JP2018001610A - 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 first polyolefin resin layer, a paper substrate layer and a second polyolefin resin layer. The first and second polyolefin resin layers include a biomass polyolefin being a polymer of a monomer including ethylene derived from biomass. A biomass degree in the first and second polyolefin resin layers is 5% or more. The biomass polyolefin has a density of 0.91 g/cm-0.93 g/cm.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminate including a polyolefin resin layer containing biomass polyolefin, and more specifically, a polyolefin resin layer containing at least a paper base layer and a biomass polyolefin which is a polymer of monomers containing biomass-derived ethylene. It is related with a laminated body provided with. Furthermore, the present invention relates to a packaged product and a liquid paper container including the laminate.

  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 first polyolefin resin layer, a paper base material layer, and a second polyolefin resin layer,
The first and second polyolefin resin layers include a biomass polyolefin that is a polymer of monomers containing biomass-derived ethylene,
The degree of biomass in the first and second polyolefin resin layers is 5% or more,
The biomass polyolefin has a density of 0.91 g / cm ³ or more 0.93 g / cm ³ or less, laminate is provided.

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

  In an aspect of the present invention, the first or second 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. Is preferred.

  In the aspect of this invention, it is preferable that the said 1st or 2nd polyolefin resin layer contains polyethylene.

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

In another aspect of the present invention, a liquid paper container comprising the laminate,
A liquid paper container is provided in which the innermost layer of the liquid paper container is the second polyolefin resin layer.

  The laminate according to the present invention includes at least a paper base material layer and a polyolefin resin layer containing biomass polyolefin, so that the amount of fossil fuel used can be reduced compared to the conventional case, and the environmental load can be reduced. it can. 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 perspective view which shows an example of a liquid paper container.

  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 laminated body by this invention is provided with the 1st polyolefin resin layer containing biomass polyolefin, the paper base material layer, and the 2nd polyolefin resin layer containing biomass polyolefin. When a liquid paper container is produced using a laminate, the layer of the laminate located outside the liquid paper container is the first polyolefin resin layer, and the layer of the laminate located inside the liquid paper container is the second. The polyolefin resin layer. 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 thermoplastic resin layer, a printed layer, a barrier layer, a plastic film, and an adhesive 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.
The laminated body 10 shown by FIG. 1 is provided with the 1st polyolefin resin layer 11, the paper base material layer 12, and the 2nd polyolefin resin layer 13 in this order. In the case of a liquid paper container provided with the laminate 10, the first polyolefin resin layer 11 is located outside the liquid paper container, and the second polyolefin resin layer 13 is located inside the liquid paper container.
A laminate 20 shown in FIG. 2 includes a first polyolefin resin layer 11, a paper base material layer 12, an adhesive layer 14, a barrier layer 15, and a second polyolefin resin layer 13 in this order. is there. In the case of a liquid paper container including the laminate 20, the first polyolefin resin layer 11 is located outside the liquid paper container, and the second polyolefin resin layer 13 is located inside the liquid paper container.
3 includes a first polyolefin resin layer 11, a paper base layer 12, an adhesive layer 14, a plastic film 16, an adhesive layer 14, and a second polyolefin resin layer 13. It is provided in this order. In the case of a liquid paper container including the laminate 30, the first polyolefin resin layer 11 is located outside the liquid paper container, and the second polyolefin resin layer 13 is located inside the liquid paper container.
In any laminate, a printed layer or a thermoplastic resin layer may be further laminated.
Hereinafter, each layer which comprises a laminated body is demonstrated.

(Paper base material layer)
In the present invention, the paper base material layer functions as a base material layer for holding the polyolefin resin layer, and is preferably capable of imparting strength as a packaged product to the laminate. The paper used as the paper base layer has a basis weight of 100 g / m ² or more and 700 g / m ² or less, preferably 150 g / m ² or more and 600 g / m ² or less, more preferably 200 g / m ² or more and 500 g / m ² or less. It is what you have. As the paper base layer, white paperboard in general is targeted, but ivory paper using natural pulp, milk carton base paper, cup base paper and the like are particularly preferable from the viewpoint of safety.

