 has 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 material layer 11 and the base material layer 11. Prepare in this order. In the case of the flexible packaging including the laminate 30, the thermoplastic resin layer 13 is located inside the flexible packaging.
In any laminate, a print layer or a second thermoplastic resin layer may be further laminated. When laminating the printing layer and the second thermoplastic resin layer, the second thermoplastic resin layer may be laminated so as to be the outermost surface.
Hereinafter, each layer constituting the laminated body will be described.

(Base layer)
In the present invention, the base material layer functions as a base material layer for holding the polyolefin resin layer, and it is preferable that the base material layer can impart strength as a packaged product to the laminate. As the base material layer, a resin base material, preferably a plastic film made 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, or may be used alone. Two or more types may be used in combination. Further, when two or more kinds are combined, they may be laminated by using a dry laminating method or may be laminated by using 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 material derived from biomass or a material derived from fossil fuel.

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

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

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

The degree of biomass in the base material layer is 5% or more, preferably 10% or more, and more preferably 15% or more. When the biomass content in the base material layer is 5% or more, the amount of polyester derived from fossil fuel can be reduced and the environmental load can be reduced as compared with the conventional case.

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

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

Biomass-derived ethylene glycol is made from ethanol (biomass ethanol) produced from biomass as a raw material. For example, biomass-derived ethylene glycol can be obtained from biomass ethanol by a method of producing ethylene glycol via ethylene oxide by a conventionally known method. Further, commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycol Co., Ltd. can be preferably used.

As the dicarboxylic acid unit of biomass polyester, a fossil fuel-derived dicarboxylic acid is used. As the dicarboxylic acid, aromatic dicarboxylic acid, aliphatic dicarboxylic acid, and derivatives thereof can be used without limitation. Examples of the aromatic dicarboxylic acid include terephthalic acid and isophthalic acid, and examples of the derivative of the aromatic dicarboxylic acid include lower alkyl esters of the aromatic dicarboxylic acid, specifically, methyl ester, ethyl ester, propyl ester and butyl. Esters and the like can be mentioned. Among these, terephthalic acid is preferable, and dimethyl terephthalate is preferable as the derivative of the aromatic dicarboxylic acid.

(Polyolefin resin layer)
In the present invention, the polyolefin resin layer contains biomass polyolefin, which is a polymer of a monomer containing ethylene derived from biomass, and may further contain polyolefin derived from fossil fuel. 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 with respect to the entire polyolefin resin layer. It may contain less than mass% of biomass polyolefin and polyolefins derived from fossil fuels exceeding 0% by mass and 95% by mass or less, and 25% by mass or more and 75% by mass or less of biomass polyolefins and 25% by mass or more and 75% by mass or less of fossil fuels. It may contain the polyolefin of origin. It suffices if the following biomass degree can be realized as the entire polyolefin resin layer. In the present invention, since the polyolefin resin layer contains biomass polyolefin, the amount of fossil fuel-derived polyolefin can be reduced and the environmental load can be reduced as compared with the conventional case.

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 content of biomass-derived carbon by radiocarbon (C14) measurement. Since carbon dioxide in the atmosphere contains C14 at a fixed ratio (105.5 pMC), the C14 content in plants that grow by taking in carbon dioxide in the atmosphere, such as corn, is also about 105.5 pMC. It is known. It is also known that fossil fuels contain almost no C14. Therefore, the proportion of biomass-derived carbon can be calculated by measuring the proportion of C14 contained in all carbon atoms in the polyolefin. In the present invention, in the case where the content of C14 in the polyolefin was P _C14, the content P _{bio Bio} carbon from biomass, can be obtained as follows.
_{P bio (%) = P C14} /105.5×100

In the present invention, theoretically, if all biomass-derived ethylene is used as the raw material for the 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 the fossil fuel-derived raw material is 0%, and the biomass degree of the fossil fuel-derived polyolefin is 0%.

In the present invention, the biomass degree in the polyolefin resin layer is 5% or more, preferably 10% or more, more preferably 15% or more, still more preferably 20% or more. The degree of biomass in the polyolefin resin layer does not have to be 100%. This is because if a raw material derived from biomass is used even in a part of the laminate, the purpose of the present invention is to reduce the amount of fossil fuel used as compared with the conventional case. When the biomass content in the polyolefin resin layer is 5% or more, the amount of fossil fuel-derived polyolefin can be reduced and the environmental load can be reduced as compared with the conventional case.

Polyolefin resin layer is preferably from 0.91 g / cm ³ or more 0.93 g / cm ³ or less, more preferably 0.911 g / cm ³ or more 0.928 g / cm ³ or less, 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 the method A of JIS K7112-1980 after performing the annealing described in JIS K6760-1980. If the density of the polyolefin resin layer is 0.91 g / cm ³ or more 0.93 g / cm ³ or less, it is possible to facilitate processing and molding.

