JP2018001613A - Laminate equipped with polyolefin resin layer and packing product equipped with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: 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, an anchor coat layer and a polyolefin resin layer directly laminated on the anchor coat 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 comprising a polyolefin resin layer containing biomass polyolefin, and more specifically, at least a base material layer, an anchor coat layer, and biomass-derived ethylene directly laminated on the anchor coat layer. It is related with a laminated body provided with the polyolefin resin layer containing biomass polyolefin which is a polymer of the monomer to contain. Furthermore, it is related with the packaging product provided with this laminated body, and flexible packaging.

  In recent years, with the growing demand for the establishment of a recycling-oriented society, the use of biomass has been attracting attention in the materials field, as it is desired to move away from fossil fuels as well as energy. Biomass is an organic compound photo-synthesized from carbon dioxide and water, and by using it, it is so-called carbon neutral renewable energy that becomes carbon dioxide and water again. In recent years, biomass plastics using these biomasses as raw materials have been rapidly put into practical use, and attempts have been made to produce various resins from biomass raw materials.

  As a biomass-derived resin, commercial production of polylactic acid (PLA) produced via lactic acid fermentation has begun, but it is biodegradable, and its performance as a plastic is now a general-purpose plastic. Therefore, it has not been widely used due to its limitations in product applications and product manufacturing methods. Moreover, life cycle assessment (LCA) evaluation is performed for PLA, and discussion is made on energy consumption at the time of PLA production, equivalence at the time of replacement of general-purpose plastics, and the like.

  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, etc., and is used for various applications such as packaging materials, and is used in large amounts all over the world. For this reason, the use of conventional fossil fuel-derived polyethylene has a large environmental impact.

  Therefore, it is desired to reduce the amount of fossil fuel used by using raw materials derived from biomass for the production of polyethylene. For example, until now, it has been studied to produce ethylene and butylene as raw materials for polyolefin resin from renewable natural raw materials (see, for example, Patent Document 1).

Special table 2011-506628 gazette

  The present inventors pay attention to ethylene, which is a raw material for polyolefin resin, and instead of ethylene obtained from conventional fossil fuel, biomass polyolefin (hereinafter simply referred to as “biomass polyolefin”) using ethylene derived from biomass as its raw material. Is a polyolefin resin layer comprising a polyolefin manufactured using ethylene obtained from a conventional fossil fuel (hereinafter sometimes simply referred to as “polyolefin derived from fossil fuel”). And the knowledge that a product comparable to physical properties such as mechanical properties can be obtained. The present invention is based on this finding.

  Accordingly, an object of the present invention is to provide a laminate comprising a polyolefin resin layer comprising a polyolefin resin layer containing biomass polyolefin, which is inferior in terms of physical properties such as mechanical properties and a laminate comprising a polyolefin resin layer comprising a polyolefin derived from a fossil fuel. That is.

In an embodiment of the present invention,
A laminate comprising at least a base material layer, an anchor coat layer, and a polyolefin resin layer directly laminated on the anchor coat layer, in this order,
The polyolefin resin layer contains biomass polyolefin which is a polymer of monomers containing ethylene derived from biomass,
There is provided a laminate in which the degree of biomass in the polyolefin resin layer is 5% or more.

  In the aspect of the present invention, it is preferable that the polyolefin resin layer further contains a polyolefin derived from fossil fuel.

  In the aspect of this invention, it is preferable that the said polyolefin resin layer contains 5 mass% or more and 100 mass% or less of the said biomass polyolefin, and 0 mass% or more and 95 mass% or less of the polyolefin derived from the said fossil fuel.

  In the aspect of this invention, it is preferable that the said polyolefin resin layer contains polyethylene.

  In the aspect of the present invention, the anchor coat layer preferably has a thickness of 0.5 μm or less.

  In the aspect of the present invention, the material of the anchor coat layer is preferably a material selected from the group consisting of organic titanium, polyurethane, polyethyleneimine, polybutadiene, and modified polyolefin.

  In the aspect of the present invention, the base material layer preferably contains 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 producing the laminate,
There is provided a method for producing a laminate, in which an anchor coat layer is formed on the base material layer, and then a polyolefin resin layer is melt-extruded using the anchor coat layer.

  In another aspect of the present invention, a packaged product comprising the laminate is provided.

  In another aspect of the present invention, a flexible package comprising the laminate is provided.

  The laminate according to the present invention includes at least a base material layer, an anchor coat layer, and a polyolefin resin layer containing a biomass polyolefin directly laminated on the anchor coat layer, so that the use of fossil fuels can be performed as compared with the conventional one. The amount can be reduced and the environmental load can be reduced. Further, the laminate according to the present invention is not inferior in terms of physical properties such as mechanical properties as compared with a conventional fossil fuel-derived polyolefin resin laminate, and therefore replaces the conventional fossil fuel-derived polyolefin resin laminate. be able to.

It is a schematic cross section which shows an example of the laminated body by this invention. It is a schematic cross section which shows an example of the laminated body by this invention. It is a schematic cross section which shows an example of the laminated body by this invention. It is a simplified diagram showing an example of a configuration of a standing pouch. It is a simplified diagram showing an example of a configuration of a laminate tube.