  Further, the paperboard used in the present invention may use neutral rosin, alkyl ketene dimer, alkenyl succinic anhydride as a sizing agent, and use cationic polyacrylamide or cationic starch as a fixing agent. Also good. It is also possible to make paper in a neutral region of pH 6 or more and pH 9 or less using a sulfuric acid band. In addition to the above sizing agents, as well as fixing agents, various papermaking fillers, yield improvers, dry paper strength enhancers, wet paper strength enhancers, binders, dispersants, flocculants, plastics An agent and an adhesive may be appropriately contained.

(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 first and second polyolefin resin layers may include 5% by mass to 100% by mass of biomass polyolefin and 0% by mass to 95% by mass of fossil fuel-derived polyolefin with respect to the entire polyolefin resin layer. 5% by mass or more and less than 100% by mass of biomass polyolefin and 0% by mass exceeding 95% by mass of fossil fuel-derived polyolefin may be included, and 25% by mass to 75% by mass of biomass polyolefin and 25% by mass It may contain 75 to 75% by mass of fossil fuel-derived polyolefin. The concentrations of biomass polyolefin in the first and second polyolefin resin layers may be the same or different. 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 first and second polyolefin resin layers is 5% or more, preferably 10% or more, more preferably 15% or more, and further preferably 20% or more. . The biomass degrees in the first and second polyolefin resin layers may be the same or different. Note that the degree of biomass in the first and second polyolefin resin layers 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 first and second polyolefin resin layers is 5% or more, the amount of polyolefin derived from fossil fuel can be reduced and the environmental load can be reduced as compared with the prior art.

The first and second polyolefin resin layer, is preferably 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 those having a density of .915g / cm ³ or more 0.925 g / cm ³ or less. The densities of the first and second polyolefin resin layers may be the same or different. The density of the first and second polyolefin resin layers is a value measured according to 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 first and second polyolefin resin layers preferably have a thickness of 5 μm to 100 μm, more preferably 10 μm to 60 μm, and still more preferably 15 μm to 40 μm. The thicknesses of the first and second polyolefin resin layers may be the same or different. If the thickness of the first and second polyolefin resin layers is in the above range, the function as a sealing layer of the packaging container 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. Further, by including such an α-olefin, the polymerized biomass 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 polyolefins, 0.91 g / cm ³ or more 0.93 g / cm ³ or less, preferably 0.912 g / cm ³ or more 0.928 g / cm ³ or less, more preferably 0.915 g / cm ³ or more 0.925 g / It has a density of 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. 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 an inner layer of a 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.

  The biomass polyolefin is preferably 0.1 g / 10 min to 10 g / 10 min, more preferably 0.2 g / 10 min to 9 g / 10 min, and even more preferably 1 g / 10 min to 8.5 g / 10 min. Having a melt flow rate (MFR) of 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.

(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.

(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. The printing layer can be provided as necessary. For example, the printing layer is provided on the first polyolefin resin layer side surface of the paper base material layer or on the surface opposite to the paper base material layer side of the first polyolefin resin layer. Can do. The printing layer may be provided on the entire surface of the paper 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 about 50 to 500 mm, more preferably about 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.

(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 is an anchor 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 or a thermoplastic resin layer by a melt extrusion laminating method. It may be a coat layer. 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. An anchor coating agent 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.

  Further, 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 using conventionally well-known methods, such as the dry laminating method, the melt extrusion laminating method, and the sand laminating method. In the present invention, it is preferable to form a polyolefin resin layer on the surface of the layer to be laminated using a melt extrusion laminating method. Moreover, you may laminate | stack a polyolefin resin layer and another layer by a co-extrusion method.