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. When the thickness of the polyolefin resin layer is about the above range, the function of adhering the two layers can be sufficiently fulfilled.

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

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

The above-mentioned α-olefin has no particular limitation on the number of carbon atoms, but usually one having 3 to 20 carbon atoms can be used, and it is preferable that the α-olefin is butylene, hexene, or octene. Butylene, hexene, or octene can be produced by polymerization of 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, so that it 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 kinds thereof may be mixed and used. 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 produce 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.

Biomass polyolefin, preferably 0.91 g / cm ³ or more 0.93 g / cm ³ or less, more preferably 0.912 g / cm ³ or more 0.928 g / cm ³ or less, more preferably 0.915 g / cm ³ or more 0 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 the method A of JIS K7112-1980 after performing the annealing described in JIS K6760-1980. When 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 the inner layer of the packaged product. Further, when 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 enhanced, and it can be suitably used as the inner layer of the packaged product.

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. It has a rate (MFR). The melt flow rate is a value measured by the method A under the conditions of a temperature of 190 ° C. and a load of 21.18 N in the method specified in JIS K7210-1995. When the MFR of the biomass polyolefin is 0.1 g / 10 minutes or more, the extrusion load during the molding process can be reduced. Further, when 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.

As the biomass polyolefin preferably used in the present invention, low-density polyethylene derived from biomass manufactured by Braskem (trade name: SBC818, density: 0.918 ^{g / cm 3} , MFR: 8.1 g / 10 minutes, biomass degree. 95%), low-density polyethylene derived from biomass manufactured by Braskem (trade name: SPB681, density: 0.922 g / cm ³ , MFR: 3.8 g / 10 minutes, biomass degree 95%) and the like.

(Manufacturing method of 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 can be obtained by a conventionally known method. Hereinafter, an example of a method for producing ethylene-derived ethylene will be described.

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 raw materials. The plant material is not particularly limited, and conventionally known plants can be used. For example, corn, sugar cane, beets, and manioc can be mentioned.

In the present invention, the fermented ethanol derived from biomass refers to ethanol purified by contacting a culture solution containing a carbon source obtained from a plant raw material with a microorganism producing ethanol or a product derived from a crushed product thereof. Conventionally known methods such as distillation, membrane separation, and extraction can be applied to the purification of ethanol from the culture broth. For example, a method of adding benzene, cyclohexane or the like and azeotropically boiling the mixture, or removing water by membrane separation or the like can be mentioned.

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

A catalyst is usually used when ethylene is obtained by a dehydration reaction of ethanol, but the catalyst is not particularly limited, and a conventionally known catalyst can be used. Advantageous in the process is a fixed bed flow reaction in which the catalyst and the product can be easily separated, and for example, γ-alumina and the like are preferable.

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

The reaction pressure is also not particularly limited, but a pressure equal to or higher than normal pressure is preferable in order to facilitate subsequent gas-liquid separation. Industrially, a fixed bed flow reaction in which the catalyst can be easily separated is preferable, but a liquid phase suspension bed, a fluidized bed, or the like may also be used.

In the dehydration reaction of ethanol, the yield of the reaction depends on the amount of water contained in the ethanol supplied as a raw material. Generally, when a dehydration reaction is carried out, it is preferable that there is no water in consideration of the efficiency of removing water. However, in the case of the dehydration reaction of ethanol using a solid catalyst, it was found that the amount of other olefins, especially butene, tends to increase in the absence of water. It is presumed that it is not possible to suppress ethylene dimerization after dehydration without the presence of a small amount of water. The lower limit of the allowable water content should be 0.1% or more, preferably 0.5% or more. The upper limit is not particularly limited, but from the viewpoint of mass balance and heat balance, it is preferably 50% by mass or less, more preferably 30% or less, still more preferably 20% or less.

By performing the ethanol dehydration reaction in this way, a mixed portion of ethylene, water and a small amount of unreacted ethanol can be obtained. However, since ethylene is a gas at about 5 MPa or less at room temperature, it is separated from these mixed portions by gas-liquid separation. Ethylene can be obtained except for water and ethanol. This method may be performed by a known method.

Ethylene obtained by gas-liquid separation is further distilled, and the distillation method, operating temperature, residence time, and the like are not particularly limited except that the operating pressure at this time is normal pressure or higher.

When the raw material is ethanol derived from ammonia, the obtained ethylene contains carbonyl compounds such as ketones, aldehydes, and esters, which are impurities mixed in the ethanol fermentation process, carbon dioxide gas, which is a decomposition product thereof, and decomposition products of enzymes. It contains a very small amount of nitrogen-containing compounds such as amines and amino acids, which are impurities, and ammonia, which is a decomposition product thereof. Depending on the use of ethylene, these trace amounts of impurities may cause 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 having a high surface area is preferable, and the type of adsorbent is selected according to the type and amount of impurities in ethylene obtained by the dehydration reaction of ethanol derived from biomass.