  In the present invention, the term “biomass polyolefin” and “polyolefin resin layer containing biomass polyolefin” are those in which a raw material derived from biomass is used as a raw material, and all of the raw material is derived from biomass. Does not mean.

<Laminated body>
The laminate according to the present invention comprises a base material layer, an anchor coat layer, and a polyolefin resin layer containing biomass polyolefin directly laminated on the anchor coat layer in this order. Since the laminate includes 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. In addition, the laminate according to the present invention is not inferior in terms of physical properties such as mechanical properties as compared with a polyolefin resin laminate produced from a raw material obtained from a conventional fossil fuel. Can be substituted.

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

The laminate according to the present invention will be described with reference to the drawings. Examples of schematic cross-sectional views of the laminate according to the present invention are shown in FIGS.
A laminate 10 shown in FIG. 1 includes a base material layer 11, an anchor coat layer 12, and a polyolefin resin layer 13 formed directly on the anchor coat layer 12. In the case of soft packaging including the laminate 10, the polyolefin resin layer 13 is located inside the soft 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 material layer 11, a barrier layer 14, an anchor coat layer 12, and a polyolefin resin layer 13 directly formed on the anchor coat layer 12 in this order. In the case of soft packaging including the laminate 20, the polyolefin resin layer 13 is located inside the soft packaging.
The laminate 30 shown in FIG. 3 includes a base material layer 11, a plastic film 15, an anchor coat layer 12, and a polyolefin resin layer 13 formed directly on the anchor coat layer 12 in this order. In the case of soft packaging including the laminate 30, the polyolefin resin layer 13 is located inside the soft packaging.
In addition, any laminate may further laminate a printing layer or a thermoplastic resin layer. When laminating the printing layer and the thermoplastic resin layer, they may be laminated so that the thermoplastic resin layer is the outermost surface.
Hereinafter, each layer which comprises a laminated body is demonstrated.

(Base material layer)
In this invention, a base material layer fulfill | performs the function as a base material layer holding a polyolefin resin layer, and what can provide the intensity | strength as a packaging product to a laminated body is preferable. As the substrate layer, a resin substrate, preferably a polyester film such as polyethylene terephthalate, a polyolefin film such as polyethylene or polypropylene, a plastic film of a resin material such as polyamide such as nylon, may be used alone, Two or more kinds may be used in combination. Moreover, when combining 2 or more types, you may laminate | stack using a dry laminating method and may laminate | stack 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 biomass-derived material or a fossil fuel-derived material.

  The base material layer may contain 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 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 content of carbon derived from biomass by measurement of radioactive carbon (C14). Since carbon dioxide in the atmosphere contains C14 at a constant ratio (105.5 pMC), the C14 content in plants that grow by incorporating carbon dioxide in the atmosphere, for example, corn, is also about 105.5 pMC. It is known. It is also known that fossil fuel contains almost no C14. Therefore, the proportion of carbon derived from biomass can be calculated by measuring the proportion of C14 contained in all the carbon atoms in the polyester. In the present invention, the biomass-derived carbon content Pbio when the content of C14 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 polymer obtained by polymerizing ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms in a molar ratio of 1: 1. Is used, the biomass-derived carbon content Pbio in the polyester is 20%. In the present invention, the content of biomass-derived carbon by radiocarbon (C14) measurement is preferably 10% or more and 20% or less, and preferably 10% or more and 19% or less, based on the total carbon in the biomass polyester. There may be. When the content of carbon derived from biomass in the biomass polyester is 10% or more, it is suitable as a carbon offset material. In addition, the biomass-derived carbon content in the fossil fuel-derived polyester produced using fossil fuel-derived ethylene glycol and the fossil fuel-derived dicarboxylic acid is 0%, and the biomass degree of the 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 degree of biomass 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 compared to the conventional case.

  A base material layer can be formed, for example, by forming a film by a T-die method using a biomass polyester resin composition or a resin composition containing biomass polyester and a 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 uses ethanol (biomass ethanol) produced from biomass as a raw material. For example, biomass-derived ethylene glycol can be obtained from biomass ethanol by a conventionally known method, such as a method of producing ethylene glycol via ethylene oxide. Moreover, you may use commercially available biomass ethylene glycol, for example, the biomass ethylene glycol marketed from India Glycol can be used conveniently.

  The dicarboxylic acid unit of biomass polyester uses a dicarboxylic acid derived from fossil fuel. 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 aromatic dicarboxylic acid derivative include lower alkyl esters of aromatic dicarboxylic acid, specifically methyl ester, ethyl ester, propyl ester, and butyl. Examples include esters. Among these, terephthalic acid is preferable, and dimethyl terephthalate is preferable as an aromatic dicarboxylic acid derivative.

(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 biomass polyolefin and 0% by mass or more and 95% by mass or less fossil fuel-derived polyolefin with respect to the entire polyolefin resin layer. It may contain less than mass% biomass polyolefin and 0 mass% more than 95 mass% fossil fuel-derived polyolefin, 25 mass% to 75 mass% biomass polyolefin and 25 mass% to 75 mass% fossil fuel And derived polyolefins. The following biomass degree should just be realizable as the whole polyolefin resin layer. In the present invention, since the polyolefin resin layer contains biomass polyolefin, the amount of polyolefin derived from fossil fuel can be reduced and the environmental load can be reduced as compared with the conventional case.