  For example, a resin composition for forming a polyolefin resin layer by supplying it to a melt extruder heated to a temperature of Tm + 70 ° C. from a temperature equal to or higher than the melting point Tm of the resin composition for forming a polyolefin resin layer by the following method The polyolefin resin layer is laminated by melting the product and extruding it onto the surface of the layer to be laminated, for example, from a die such as a T die, and then rapidly cooling and solidifying the extruded sheet with a rotating cooling drum or the like. can do. As the melt extruder, a single screw extruder, a twin screw extruder, a vent extruder, a tandem extruder, or the like can be used depending on the purpose.

  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 such as liquid paper containers, paper cups, label materials, and lid materials.

(Liquid paper container)
Since the liquid paper container according to the present invention has excellent barrier properties, alcohol such as sake, shochu and wine, milk beverages such as milk, foods such as soft drinks such as orange juice and tea, car wax, shampoo and detergent, etc. It can be suitably used as a packaging paper container for all liquids such as chemical products. The case where a paper container is formed using the laminated body by this invention is demonstrated. For example, the liquid paper container 40 shown in FIG. 4 can be formed after the ruled line processing is performed on the laminated body shown in FIGS.

  As shown in FIG. 4, the liquid paper container 40 has a quadrangular cylindrical body portion 41 including a side surface, a square plate-like bottom portion 42, and an upper portion 43. Yes. The upper portion 43 includes a pair of opposed inclined plates 44 and a pair of folding portions 45 that are positioned between the pair of inclined plates 44 and are folded between the inclined plates 44. The pair of inclined plates 44 are bonded to each other by a margin 46 provided at each upper end. Note that a spout may be attached to one of the pair of inclined plates 44 and the spout may be sealed with a cap. Further, a flat top type container may be formed.

  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>
Milk carton base paper (manufactured by Clearwater, basis weight 320 g / m ² ) is prepared as a paper base layer, and biomass-derived low-density polyethylene (BBC, manufactured by SBC818, density: 0.918 g / cm ^{3) on one side.} MFR: 8.1 g / 10 min, biomass degree: 95%) is melt extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and the first polyolefin resin layer (biomass degree: 95%, thickness) 17 μm) was formed. Next, biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 minutes) on the surface opposite to the first polyolefin resin layer of the paper base material layer , Biomass degree: 95%) is melt extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a second polyolefin resin layer (biomass degree: 95%, thickness 28 μm). The laminate 1 in which the polyolefin resin layer, the paper base material layer, and the second polyolefin resin layer were sequentially laminated was obtained.

[Example 2]
<Preparation of laminated body 2>
Milk carton base paper (manufactured by Clearwater, basis weight 320 g / m ² ) is prepared as a paper base layer, and biomass-derived low-density polyethylene (BBC, manufactured by SBC818, density: 0.918 g / cm ^{3) on one side.} , MFR: 8.1 g / 10 min, biomass degree: 95%) and low density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / A mixed resin obtained by dry blending 50 parts by mass for 10 minutes with a biomass degree of 0% was melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to obtain a first polyolefin resin layer (biomass degree: 48 %, Thickness 17 μm). Next, biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 minutes) on the surface opposite to the first polyolefin resin layer of the paper base material layer , Biomass degree: 95%) Low-density polyethylene derived from fossil fuel with 50 parts by mass (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) A mixed resin obtained by dry blending 50 parts by mass is melt extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a second polyolefin resin layer (biomass degree: 48%, thickness 28 μm). A laminate 2 was obtained in which a first polyolefin resin layer, a paper base material layer, and a second polyolefin resin layer were sequentially laminated.

[Comparative Example 1]
<Preparation of laminate 3>
Milk carton base paper (manufactured by Clearwater, basis weight 320 g / m ² ) is prepared as a paper base layer, and low-density polyethylene derived from fossil fuels (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / min) on one side. cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is melt extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and a resin layer (biomass degree: 0%, thickness: 17 μm) Formed. Next, fossil fuel-derived low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass on the surface opposite to the resin layer of the paper base material layer Degree: 0%) is extruded at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a resin layer (biomass degree: 0%, thickness 28 μm), resin layer, paper base layer, resin A laminate 3 was obtained in which the layers were sequentially laminated.