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

(Manufacturing method of biomass polyolefin)
In the present invention, the method for polymerizing a monomer containing ethylene derived from biomass is not particularly limited, and a conventionally known method can be used. The polymerization temperature and the polymerization pressure may be appropriately adjusted according to the polymerization method and the polymerization apparatus. The polymerization apparatus is not particularly limited, and conventionally known apparatus can be used. Hereinafter, an example of a method for polymerizing a monomer containing ethylene will be described.

The method for polymerizing a polyolefin, particularly an ethylene polymer or a copolymer of ethylene and α-olefin, is a method of polymerizing a target type of polyethylene, for example, high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE). ), And linear low-density polyethylene (LLDPE) or the like, which can be appropriately selected depending on the difference in density and branching.
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. .. Compared with the multisite catalyst, the single-site catalyst is preferable because it has a uniform active site structure and 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 to form an indenyl ring, a fluorenyl ring, an azulenyl ring, a hydrogenated product thereof, or the like. 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.

In the transition metal compound of Group IV of the periodic table, typical ligands other than the ligand having a cyclopentadienyl skeleton are hydrogen and 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 and the like.

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, 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, organozinc compounds and the like. Of these, organoaluminum is preferably used.

In addition to the polyolefin as the main component, various additives may be added to the biomass polyolefin as long as its properties are not impaired. Additives include, for example, plasticizers, UV stabilizers, color inhibitors, matting agents, deodorants, flame retardants, weatherproofing agents, antistatic agents, thread friction reducing agents, slipping agents, mold release agents, anti-flammants. Excipients, ion exchangers, coloring pigments and the like can be added. These additives are preferably added in the range 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 total biomass polyolefin.

(Thermoplastic resin layer)
The thermoplastic resin layer can be formed by using a conventionally known thermoplastic resin. By further providing the laminate with a thermoplastic resin layer, the same heat resistance, pressure resistance, water resistance, heat sealability, pinhole resistance, puncture resistance, and other physical properties as those of the conventional laminate are imparted. be able to.

Examples of the thermoplastic resin 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. Combined, ethylene-methacrylic acid copolymer, ethylene-methylacrylate copolymer, ethylene-ethylacrylate copolymer, ethylene-methylmethacrylate copolymer, ionomer resin, polyester resin, polyvinyl chloride resin, polystyrene resin, nylon, etc. Examples thereof include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, and ethylene-methacrylic acid copolymers.

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

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

(Print layer)
The printing layer is used for decoration, display of contents, display of expiration date, display of manufacturers, sellers, etc., and for display of other things and giving aesthetics, such as letters, numbers, patterns, figures, symbols, patterns, etc. A layer that forms any desired print pattern. The printing layer can be provided as needed, and can be provided, for example, 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 printed layer can be formed by using a conventionally known pigment or dye, and the forming method thereof 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 an inorganic substance or a vapor-deposited film of an inorganic oxide or a metal foil. The vapor-deposited film can be formed by a conventionally known method using a conventionally known inorganic substance or an inorganic oxide, and the composition and the forming method thereof are not particularly limited. When the laminate further has a barrier layer, it is possible to impart or improve a gas barrier property that blocks the permeation of oxygen gas, water vapor, and the like, and a light-shielding property that blocks the permeation of visible light, ultraviolet rays, and the like. The laminated body may have two or more barrier layers. When two or more barrier layers are provided, they may have the same composition or different compositions.

Examples of the vapor deposition 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) and other inorganic substances or inorganic oxide vapor deposition films can be used. In particular, as a material (bag) for packaging or the like, it is preferable to use an aluminum metal vapor deposition film or a silicon oxide or aluminum metal or aluminum oxide vapor deposition film.

Representation of the inorganic oxide, for _example, SiO X, as such AlO _X MO _X (In the formula, M represents an inorganic element, the value of X, varies each of an inorganic element range.) In expressed. The range of X values is 0 to 2 for silicon (Si), 0 to 1.5 for aluminum (Al), 0 to 1 for magnesium (Mg), and 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, and titanium (Ti). Can take a value in the range of 0 to 2, lead (Pb) 0 to 1, zirconium (Zr) 0 to 2, and yttrium (Y) 0 to 1.5. In the above, when X = 0, it is a completely inorganic simple 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 as 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 one with the value of.