In the present invention, the “biomass degree” in the polyolefin resin layer (the biomass-derived carbon concentration in the biomass polyolefin) is a value obtained by measuring the content of biomass-derived carbon by radioactive carbon (C14) measurement. Since carbon dioxide in the atmosphere contains C14 at a constant ratio (105.5 pMC), the C14 content in plants that grow by incorporating carbon dioxide in the atmosphere, for example, corn, is also about 105.5 pMC. It is known. It is also known that fossil fuel contains almost no C14. Therefore, the proportion of carbon derived from biomass 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, when all the biomass-derived ethylene is used as the polyolefin raw material, 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 degree of biomass in the polyolefin resin layer is 5% or more, preferably 10% or more, more preferably 15% or more, and further preferably 20% or more. Note that the degree of biomass in the polyolefin resin layer need not be 100%. This is because if the biomass-derived raw material is used even in a part of the laminate, the amount of the fossil fuel used is reduced as compared with the conventional case. If the degree of biomass in the polyolefin resin layer is 5% or more, the amount of polyolefin derived from fossil fuel can be reduced and the environmental load can be reduced compared to 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 in accordance with the method defined in Method A of JIS K7112-1980 after annealing described in JIS K6760-1995. 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 to 100 μm, preferably 10 μm to 60 μm, more preferably 15 μm to 40 μm. If the thickness of the polyolefin resin layer is in the above range, the function of bonding the two layers can be sufficiently achieved.

(Biomass polyolefin)
In the present invention, biomass polyolefin is a polymer of monomers containing ethylene derived from biomass. It is preferable to use what was obtained by the manufacturing method mentioned later for ethylene derived from biomass. Since ethylene derived from biomass is used as a monomer as a raw material, the polymerized polyolefin is derived from biomass. In addition, the raw material monomer of polyolefin does not need to contain 100 mass% of ethylene derived from biomass.

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

  The α-olefin is not particularly limited, but can usually be one having 3 to 20 carbon atoms, and is preferably butylene, hexene or octene. This is because if it is butylene, hexene or octene, it can be produced by polymerization of ethylene which is a biomass-derived raw material. In addition, by including such an α-olefin, the polymerized polyolefin has an alkyl group as a branched structure, and therefore can be 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 may be mixed and used. In particular, the biomass polyolefin is preferably polyethylene. This is because, by using ethylene, which is a biomass-derived raw material, 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 should be within the above range as the whole polyolefin resin layer.

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 biomass polyolefin is a value measured according to the method prescribed | regulated to A method among JISK7112-1980 after performing annealing as described in JISK6760-1995. 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 the inner layer of the packaged product. Moreover, if the density of biomass polyolefin is 0.93 g / cm < ³ > or less, the transparency and mechanical strength of the polyolefin resin layer containing biomass polyolefin can be improved, and it can be used suitably as an inner layer of a packaged product.

  Biomass polyolefin has a melt flow of 0.1 g / 10 min to 10 g / 10 min, preferably 0.2 g / 10 min to 9 g / 10 min, more preferably 1 g / 10 min to 8.5 g / 10 min. 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 defined in JIS K7210-1995. If the MFR of the biomass polyolefin is 0.1 g / 10 min or more, the extrusion load during the molding process can be reduced. Moreover, if MFR of biomass polyolefin is 10 g / 10min or less, the mechanical strength of the polyolefin resin layer containing biomass polyolefin can be raised.

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

(Method for producing biomass-derived ethylene)
In the present invention, the method for producing biomass-derived ethylene as 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 biomass-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 biomass-derived fermented ethanol obtained from plant raw materials. A plant raw material is not specifically limited, A conventionally well-known plant can be used. For example, corn, sugar cane, beet, and manioc can be mentioned.

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

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

  When ethylene is obtained by a dehydration reaction of ethanol, a catalyst is usually used, but this 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. For example, γ-alumina is preferable.

  Since this dehydration reaction is an endothermic reaction, it is usually carried out under heating conditions. If the reaction proceeds at a commercially useful reaction rate, the heating temperature is not limited, but a temperature of preferably 100 ° C. or higher, more preferably 250 ° C. or higher, further preferably 300 ° C. or higher is appropriate. 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 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 separation of the catalyst is easy is suitable, but a liquid phase suspension bed, a fluidized bed, or the like may be used.

  In the dehydration reaction of ethanol, the yield of the reaction depends on the amount of water contained in ethanol supplied as a raw material. Generally, when performing a dehydration reaction, it is preferable that there is no water in view of water removal efficiency. However, in the case of ethanol dehydration reaction using a solid catalyst, it has been found that in the absence of water, the production of other olefins, particularly butene, tends to increase. It is presumed that 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. Although an upper limit is not specifically limited, From a viewpoint of a mass balance and a heat balance, Preferably it is 50 mass% or less, More preferably, it is 30% or less, More preferably, it is 20% or less.