[Example 3]
<Preparation of laminate 4>
Milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) is prepared as a paper base layer, and biomass-derived low-density polyethylene (Brasschem, SBC818, density: 0.918 g / cm ^{3) on one side.} , MFR: 8.1 g / 10 minutes, biomass degree: 95%) is melt extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / minute, and the first polyolefin resin layer (biomass degree: 95%, thickness) 20 μm) was formed. Next, a fossil fuel-derived ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemical Co., Ltd., Nucrel N0908C) is formed on the surface opposite to the first polyolefin resin layer of the paper base material layer using a sand lamination method. Through the adhesive resin layer (biomass degree 0%, thickness 20 μm), the aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, thickness 7 μm) and fossil fuel-derived polyethylene terephthalate film (manufactured by Toyobo Co., Ltd .: E5100) The aluminum foil surface of a dry laminate film obtained by dry lamination using a two-component curable adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90) was bonded together. Subsequently, a two-component curable anchor agent (manufactured by Mitsui Chemicals, Inc .: A3210 / A3075) was coated on the polyethylene terephthalate film surface of the dry laminate film to form an anchor coat layer. Thereafter, 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: 95%) on the anchor coat layer is a resin temperature of 320 ° C. , Melt extrusion extrusion at a line speed of 100 m / min to form a second polyolefin resin layer (biomass degree: 95%, thickness 55 μm), and the first polyolefin resin layer, paper base material layer, adhesive resin layer Thus, a laminate 4 was obtained in which a barrier layer, an adhesive layer, a plastic film, an anchor coat layer, and a second polyolefin resin layer were laminated in this order.

[Example 4]
<Preparation of laminated body 5>
Milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) is prepared as a paper base layer, and biomass-derived low-density polyethylene (Brasschem, SBC818, density: 0.918 g / cm ^{3) on one side.} , MFR: 8.1 g / 10 min, biomass degree: 95%) and low density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / A mixed resin obtained by dry blending 50 parts by mass for 10 minutes with a biomass degree of 0% was melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to obtain a first polyolefin resin layer (biomass degree: 48 %, Thickness 20 μm). Next, a fossil fuel-derived ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemical Co., Ltd., Nucrel N0908C) is formed on the surface opposite to the first polyolefin resin layer of the paper base material layer using a sand lamination method. Through the adhesive resin layer (biomass degree 0%, thickness 20 μm), the aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, thickness 7 μm) and fossil fuel-derived polyethylene terephthalate film (manufactured by Toyobo Co., Ltd .: E5100) The aluminum foil surface of a dry laminate film obtained by dry lamination using a two-component curable adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90). Subsequently, a two-component curable anchor agent (manufactured by Mitsui Chemicals, Inc .: A3210 / A3075) was coated on the polyethylene terephthalate film surface of the dry laminate film to form an anchor coat layer. Then, 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 and fossil fuel A mixed resin obtained by dry blending 50 parts by mass of low-density polyethylene derived from Nippon Polyethylene (LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%), 320 A second polyolefin resin layer (biomass degree: 48%, thickness 55 μm) is formed by melt extrusion lamination at a resin temperature of ° C. and a line speed of 100 m / min to form a first polyolefin resin layer and a paper base material layer. , Adhesive resin layer, barrier layer, adhesive layer, plastic film, anchor coat layer, second polyolefin resin layer are laminated in order To obtain a laminate 5 which.