In the present invention, the film thickness of the thin-film film of the inorganic substance or the inorganic oxide as described above varies depending on the type of the inorganic substance or the inorganic oxide used, and 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 within the range of. More specifically, in the case of a thin-film aluminum film, a film thickness of 50 Å or more and 600 Å or less, more preferably 100 Å or more and 450 Å or less is desirable, and in the case of an aluminum oxide or silicon oxide film. A film thickness of 50 Å or more and 500 Å or less, more preferably 100 Å or more and 300 Å or less is desirable.

The vapor-deposited film can be formed on a plastic film such as polyethylene terephthalate or nylon by the following forming method. Examples of the method for forming the vapor deposition film include a physical vapor deposition method (PVD method) such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, or a plasma chemical vapor deposition method and thermochemistry. Examples thereof include a chemical vapor deposition method (Chemical Vapor Deposition method, CVD method) such as a vapor phase growth method and a photochemical vapor deposition method.

Further, according to another aspect, the barrier layer may be a metal foil obtained by rolling a metal. As the metal foil, a conventionally known metal foil can be used. Aluminum foil is preferable from the viewpoint of gas barrier property that blocks the transmission of oxygen gas, water vapor, and the like, and light-shielding property that blocks the transmission of visible light, ultraviolet rays, and the like.

(Plastic film)
In the present invention, various plastic films may be used as other layers. For example, either a stretched polyethylene terephthalate film, a stretched nylon film, a stretched polypropylene film, a nylon 6 / metaxylylene diamine nylon 6 co-pressed co-stretched film or a polypropylene / ethylene-vinyl alcohol copolymer co-pressed co-stretched film, or It may be a composite film in which these two or more films are laminated. The plastic film may be coated with polyvinyl alcohol or the like.

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

(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 the two layers are bonded by the dry laminating method.
Examples of the adhesive include one-component or two-component curable or non-curable vinyl type, (meth) acrylic type, polyamide type, polyester type, polyether type, polyurethane type, epoxy type, rubber type, and others. Such solvent type, water-based type, or emulsion type adhesives can be used. As a coating method of the above-mentioned adhesive for laminating, for example, a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a fonten method, a transfer roll coating method, or other methods are used to form a laminate. It can be applied to the coated surface of the layer. The coating amount is preferably 0.1 g / m ² or more and 10 g / m ² or less (dry state), and more preferably 1 g / m ² or more and 5 g / m ² or less (dry state).

Further, the adhesive layer is formed by applying an anchor coating agent to the surface of the layer to be laminated and drying it when laminating a polyolefin resin layer, a thermoplastic resin layer, or the like by a melt extrusion laminating method. It may be a coat layer. Examples of the anchor coating agent include an anchor coating agent made of any resin having a heat resistant temperature of 135 ° C. or higher, for example, a vinyl-modified resin, an epoxy resin, a urethane resin, a polyester resin, or the like. An anchor coating agent composed 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 in combination with this as an additive, or nitric acid cotton may be used in combination to increase heat resistance.

Further, the adhesive layer may be an adhesive resin layer used when two layers are bonded by a sand laminating method or a melt extrusion laminating method. The thermoplastic resin that can be used for the adhesive resin layer includes a polyethylene resin, a polypropylene resin, a cyclic polyolefin resin, or a copolymer resin containing these resins as a main component, a modified resin, or a mixture (including an alloy). ) Can be used. Examples of the polyolefin resin include low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear (linear) low density polyethylene (LLDPE), polypropylene (PP), and metallocene catalyst. Ethylene-α / olefin copolymer, random or block copolymer of ethylene / polypropylene, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene / Ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-maleic acid copolymer, ionomer resin, and adhesion between layers. It is possible to use an acid-modified polyolefin-based resin obtained by modifying the above-mentioned polyolefin-based resin with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid. it can. Further, as the polyolefin resin, an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, a resin obtained by graft-polymerizing or copolymerizing an ester monomer and the like 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 polynorbonene can be used. These resins can be used alone or in combination of two or more. Needless to say, as the above-mentioned polyethylene-based resin, one using the above-mentioned biomass-derived ethylene as a monomer unit can be used.

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

(Manufacturing method of laminated body)
The method for producing the laminate according to the present invention is not particularly limited, and the laminate can be produced by using conventionally known methods such as a dry laminating method, a melt extrusion laminating method, and a sand laminating method. In the present invention, it is preferable to laminate another layer via the polyolefin resin layer melt-extruded by using the sand laminating method. Further, the polyolefin resin layer and another layer may be laminated by a co-extrusion method.

The thickness of the laminate obtained as described above is arbitrary depending on the intended 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 is provided with chemical functions, electrical functions, magnetic functions, mechanical functions, friction / wear / lubrication functions, optical functions, thermal functions, surface functions such as biocompatibility, and the like. It is also possible to perform secondary processing for the purpose. Examples of secondary processing include embossing, painting, adhesion, printing, metallizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, etc.) Coating, etc.) and the like. Further, the laminated body according to the present invention may be subjected to laminating processing (dry laminating or extruded laminating), bag making processing, and other post-treatment processing to produce a molded product.