  By performing a dehydration reaction of ethanol in this way, a mixed part of ethylene, water and a small amount of unreacted ethanol can be obtained. Ethylene can be obtained except 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, etc. 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 biomass, the obtained ethylene contains carbonyl compounds such as ketones, aldehydes, and esters, which are impurities mixed in the ethanol fermentation process, as well as carbon dioxide gas that is a decomposition product thereof, enzyme decomposition products, It contains trace amounts 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 and may be removed by purification. The purification method is not particularly limited, and can be performed by a conventionally known method. A suitable purification operation is, for example, an adsorption purification method. The adsorbent used is not particularly limited, and a conventionally known adsorbent can be used. For example, a high surface area material is preferable, and the type of adsorbent is selected according to the type and amount of impurities in ethylene obtained by dehydration of biomass-derived ethanol.

  In addition, you may use caustic water treatment together as a refinement | purification method of the impurity in ethylene. In the case of performing caustic water treatment, 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.

(Method for producing biomass polyolefin)
In the present invention, the polymerization method of the monomer containing ethylene derived from biomass is not particularly limited, and can be performed by a conventionally known method. The polymerization temperature and polymerization pressure are preferably adjusted as appropriate according to the polymerization method and polymerization apparatus. The polymerization apparatus is not particularly limited, and a conventionally known apparatus can be used. Hereinafter, an example of a method for polymerizing a monomer containing ethylene will be described.

  The polymerization method of polyolefins, particularly ethylene polymers and copolymers of ethylene and α-olefins, is the type of polyethylene of interest, such as high density polyethylene (HDPE), medium density polyethylene (MDPE), and low density polyethylene (LDPE). ), And linear low density polyethylene (LLDPE), etc. For example, as a polymerization catalyst, using a multi-site catalyst such as a Ziegler-Natta catalyst or a single site catalyst such as a metallocene catalyst, by any of gas phase polymerization, slurry polymerization, solution polymerization, and high-pressure ion polymerization, It is preferable to carry out by one stage or two or more stages.

  The above single-site catalyst is a catalyst that can form a uniform active species, and is usually adjusted by bringing a metallocene transition metal compound or a nonmetallocene transition metal compound into contact with an activation cocatalyst. . The single site catalyst is preferable because the active site structure is uniform as compared with the multisite catalyst, and a polymer having a high molecular weight and a high degree of uniformity can be polymerized. As the single site catalyst, it is particularly preferable to use a metallocene catalyst. The metallocene-based 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, and if necessary, an organometallic compound, and each catalyst component of the support. is there.

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

  In the group IV transition metal compound containing a ligand having a cyclopentadienyl skeleton, examples of the transition metal include zirconium, titanium, hafnium, and zirconium and hafnium are particularly preferable. The transition metal compound usually has two ligands having a cyclopentadienyl skeleton, and each ligand having a cyclopentadienyl skeleton is preferably bonded to each other via a bridging group. Examples of the crosslinking group include substituted alkylene groups such as C1-C4 alkylene groups, silylene groups, dialkylsilylene groups, and diarylsilylene groups, dialkylgermylene groups, and diarylgermylene groups. Preferably, it is a substituted silylene group.

  In the transition metal compound of Group IV of the periodic table, as a ligand other than a ligand having a cyclopentadienyl skeleton, hydrogen, a hydrocarbon group having 1 to 20 carbon atoms (an alkyl group) is typical. Alkenyl group, aryl group, alkylaryl group, aralkyl group, polyenyl group, etc.), halogen, metaalkyl group, metaaryl group and the like.

  The transition metal compound of Group IV of the Periodic Table containing a ligand having a cyclopentadienyl skeleton can use one or a mixture of two or more as a catalyst component.

  The co-catalyst is one that can effectively make the above-mentioned group IV transition metal compound as a polymerization catalyst, or can neutralize ionic charges in a catalytically activated state. Co-catalysts include benzene-soluble aluminoxanes of organoaluminum oxy compounds, benzene-insoluble organoaluminum oxy compounds, ion-exchange layered silicates, boron compounds, active hydrogen group-containing or non-containing cations and non-coordinating anions. Ionic compounds, lanthanoid salts such as lanthanum oxide, tin oxide, phenoxy compounds containing a fluoro group, and the like.

The group IV transition metal compound containing a ligand having a cyclopentadienyl skeleton may be used by being supported on an inorganic or organic compound carrier. The support is preferably a porous oxide of an inorganic or organic compound. Specifically, an ion-exchange layered silicate such as montmorillonite, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _{2 and the} like, or a mixture thereof.

  Furthermore, examples of the organometallic compound used as necessary include organoaluminum compounds, organomagnesium compounds, and organozinc compounds. Of these, organic aluminum is preferably used.

  Various additives other than the main component polyolefin may be added to the biomass polyolefin as long as the characteristics are not impaired. Examples of additives include plasticizers, UV stabilizers, anti-coloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, yarn friction reducing agents, slip agents, mold release agents, An oxidizing agent, an ion exchange agent, a coloring pigment, and the like 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 whole biomass polyolefin.

(Anchor coat layer)
The anchor coat layer can be formed by applying and drying an anchor coat agent on the surface of the base material layer when the polyolefin resin layer is laminated on the base material layer by a melt extrusion laminating method or the like. Examples of the anchor coating agent include any resin having a heat-resistant temperature of 135 ° C. or higher, such as a vinyl-modified resin, an epoxy resin, a urethane resin, a polyester resin, and the like. A two-component curable anchor coating agent (polyurethane type) comprising a polyacrylic or polymethacrylic resin having a hydroxyl group and an isocyanate compound as a curing agent can be preferably used. Moreover, a silane coupling agent may be used in combination as an additive, and nitrified cotton may be used in combination in order to improve heat resistance.