[Comparative Example 2]
<Preparation of laminate 6>
Milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) is prepared as a paper base layer, and low-density polyethylene derived from fossil fuels (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / min) on one side. cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is melt extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and a resin layer (biomass degree: 0%, thickness 20 μm) is obtained. ) Was formed. Next, a fossil fuel-derived ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemical Co., Ltd., Nucrel N0908C) is formed on the surface opposite to the first polyolefin resin layer of the paper base material layer using a sand lamination method. Through the adhesive resin layer (biomass degree 0%, thickness 20 μm), the aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, thickness 7 μm) and fossil fuel-derived polyethylene terephthalate film (manufactured by Toyobo Co., Ltd .: E5100) The aluminum foil surface of a dry laminate film obtained by dry lamination using a two-component curable adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90) was bonded together. Subsequently, a two-component curable anchor agent (manufactured by Mitsui Chemicals, Inc .: A3210 / A3075) was coated on the polyethylene terephthalate film surface of the dry laminate film to form an anchor coat layer. Thereafter, low-density polyethylene derived from fossil fuel (LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) derived from fossil fuel on the anchor coat layer is 320 ° C. The resin layer is melt-extruded and laminated at a line speed of 100 m / min to form a resin layer (biomass degree: 0%, thickness 55 μm), resin layer, paper base layer, adhesive resin layer, barrier layer, adhesion A laminate 6 was obtained in which the agent layer, the plastic film, the anchor coat layer, and the resin layer were sequentially laminated.

[Example 5]
<Preparation of laminate 7>
As the aluminum vapor-deposited polyethylene terephthalate film 1, a polyethylene terephthalate film (MWR7, thickness 12 μm) derived from a fossil fuel having an aluminum vapor-deposited film formed thereon was prepared.

Milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) is prepared as a paper base layer, and biomass-derived low-density polyethylene (Brasschem, SBC818, density: 0.918 g / cm ^{3) on one side.} , MFR: 8.1 g / 10 minutes, biomass degree: 95%) is melt extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / minute, and the first polyolefin resin layer (biomass degree: 95%, thickness) 20 μm) was formed. Next, a fossil fuel-derived ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemical Co., Ltd., Nucrel N0908C) is formed on the surface opposite to the first polyolefin resin layer of the paper base material layer using a sand lamination method. The extruded surface of the aluminum vapor-deposited polyethylene terephthalate film 1 was bonded through this adhesive resin layer (biomass degree 0%, thickness 20 μm). Subsequently, on the polyethylene terephthalate film surface of the aluminum vapor-deposited polyethylene terephthalate film 1, a two-component curable anchor agent (manufactured by Mitsui Chemicals: A3210 / A3075) was coated to form an anchor coat layer. Thereafter, 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: 95%) on the anchor coat layer is a resin temperature of 320 ° C. , Melt extrusion extrusion at a line speed of 100 m / min to form a second polyolefin resin layer (biomass degree: 95%, thickness 55 μm), and the first polyolefin resin layer, paper base material layer, adhesive resin layer Thus, a laminate 7 in which a barrier layer, a plastic film, an anchor coat layer, and a second polyolefin resin layer were sequentially laminated was obtained.

[Example 6]
<Preparation of laminated body 8>
Milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) is prepared as a paper base layer, and biomass-derived low-density polyethylene (Brasschem, SBC818, density: 0.918 g / cm ^{3) on one side.} , MFR: 8.1 g / 10 min, biomass degree: 95%) and low density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / A mixed resin obtained by dry blending 50 parts by mass for 10 minutes with a biomass degree of 0% was melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to obtain a first polyolefin resin layer (biomass degree: 48 %, Thickness 20 μm). Next, a fossil fuel-derived ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemical Co., Ltd., Nucrel N0908C) is formed on the surface opposite to the first polyolefin resin layer of the paper base material layer using a sand lamination method. The extruded surface of the aluminum vapor-deposited polyethylene terephthalate film 1 was bonded through this adhesive resin layer (biomass degree 0%, thickness 20 μm). Subsequently, on the polyethylene terephthalate film surface of the aluminum vapor-deposited polyethylene terephthalate film 1, a two-component curable anchor agent (manufactured by Mitsui Chemicals: A3210 / A3075) was coated to form an anchor coat layer. Then, 50 parts by mass of low density polyethylene derived from biomass on the anchor coat layer (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%) and fossil fuel Of low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) 50 parts by mass, Are melt-extruded and laminated at a line speed of 100 m / min to form a second polyolefin resin layer (biomass degree: 48%, thickness 55 μm), and the first polyolefin resin layer, paper substrate layer, A laminate in which an adhesive resin layer, a barrier layer, a plastic film, an anchor coat layer, and a second polyolefin resin layer are sequentially laminated It was obtained.