(Use)
The laminate according to the present invention can be used for a packaging product, and the packaging product is preferably used for flexible packaging such as a packaging bag, a laminate tube, and a lid material. Examples of the packaging bag include a standing pouch type, a side seal type, a two-way seal type, a three-way seal type, a four-way seal type, an envelope-attached seal type, a gassho-attached seal type (pillow-seal type), a fold-attached seal type, and a flat-bottom seal. Examples include various types of packaging bags such as a mold, a square bottom seal type, and a gusset type. The thickness of the laminated body in that case can be appropriately determined depending on the application, and is used, for example, in the form of a film having a thickness of 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 where a packaging bag, for example, a standing pouch is formed by using the laminate according to the present invention will be described. FIG. 4 is a simplified diagram showing an example of the configuration of the standing pouch.
As shown in FIG. 4, the standing pouch 40 is composed of two body portions (side sheet) 41 and a bottom portion (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 different members. The side sheet 41 and the bottom sheet 42 of the standing pouch 40 can be formed by using the laminated body according to the present invention.

Next, a case where a laminated tube is formed by using the laminated body according to the present invention will be described. FIG. 5 is a simplified view showing an example of a laminated tube. As shown in FIG. 5, the laminated tube 50 includes a head portion 51 and a tubular body portion 32. The head 51 is composed of a hollow conical shoulder portion 53 and a spout portion 54, and is integrally formed. The tubular body portion 52 is continuously provided with the shoulder portion 53 of the head portion 51. The tubular body portion 52 can be formed by using at least a laminate in which 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 have focused on ethylene, which is a raw material for polyolefin resins, and instead of ethylene obtained from conventional fossil fuels, biomass polyolefins using ethylene derived from biomass as a raw material (hereinafter, simply referred to as "biomass polyolefin"). The laminate including the polyolefin resin layer containing (there is) is a polyolefin resin layer made of a polyolefin produced using ethylene obtained from a conventional fossil fuel (hereinafter, may be simply referred to as “polyolefin derived from fossil fuel”). It was found that a laminate provided with the above-mentioned material can be obtained in terms of physical properties such as mechanical properties. Another aspect of the invention is based on such findings.
Therefore, an object of another aspect of the present invention is a laminate having a polyolefin resin layer containing a polyolefin resin derived from a conventional fossil fuel and a laminate having a polyolefin resin layer containing a biomass polyolefin, which is comparable in physical properties such as mechanical properties. To provide the body.
In another aspect of the invention
A laminate including at least a base material layer, a polyolefin resin layer, and a thermoplastic resin layer in this order.
The polyolefin resin layer contains biomass polyolefin, which is a polymer of a monomer containing ethylene derived from biomass.
A laminate having a biomass content of 5% or more in the polyolefin resin layer is provided.
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, it is preferable that the polyolefin resin layer contains 5% by mass or more and 100% by mass or less of the biomass polyolefin and 0% by mass or more and 95% by mass or less of the polyolefin derived from the fossil fuel.
In another aspect of the present invention, the polyolefin resin layer preferably contains polyethylene.
In another aspect of the invention, the thermoplastic resin layer comprises a resin material selected from the group consisting of low density polyethylene, linear low density polyethylene, medium density polyethylene, and ethylene-methacrylic acid copolymers. Is preferable.
In another aspect of the invention, the substrate layer preferably comprises a resin material selected from the group consisting of polyester, polyolefin, and polyamide.
In another aspect of the present invention, there is a method for producing the laminate.
Provided is a method for producing a laminate in which the base material layer and the thermoplastic resin layer are bonded to each other via the polyolefin resin layer that has been melt-extruded.
In another aspect of the invention, a packaged product comprising the laminate is provided.
In another aspect of the invention, flexible packaging with said laminate is provided.
The 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 as compared with the conventional one. Can reduce the environmental load. Further, since the laminate according to another aspect of the present invention is not inferior to the conventional fossil fuel-derived polyolefin resin laminate in terms of physical properties such as mechanical properties, the conventional fossil fuel-derived polyolefin resin laminate is not inferior. Can replace the body.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

<Measurement / conditions>
In the following Reference Examples, Reference Comparative Examples, Examples, and Comparative Examples, the biomass degree is a value of carbon concentration derived from biomass as measured by radiocarbon (C14).