  The anchor coat layer has a thickness of 0.5 μm or less (dry state), preferably 0.1 μm or less (dry state).

(Thermoplastic resin layer)
The thermoplastic resin layer can be formed using a conventionally known thermoplastic resin. The laminate further includes a thermoplastic resin layer to provide the same heat resistance, pressure resistance, water resistance, heat sealability, pinhole resistance, puncture resistance, and other physical properties as those of the conventional laminate. 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, ethylene-acrylic acid copolymer. Copolymer, 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. Low density polyethylene, linear low density polyethylene, medium density polyethylene, and ethylene-methacrylic acid copolymers 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 biomass-derived material, biomass polyolefin, which is a polymer of monomers containing biomass-derived ethylene, may be contained in the same manner as the polyolefin resin layer.

  Further, as described above, a thermoplastic resin layer may be provided on the surface of the base material layer opposite to the polyolefin resin layer.

(Print layer)
The printed layer can be used to display decorations, contents, display of the best-before period, display of manufacturers, sellers, etc., and display of other characters and letters, numbers, pictures, figures, symbols, patterns, etc. It is a layer for forming a desired arbitrary printed pattern. A printing layer can be provided as needed, for example, can be provided in a 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 thereof. A printing layer can be formed using a conventionally well-known pigment and dye, The formation method is not specifically 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. A vapor deposition 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 prevent transmission of oxygen gas, water vapor, and the like, and light shielding properties that prevent transmission of visible light, ultraviolet light, and the like can be imparted or improved. Note that the laminate may have two or more barrier layers. When two or more barrier layers are provided, each may have the same composition or a different composition.

  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) and other inorganic or inorganic oxide vapor deposition films can be used. In particular, an aluminum metal vapor-deposited film or a silicon oxide or aluminum metal or aluminum oxide vapor-deposited film is preferably used as a packaging material (bag) or the like.

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. As a range of the value of X, silicon (Si) is 0 to 2, aluminum (Al) is 0 to 1.5, magnesium (Mg) is 0 to 1, calcium (Ca) is 0 to 1, 0 to 0.5 for potassium (K), 0 to 2 for tin (Sn), 0 to 0.5 for sodium (Na), 0 to 1,5 for boron (B), titanium (Ti) Can take values in the range of 0 to 2, lead (Pb) in the range of 0 to 1, zirconium (Zr) in the range of 0 to 2, and yttrium (Y) in the range of 0 to 1.5. In the above, when X = 0, it is a complete 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 suitably used for the packaging material, silicon (Si) is in the range of 1.0 to 2.0, and aluminum (Al) is in the range of 0.5 to 1.5. Can be used.

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

  The deposited film can be formed on a plastic film such as polyethylene terephthalate or nylon using the following forming method. As a method for forming a vapor deposition film, for example, a physical vapor deposition method (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, a thermochemical method, or the like. 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.

  According to another aspect, the barrier layer may be a metal foil obtained by rolling a metal. A conventionally known metal foil can be used as the metal foil. Aluminum foil is preferred from the viewpoints of gas barrier properties that prevent transmission of oxygen gas, water vapor, and the like, and light shielding properties that prevent transmission of visible light, ultraviolet light, and the like.

(Plastic film)
In the present invention, various plastic films may be used as other layers. For example, any of a stretched polyethylene terephthalate film, a stretched nylon film, a stretched polypropylene film, a nylon 6 / metaxylylenediamine nylon 6 co-extrusion co-stretch film, a polypropylene / ethylene-vinyl alcohol copolymer co-extrusion co-stretch film, or the like, or The composite film which laminated | stacked these two or more films may be sufficient. The plastic film may be coated with polyvinyl alcohol or the like.

  The plastic film may contain a biomass-derived material or a fossil fuel-derived material. When the plastic film includes a biomass-derived material, it may further include 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.

(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 laminating method. Examples of the adhesive include one-part or two-part cured or non-cured vinyl, (meth) acrylic, polyamide, polyester, polyether, polyurethane, epoxy, rubber, etc. An adhesive such as a solvent type, an aqueous type, or an emulsion type can be used. Examples of the coating method for the laminating adhesive include a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a fountain method, a transfer roll coating method, and other methods to form a laminate. It can apply | coat to the application surface of a 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).

  The adhesive layer may be an adhesive resin layer used when two layers are bonded by the sand lamination method or used in the melt extrusion lamination method. Examples of the thermoplastic resin that can be used for the adhesive resin layer include a polyethylene resin, a polypropylene resin, or a cyclic polyolefin resin, or a copolymer resin, a modified resin, or a mixture (including alloy) containing these resins as a main component. ) Can be used. Examples of polyolefin resins include low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear (linear) low density polyethylene (LLDPE), polypropylene (PP), and metallocene catalysts. Ethylene-α / olefin copolymer, ethylene / polypropylene random or block copolymer, 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 interlayer adhesion In order to improve the , It can be used acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and an acid-modified polyolefin resin modified with an unsaturated carboxylic acid such as itaconic acid. Further, a resin obtained by graft polymerization or copolymerization of an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or an ester monomer can be used as the polyolefin resin. These materials can be used alone or in combination of two or more. As the cyclic polyolefin-based 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. In addition, it cannot be overemphasized that what uses the above-mentioned ethylene derived from biomass as a monomer unit can be used as above-mentioned polyethylene-type resin.