[Comparative Example 3]
<Preparation of laminated body 9>
Milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) is prepared as a paper base layer, and low-density polyethylene derived from fossil fuels (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / min) on one side. cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is melt extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and a resin layer (biomass degree: 0%, thickness 20 μm) is obtained. ) Was formed. Next, a fossil fuel-derived ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemical Co., Ltd., Nucrel N0908C) is formed on the surface opposite to the first polyolefin resin layer of the paper base material layer using a sand lamination method. The extruded surface of the aluminum vapor-deposited polyethylene terephthalate film 1 was bonded through this adhesive resin layer (biomass degree 0%, thickness 20 μm). Subsequently, on the polyethylene terephthalate film surface of the aluminum vapor-deposited polyethylene terephthalate film 1, a two-component curable anchor agent (manufactured by Mitsui Chemicals: A3210 / A3075) was coated to form an anchor coat layer. Then, low-density polyethylene derived from fossil fuel on the anchor coat layer (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%), 320 ° C. Melt extrusion lamination at resin temperature and line speed of 100 m / min to form a resin layer (biomass degree: 0%, thickness 55 μm), resin layer, paper base material layer, adhesive resin layer, barrier layer, plastic film Then, 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>
Milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) is prepared as a paper base layer, and biomass-derived low-density polyethylene (Brasschem, SBC818, density: 0.918 g / cm ^{3) on one side.} , MFR: 8.1 g / 10 minutes, biomass degree: 95%) is melt extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / minute, and the first polyolefin resin layer (biomass degree: 95%, thickness) 20 μm) was formed. Next, on the surface opposite to the first polyolefin resin layer of the paper base material layer, a low-density polyethylene derived from fossil fuel (LC520, manufactured by Nippon Polyethylene Co., Ltd., density: 0.923 g / cm) using a sand lamination method. ^3. MFR: 3.6 g / 10 min, biomass degree: 0%), while extruding this adhesive resin layer (biomass degree: 0%, thickness 15 μm), a polyethylene terephthalate film derived from fossil fuel (Toyobo Co., Ltd.) Manufactured, T4100, thickness 12 μm). Subsequently, an anchor coat agent (EL540 / CAT-RT32 manufactured by Toyo Morton Co., Ltd.) was applied and dried on the polyethylene terephthalate film to form an anchor coat layer. Thereafter, 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: 95%) on the anchor coat layer is a resin temperature of 320 ° C. , Melt extrusion extrusion at a line speed of 100 m / min to form a second polyolefin resin layer (biomass degree: 95%, thickness 55 μm), and the first polyolefin resin layer, paper base material layer, adhesive resin layer A laminate 10 was obtained in which a plastic film, an anchor coat layer, and a second polyolefin resin layer were laminated in this order.