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

[Example 1]
<Preparation of laminated body 1>
A fossil fuel-derived polyethylene terephthalate film (Toyobo Co., Ltd .: E5100, thickness 12 μm) was prepared as a base material layer, and a two-component curable anchor coating agent (Mitsui Chemicals Co., Ltd .: A3210 / A3075, polyurethane-based) was prepared on the corona-treated surface. ) Was coated to form an anchor coat layer. Subsequently, a low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0.918 ^{g / cm 3} , MFR: 8.1 g / 10 minutes, degree of biomass: While extruding 95%), a linear low-density polyethylene film derived from fossil fuel (manufactured by Mitsui Chemicals Tohcello: TUX FC-) is passed through this polyolefin resin layer (biomass degree: 95%, thickness 15 μm). A corona-treated surface (S, thickness 40 μm) was laminated to obtain 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.

[Example 2]
<Preparation of laminated body 2>
A fossil fuel-derived polyethylene terephthalate film (Toyobo Co., Ltd .: E5100, thickness 12 μm) is prepared as a base material layer, and a two-component curable anchor coating agent (Mitsui Chemicals Co., Ltd .: A3210 / A3075) is coated on the corona-treated surface. Then, an anchor coat layer was formed. Subsequently, a low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0.918 ^{g / cm 3} , MFR: 8.1 g / 10 minutes, degree of biomass: 95%) 50 parts by mass and low density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene, LC600A, density: 0.918 ^{g / cm 3} , MFR: 7.0 g / 10 minutes, biomass degree: 0%) 50 parts by mass Through this polyolefin resin layer (biomass degree: 48%, thickness 15 μm), a linear low-density polyethylene film derived from fossil fuel (manufactured by Mitsui Kagaku Tohcello: TU. The corona-treated surfaces of XFC-S (thickness 40 μm) were laminated to obtain 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.

[Comparative Example 1]
<Preparation of laminated body 3>
A fossil fuel-derived polyethylene terephthalate film (Toyobo Co., Ltd .: E5100, thickness 12 μm) is prepared as a base material layer, and a two-component curable anchor coating agent (Mitsui Chemicals Co., Ltd .: A3210 / A3075) is coated on the corona-treated surface. Then, an anchor coat layer was formed. Subsequently, on the anchor coat layer, a low density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., LC600A, density: 0.918 ^{g / cm 3} , MFR: 7.0 g / 10 minutes, biomass) was used by a sand laminating method. While extruding (degree: 0%), a linear low-density polyethylene film derived from fossil fuel (manufactured by Mitsui Kagaku Tohcello: TUX: TUX) is passed through this adhesive resin layer (biomass degree: 0%, thickness 15 μm). The corona-treated surfaces of FC-S (thickness 40 μm) were laminated to obtain a laminate 3 in which a base material layer, an anchor coat layer, an adhesive resin layer, and a thermoplastic resin layer were laminated in this order.

[Example 3]
<Preparation of laminated body 4>
A fossil fuel-derived polyethylene terephthalate film (Toyobo Co., Ltd .: E5100, thickness 12 μm) is prepared as a base material layer, and a two-component curable anchor coating agent (Mitsui Chemicals Co., Ltd .: A3210 / A3075) is coated on the corona-treated surface. Then, an anchor coat layer was formed. Subsequently, on the anchor coat layer, a low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0.918 ^{g / cm 3} , MFR: 8.1 g / 10 minutes, biomass degree: While extruding (95%), an aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, thickness 7 μm) was laminated via this polyolefin resin layer (biomass degree: 95%, thickness 15 μm). Subsequently, the aluminum foil was coated with a two-component curable anchor coating agent (manufactured by Mitsui Chemicals, Inc .: A3210 / A3075) to form an anchor coating layer. Subsequently, a low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., LC600A, density: 0.918 ^{g / cm 3} , MFR: 7.0 g / 10 minutes, biomass degree: 0%) was placed on the anchor coat layer at 320 ° C. A thermoplastic resin layer (biomass degree: 0%, thickness 30 μm) is formed by melt-extruding and laminating at a resin temperature of 100 m / min and a line speed of 100 m / min to form a base material layer, an anchor coat layer, a polyolefin resin layer, and a barrier layer. A laminated body 4 in which an anchor coat layer and a thermoplastic resin layer were laminated in this order was obtained.