  The adhesive resin layer may contain a material derived from biomass or 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 monomers containing biomass-derived ethylene, like the polyolefin resin layer.

(Laminate manufacturing method)
The manufacturing method of the laminated body by this invention is not specifically limited, It can manufacture by conventionally well-known methods, such as the dry lamination method, the melt extrusion lamination method, and the sand lamination method. In the present invention, it is preferable to laminate other layers through a melt-extruded polyolefin resin layer using a sand laminating method. Moreover, you may laminate | stack a polyolefin resin layer and another layer by a co-extrusion method.

  The thickness of the laminate obtained as described above is arbitrary depending on the application, 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 / abrasion / lubrication functions, optical functions, thermal functions, surface functions such as biocompatibility, etc. For the purpose, it is also possible to perform secondary processing. Examples of secondary processing include embossing, painting, adhesion, printing, metalizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, Coating, etc.). Further, the laminate according to the present invention can be subjected to laminating processing (dry laminating or extrusion laminating), bag making processing, and other post-processing processing to produce a molded product.

(Use)
The laminate according to the present invention can be used for packaging products, and the packaging products are preferably used for flexible packaging such as packaging bags, laminate tubes, and lid materials. As packaging bags, for example, standing pouch type, side seal type, two-side seal type, three-side seal type, four-side seal type, envelope-attached seal type, joint-attached seal type (pillow seal type), pleated seal type, flat bottom seal Various types of packaging bags such as a mold, a square bottom seal type, and a gusset type are included. In that case, the thickness of the laminate can be appropriately determined depending on the application, and is used in the form of a film having a thickness of 30 μm to 300 μm, preferably 35 μm to 180 μm.

(Soft packaging)
The laminated body by this invention can be used conveniently for flexible packaging, especially a packaging bag and a laminate tube. A case where a packaging bag, as an example, a standing pouch is formed using the laminate according to the present invention will be described. 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 sheet) 41 and a bottom part (bottom sheet) 42. In the standing pouch 40, the side sheet 41 and the bottom sheet 42 may be formed of the same member, or may be formed of separate members. The side sheet 41 and the bottom sheet 42 of the standing pouch 40 can be formed using the laminate according to the present invention.

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

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples.

<Measurement and conditions>
In the following reference examples, reference comparative examples, examples, and comparative examples, the biomass degree is the value of the biomass-derived carbon concentration as measured by radioactive carbon (C14).

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 laminated body 1>
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, polyurethane) is used 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: 95%) is 320 ° C. on the anchor coat layer. Lamination by laminating at a resin temperature and a line speed of 100 m / min to form a polyolefin resin layer (biomass degree: 95%, thickness 30 μm), and then laminating a base material layer, an anchor coat layer, and a polyolefin resin layer in this order Body 1 was obtained.

[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. Thus, an anchor coat layer was formed. Subsequently, 50 parts by mass of biomass-derived low density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%) on the anchor coat layer; A mixed resin obtained by dry blending 50 parts by mass of 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 min, biomass degree: 0%) Melt extrusion lamination at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a polyolefin resin layer (biomass degree: 48%, thickness 30 μm), and a base material layer, an anchor coat layer, and a polyolefin resin layer are laminated in order. Thus obtained laminate 2 was obtained.

[Comparative Example 1]
<Preparation of laminate 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. Thus, an anchor coat layer was formed. Subsequently, low-density polyethylene derived from fossil fuel (LC600A, density: 0.918 g / cm ³ , MFR: 7.0 g / 10 min, biomass degree: 0%) 320 derived from fossil fuel on the anchor coat layer. Lamination by melt extrusion lamination at a resin temperature of 0 ° C. and a line speed of 100 m / min to form a resin layer (biomass degree: 0%, thickness 30 μm), and a base material layer, an anchor coat layer, and a resin layer are laminated in that order. Body 3 was obtained.