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

[Comparative Example 2]
<Preparation of laminated body 6>
A fossil fuel-derived polyethylene terephthalate film (Toyobo Co., Ltd .: E5100, thickness 12 μm) is prepared as a base material layer, and a two-component curable anchor coating agent (Mitsui Chemicals Co., Ltd .: A3210 / A3075) is coated on the corona-treated surface. Then, an anchor coat layer was formed. Subsequently, on the anchor coat layer, a fossil fuel-derived low-density polyethylene (manufactured by Japan Polyethylene Corporation, LC600A, density: 0.918 ^{g / cm 3} , MFR: 7.0 g / 10 minutes, biomass) was used by the sand laminating method. While extruding (degree: 0%), an aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, thickness 7 μm) was laminated through this adhesive resin layer (biomass degree: 0%, thickness 15 μm). Subsequently, the aluminum foil was coated with a two-component curable anchor coating agent (manufactured by Mitsui Chemicals, Inc .: A3210 / A3075) to form an anchor coating layer. Subsequently, low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., LC600A, density: 0.918 ^{g / cm 3} , MFR: 7.0 g / 10 minutes, biomass degree: 0%) was placed on the anchor coat layer at 320 ° C. A thermoplastic resin layer (biomass degree: 0%, thickness 30 μm) is formed by melt-extruding and laminating at a resin temperature of 100 m / min and a line speed of 100 m / min to form a base material layer, an anchor coat layer, an adhesive resin layer, and a barrier layer. A laminated body 6 in which an anchor coat layer and a thermoplastic resin layer were laminated in this order was obtained.

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

A biaxially stretched polypropylene film (manufactured by Toyobo Co., Ltd .: P2161, thickness 20 μm) is prepared as a base material layer, and a two-component curable anchor coating agent (manufactured by Mitsui Chemicals Co., Ltd .: A3210 / A3075) is coated on the corona-treated surface. , Anchor coat layer was formed. Subsequently, on the anchor coat layer, a low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0.918 ^{g / cm 3} , MFR: 8.1 g / 10 minutes, biomass degree: While extruding (95%), the aluminum-deposited surface of the above-mentioned aluminum-deposited polyethylene terephthalate film 1 was bonded through the polyolefin resin layer (biomass degree: 95%, thickness 15 μm). Subsequently, a two-component curable anchor coating agent (manufactured by Mitsui Chemicals, Inc .: A3210 / A3075) was coated on the surface of the polyethylene terephthalate film 1 of the aluminum-deposited polyethylene terephthalate film 1 to form an anchor coat layer. Then, on the anchor coat layer, a low density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0.918 ^{g / cm 3} , MFR: 8.1 g / 10 minutes, degree of biomass: 95) is used by a sand laminating method. %) While extruding, through this adhesive resin layer (biomass degree: 95%, thickness 15 μm), a linear low-density polyethylene film derived from fossil fuel (manufactured by Mitsui Kagaku Tohcello: TUX FC-S). , 40 μm in thickness), and the 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]
<Preparation of laminated body 8>
A biaxially stretched polypropylene film (manufactured by Toyobo Co., Ltd .: P2161, thickness 20 μm) is prepared as a base material layer, and a two-component curable anchor coating agent (manufactured by Mitsui Chemicals Co., Ltd .: A3210 / A3075) is coated on the corona-treated surface. , Anchor coat layer was formed. Subsequently, a low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0.918 ^{g / cm 3} , MFR: 8.1 g / 10 minutes, degree of biomass: 95%) 50 parts by mass and low density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene, LC600A, density: 0.918 ^{g / cm 3} , MFR: 7.0 g / 10 minutes, biomass degree: 0%) 50 parts by mass The aluminum-deposited surface of the above-mentioned aluminum-deposited polyethylene terephthalate film 1 was bonded through the polyolefin resin layer (biomass degree: 48%, thickness 15 μm) while extruding the mixed resin obtained by dry-blending. Subsequently, a two-component curable anchor coating agent (manufactured by Mitsui Chemicals, Inc .: A3210 / A3075) was coated on the surface of the polyethylene terephthalate film 1 of the aluminum-deposited polyethylene terephthalate film 1 to form an anchor coat layer. Then, on the anchor coat layer, a low density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0.918 ^{g / cm 3} , MFR: 8.1 g / 10 minutes, degree of biomass: 95) is used by a sand laminating method. %) 50 parts by mass and 50 parts by mass of low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene, LC600A, density: 0.918 ^{g / cm 3} , MFR: 7.0 g / 10 minutes, biomass degree: 0%) While extruding the dry-blended mixed resin, a linear low-density polyethylene film derived from fossil fuel (manufactured by Mitsui Kagaku Tohcello: TUX: TUX) is passed through this adhesive resin layer (biomass degree: 48%, thickness 15 μm). FC-S (thickness 40 μm) corona-treated surfaces are laminated, and a base material layer, an anchor coat layer, a polyolefin resin layer, a barrier layer, a plastic film, an anchor coat layer, an adhesive resin layer, and a thermoplastic resin layer are laminated in this order. The laminated body 8 was obtained.

[Comparative Example 3]
<Preparation of laminated body 9>
A biaxially stretched polypropylene film (manufactured by Toyobo Co., Ltd .: P2161, thickness 20 μm) is prepared as a base material layer, and a two-component curable anchor coating agent (manufactured by Mitsui Chemicals Co., Ltd .: A3210 / A3075) is coated on the corona-treated surface. , Anchor coat layer was formed. Subsequently, on the anchor coat layer, a fossil fuel-derived low-density polyethylene (manufactured by Japan Polyethylene Corporation, LC600A, density: 0.918 ^{g / cm 3} , MFR: 7.0 g / 10 minutes, biomass) was used by the sand laminating method. While extruding (degree: 0%), the aluminum-deposited surface of the above-mentioned aluminum-deposited polyethylene terephthalate film 1 was bonded through the adhesive resin layer (biomass degree: 0%, thickness 15 μm). Subsequently, a two-component curable anchor coating agent (manufactured by Mitsui Chemicals, Inc .: A3210 / A3075) was coated on the surface of the polyethylene terephthalate film 1 of the aluminum-deposited polyethylene terephthalate film 1 to form an anchor coat layer. Then, on the anchor coat layer, using the sand laminating method, low density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., LC600A, density: 0.918 ^{g / cm 3} , MFR: 7.0 g / 10 minutes, degree of biomass Through this adhesive resin layer (biomass degree: 0%, thickness 15 μm) while extruding (: 0%), a linear low-density polyethylene film derived from fossil fuel (manufactured by Mitsui Kagaku Tohcello: TUX FC). The base material layer, the anchor coat layer, the adhesive resin layer, the barrier layer, the plastic film, the anchor coat layer, the adhesive resin layer, and the thermoplastic resin layer are laminated in this order by laminating the corona-treated surfaces of −S, thickness 40 μm). The laminated body 9 was obtained.

[Example 7]
<Preparation of laminated body 10>
Biaxially stretched polyester film 1 (biomass degree: 20%, manufactured by Toyobo Co., Ltd., DE024, thickness) formed by using terephthalic acid derived from fossil fuel and ethylene glycol derived from biomass (biomass polyester) as a base material layer. 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, Inc .: A3210 / A3075, polyurethane type) to form an anchor coating layer. Subsequently, a low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0.918 ^{g / cm 3} , MFR: 8.1 g / 10 minutes, degree of biomass: While extruding 95%), a linear low-density polyethylene film derived from fossil fuel (manufactured by Mitsui Chemicals Tohcello: TUX FC-) is passed through this polyolefin resin layer (biomass degree: 95%, thickness 15 μm). A corona-treated surface (S, thickness 40 μm) was laminated to obtain 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.

[Example 8]
<Preparation of laminated body 11>
Biaxially stretched polyester film 1 (biomass degree: 20%, manufactured by Toyobo Co., Ltd., DE024, thickness) formed by using terephthalic acid derived from fossil fuel and ethylene glycol derived from biomass (biomass polyester) as a base material layer. 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, Inc .: A3210 / A3075) to form an anchor coating layer. Subsequently, a low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0.918 ^{g / cm 3} , MFR: 8.1 g / 10 minutes, degree of biomass: 95%) 50 parts by mass and low density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene, LC600A, density: 0.918 ^{g / cm 3} , MFR: 7.0 g / 10 minutes, biomass degree: 0%) 50 parts by mass Through this polyolefin resin layer (biomass degree: 48%, thickness 15 μm), a linear low-density polyethylene film derived from fossil fuel (manufactured by Mitsui Kagaku Tohcello: TU. The corona-treated surfaces of XFC-S (thickness 40 μm) were laminated to obtain 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.

[Manufacturing Examples 1 to 11]
<Making a 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 by the following steps. Specifically, the two side sheets are overlapped with the side sheets facing each other so that the thermoplastic resin layer is the innermost layer, and the bottom sheet is inserted between the two side sheets to form the side sheets. And the bottom sheet was heat-sealed to prepare standing pouches 1 to 11 having the form shown in FIG.

(Liquid leak test)
The standing pouches 1 to 11 prepared above are filled with a test solution (ageless seal check (manufactured by Mitsubishi Gas Chemical Company, Inc.)), stored at room temperature and humidity for 1 hour, and then the liquid leakage is visually evaluated according to the following evaluation criteria. did. The evaluation results are shown in Table 1.
(Evaluation criteria)
◯: There was no liquid leakage from the heat seal part, and the performance as a standing pouch was good.
X: There was liquid leakage from the heat seal 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 Outlet part

Claims (6)

A laminate including 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 material layer contains polypropylene and contains
The polyolefin resin layer contains low density polyethylene derived from biomass and contains
The degree of biomass in the polyolefin resin layer is 5% or more, and the degree of biomass is 5% or more.
The base material layer constitutes the outermost layer, and
A laminate in which the thermoplastic resin layer constitutes the innermost layer. 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. The method for producing a laminate according to claim 1 or 2.
A method for producing a laminate, in which the base material layer and the plastic layer having the barrier layer are bonded together via the polyolefin resin layer that has been melt-extruded. A packaged product comprising the laminate according to claim 1 or 2. 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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