[Example 3]
<Preparation of laminate 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. Thus, an anchor coat layer was formed. 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 min, biomass is formed on the anchor coat layer using a sand laminate method. While extruding (degree: 0%), an aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, thickness 7 μm) was bonded through this adhesive resin layer (biomass degree: 0%, thickness 15 μm). Subsequently, a two-component curable anchor coating agent (Mitsui Chemical Co., Ltd .: A3210 / A3075) was coated on the aluminum foil to form an anchor coating layer. Subsequently, a biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%) is a resin at 320 ° C. on the anchor coat layer. Melt extrusion lamination at a temperature and a line speed of 100 m / min to form a polyolefin resin layer (biomass degree: 95%, thickness 30 μm), base material layer, anchor coat layer, adhesive resin layer, barrier layer, anchor coat layer Thus, a laminate 4 in which the polyolefin resin layers were sequentially laminated 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. Thus, an anchor coat layer was formed. 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 min, biomass is formed on the anchor coat layer using a sand laminate method. While extruding (degree: 0%), an aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, thickness 7 μm) was bonded through this adhesive resin layer (biomass degree: 0%, thickness 15 μm). Subsequently, a two-component curable anchor coating agent (Mitsui Chemical Co., Ltd .: A3210 / A3075) was coated on the aluminum foil to form an anchor coating layer. Subsequently, 50 parts by mass of fossil and low density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%) on the anchor coat layer 320 mixed resins obtained by dry blending 50 parts by mass of low density polyethylene derived from fuel (manufactured by Nippon Polyethylene Co., Ltd., LC600A, density: 0.918 g / cm ³ , MFR: 7.0 g / 10 min, biomass degree: 0%) Melt extrusion extrusion lamination at a resin temperature of 100 ° C. and a line speed of 100 m / min to form a polyolefin resin layer (biomass degree: 48%, thickness 30 μm), a base material layer, an anchor coat layer, an adhesive resin layer, a barrier layer, A laminate 5 in which an anchor coat layer and a polyolefin resin layer were laminated in order was obtained.

[Comparative Example 2]
<Preparation of laminate 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. Thus, an anchor coat layer was formed. 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 min, biomass is formed on the anchor coat layer using a sand laminate method. While extruding (degree: 0%), an aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, thickness 7 μm) was bonded through this adhesive resin layer (biomass degree: 0%, thickness 15 μm). Subsequently, a two-component curable anchor coating agent (Mitsui Chemical Co., Ltd .: A3210 / A3075) was coated on the aluminum foil to form an anchor coating layer. Subsequently, fossil fuel-derived low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., LC600A, density: 0.918 g / cm ³ , MFR: 7.0 g / 10 min, biomass degree: 0%) is 320 ° C. on the anchor coat layer. And melt extrusion lamination at a line speed of 100 m / min to form a resin layer (biomass degree: 0%, thickness 30 μm), base material layer, anchor coat layer, adhesive resin layer, barrier layer, anchor coat A laminate 6 was obtained in which a layer and a resin layer were sequentially laminated.

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

A biaxially stretched polypropylene film (Toyobo Co., Ltd .: P2161, thickness 20 μm) is prepared as a base material layer, and the corona-treated surface is coated with a two-component curable anchor coating agent (Mitsui Chemicals Co., Ltd .: A3210 / A3075). 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 min, biomass degree: sand laminate method) 95%) was extruded, and the aluminum vapor-deposited surface of the aluminum vapor-deposited polyethylene terephthalate film 1 was bonded through this adhesive resin layer (biomass degree: 95%, thickness 15 μm). Subsequently, on the polyethylene terephthalate film surface of the aluminum vapor-deposited polyethylene terephthalate film 1, a two-component curable anchor coating agent (manufactured by Mitsui Chemicals: A3210 / A3075) was coated to form an anchor coat layer. Thereafter, a low-density polyethylene derived from biomass (SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%) of 320 ° C. on the anchor coat layer. A polyolefin resin layer (biomass degree: 95%, thickness 30 μm) is formed by melt extrusion lamination at a temperature and a line speed of 100 m / min, and a substrate layer, an anchor coat layer, an adhesive resin layer, a barrier layer, a plastic film, an anchor A laminate 7 in which a coat layer and a polyolefin resin layer were sequentially laminated was obtained.

[Example 6]
<Preparation of laminated body 8>
A biaxially stretched polypropylene film (Toyobo Co., Ltd .: P2161, thickness 20 μm) is prepared as a base material layer, and the corona-treated surface is coated with a two-component curable anchor coating agent (Mitsui Chemicals Co., Ltd .: A3210 / A3075). 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 min, biomass degree: sand laminate method) 95%) 50 parts by mass of 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 min, biomass degree: 0%) The aluminum vapor-deposited surface of the above-mentioned aluminum vapor-deposited polyethylene terephthalate film 1 was bonded through this adhesive resin layer (biomass degree: 48%, thickness 15 μm) while extruding the dry blended resin. Subsequently, on the polyethylene terephthalate film surface of the aluminum vapor-deposited polyethylene terephthalate film 1, a two-component curable anchor coating agent (manufactured by Mitsui Chemicals: A3210 / A3075) was coated to form an anchor coat layer. Then, on the anchor coat layer, 50 parts by mass of fossil and low density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%) 320 mixed resins obtained by dry blending 50 parts by mass of low density polyethylene derived from fuel (manufactured by Nippon Polyethylene Co., Ltd., LC600A, density: 0.918 g / cm ³ , MFR: 7.0 g / 10 min, biomass degree: 0%) A polyolefin resin layer (biomass degree: 48%, thickness 30 μm) is formed by melt extrusion lamination at a resin temperature of ℃ and a line speed of 100 m / min, and a base material layer, anchor coat layer, adhesive resin layer, barrier layer, plastic A laminate 8 in which a film, an anchor coat layer, and a polyolefin resin layer were laminated in order was obtained.

[Comparative Example 3]
<Preparation of laminated body 9>
A biaxially stretched polypropylene film (Toyobo Co., Ltd .: P2161, thickness 20 μm) is prepared as a base material layer, and the corona-treated surface is coated with a two-component curable anchor coating agent (Mitsui Chemicals Co., Ltd .: A3210 / A3075). An anchor coat layer was formed. 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 min, biomass is formed on the anchor coat layer using a sand laminate method. The aluminum vapor-deposited surface of the aluminum vapor-deposited polyethylene terephthalate film 1 was bonded through this adhesive resin layer (biomass degree: 0%, thickness 15 μm) while extruding (degree: 0%). Subsequently, on the polyethylene terephthalate film surface of the aluminum vapor-deposited polyethylene terephthalate film 1, a two-component curable anchor coating agent (manufactured by Mitsui Chemicals: A3210 / A3075) was coated to form an anchor coat layer. Then, fossil fuel-derived low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., LC600A, density: 0.918 g / cm ³ , MFR: 7.0 g / 10 min, biomass degree: 0%) is 320 ° C. on the anchor coat layer. The resin layer (biomass degree: 0%, thickness 30 μm) is formed by melt extrusion lamination at a resin temperature of 100 m / min, and a substrate layer, an anchor coat layer, an adhesive resin layer, a barrier layer, a plastic film, A laminate 9 in which an anchor coat layer and a resin layer were laminated in order was obtained.

[Example 7]
<Preparation of Laminate 10>
Biaxially stretched polyester film 1 formed using terephthalic acid derived from fossil fuel and biomass-derived ethylene glycol (biomass polyester) as a base material layer (biomass degree: 20%, manufactured by Toyobo, DE024, thickness 12 μm) ) Was prepared. The corona-treated surface of the polyester film 1 was coated with a two-component curable anchor coating agent (Mitsui Chemicals, Inc .: A3210 / A3075, polyurethane) to form an anchor coating 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%) is 320 ° C. on the anchor coat layer. Lamination by laminating at a resin temperature and a line speed of 100 m / min to form a polyolefin resin layer (biomass degree: 95%, thickness 30 μm), and then laminating a base material layer, an anchor coat layer, and a polyolefin resin layer in this order Body 10 was obtained.

[Example 8]
<Preparation of Laminate 11>
A polyester film 1 was prepared as a base material layer, and a two-component curable anchor coating agent (Mitsui Chemicals, Inc .: A3210 / A3075) was coated on the corona-treated surface to form an anchor coating layer. Subsequently, 50 parts by mass of biomass-derived low density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%) on the anchor coat layer; A mixed resin obtained by dry blending 50 parts by mass of 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 min, biomass degree: 0%) Melt extrusion lamination at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a polyolefin resin layer (biomass degree: 48%, thickness 30 μm), and a base material layer, an anchor coat layer, and a polyolefin resin layer are laminated in order. Thus obtained laminate 11 was obtained.

[Production Examples 1 to 11]
<Production of packaging bag>
A standing pouch was formed by the following steps by combining the body member laminate (side sheet) and the bottom member laminate (bottom sheet) shown in Table 1 below. Specifically, the two side sheets are overlapped with the side sheets facing each other so that the thermoplastic resin layer becomes the innermost layer, and the bottom sheet is inserted between the two side sheets, And the bottom sheet was heat-sealed to produce 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 (Mitsubishi Gas Chemical Co., Ltd.)) and stored at room temperature and humidity for 1 hour, and then the 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.

DESCRIPTION OF SYMBOLS 10, 20, 30 Laminated body 11 Base material layer 12 Anchor coat layer 13 Polyolefin resin layer 14 Barrier layer 15 Plastic film 40 Standing pouch 41 Trunk part 42 Bottom part 50 Laminated tube 51 Head part 52 Cylindrical trunk part 53 Shoulder part 54 Outlet Part

Claims (10)

A laminate comprising at least a base material layer, an anchor coat layer, and a polyolefin resin layer directly laminated on the anchor coat layer, in this order,
The polyolefin resin layer contains biomass polyolefin which is a polymer of monomers containing ethylene derived from biomass,
The laminated body whose biomass degree in the said polyolefin resin layer is 5% or more.   The laminate according to claim 1, wherein the polyolefin resin layer further contains a polyolefin derived from fossil fuel.   The laminate according to claim 2, wherein the polyolefin resin layer contains 5% by mass to 100% by mass of the biomass polyolefin and 0% by mass to 95% by mass of the polyolefin derived from the fossil fuel.   The laminate according to any one of claims 1 to 3, wherein the polyolefin resin layer contains polyethylene.   The laminated body as described in any one of Claims 1-4 whose thickness of the said anchor coat layer is 0.5 micrometer or less.   The material of the said anchor coat layer is a material selected from the group which consists of an organic titanium type | system | group, a polyurethane type, a polyethyleneimine type | system | group, a polybutadiene type | system | group, and a modified polyolefin type | system | group as described in any one of Claims 1-5. Laminated body.   The laminate according to any one of claims 1 to 6, wherein the base material layer includes a resin material selected from the group consisting of polyester, polyolefin, and polyamide. It is a manufacturing method of the layered product according to any one of claims 1 to 7,
A method for producing a laminate, in which an anchor coat layer is formed on the base material layer, and then a polyolefin resin layer is melt-extruded using the anchor coat layer.   Packaged product provided with the laminated body as described in any one of Claims 1-7.   Flexible packaging provided with the laminated body as described in any one of Claims 1-7.

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