[Example 8]
<Preparation of Laminate 11>
Milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) is prepared as a paper base layer, and biomass-derived low-density polyethylene (Brasschem, SBC818, density: 0.918 g / cm ^{3) on one side.} , MFR: 8.1 g / 10 min, biomass degree: 95%) and low density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / A mixed resin obtained by dry blending 50 parts by mass for 10 minutes with a biomass degree of 0% was melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to obtain a first polyolefin resin layer (biomass degree: 48 %, Thickness 20 μm). Next, on the surface opposite to the first polyolefin resin layer of the paper base material layer, a low-density polyethylene derived from fossil fuel (LC520, manufactured by Nippon Polyethylene Co., Ltd., density: 0.923 g / cm) using a sand lamination method. ^3. MFR: 3.6 g / 10 min, biomass degree: 0%), while extruding this adhesive resin layer (biomass degree: 0%, thickness 15 μm), a polyethylene terephthalate film derived from fossil fuel (Toyobo Co., Ltd.) Manufactured, T4100, thickness 12 μm). Subsequently, an anchor coat agent (EL540 / CAT-RT32 manufactured by Toyo Morton Co., Ltd.) was applied and dried on the polyethylene terephthalate film to form an anchor coat layer. Then, 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 and fossil fuel A mixed resin obtained by dry blending 50 parts by mass of low-density polyethylene derived from Nippon Polyethylene (LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%), 320 A second polyolefin resin layer (biomass degree: 48%, thickness 55 μm) is formed by melt extrusion lamination at a resin temperature of ° C. and a line speed of 100 m / min to form a first polyolefin resin layer and a paper base material layer. A laminate 11 in which an adhesive resin layer, a plastic film, an anchor coat layer, and a second polyolefin resin layer are sequentially laminated is obtained. .

[Comparative Example 4]
<Preparation of laminated body 12>
Milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) is prepared as a paper base layer, and low-density polyethylene derived from fossil fuels (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / min) on one side. cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is melt extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and a resin layer (biomass degree: 0%, thickness 20 μm) is obtained. ) Was formed. Next, on the surface opposite to the first polyolefin resin layer of the paper base material layer, a low-density polyethylene derived from fossil fuel (LC520, manufactured by Nippon Polyethylene Co., Ltd., density: 0.923 g / cm) using a sand lamination method. ^3. MFR: 3.6 g / 10 min, biomass degree: 0%), while extruding this adhesive resin layer (biomass degree: 0%, thickness 15 μm), a polyethylene terephthalate film derived from fossil fuel (Toyobo Co., Ltd.) Manufactured, T4100, thickness 12 μm). Subsequently, an anchor coat agent (EL540 / CAT-RT32 manufactured by Toyo Morton Co., Ltd.) was applied and dried on the polyethylene terephthalate film to form an anchor coat layer. Thereafter, low-density polyethylene derived from fossil fuel (LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) derived from fossil fuel on the anchor coat layer is 320 ° C. The resin layer is melt-extruded and laminated at a line speed of 100 m / min to form a resin layer (biomass degree: 0%, thickness 55 μm), and the resin layer, paper base layer, adhesive resin layer, plastic film, anchor A laminate 12 in which a coat layer and a resin layer were sequentially laminated was obtained.

[Production Examples 1 to 12]
<Production of liquid paper container>
The laminates 1 to 12 were pressed with a male mold and a female mold to perform ruled line processing and punched into a paper container blank. Thereafter, with the liquid paper container filling machine “DR-10”, the center value of the seal temperature condition is set to the top heater temperature of 320 ° C. and the bottom heater temperature of 340 ° C. 12 was produced.

(Leakage and pinhole test)
After the top and bottom of the liquid paper containers 1 to 12 prepared above are cut off, the test solution (Microcheck penetrant (made by Taiho Kozai)) is poured into the top and bottom, left at room temperature for 30 minutes, and then checked. Washing was performed with a washing solution (manufactured by Taiho Kozai). Thereafter, the top and bottom portions were opened in a flat plate shape by heating with hot air, and leakage and pinholes were visually evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1.
(Evaluation criteria for liquid leakage)
◯: There was no liquid leakage from the top seal part and the bottom seal part, and the performance as a liquid paper container was good.
X: There was liquid leakage from the top seal part and the bottom seal part, and the performance as a liquid paper container was poor.
(Pinhole evaluation criteria)
A: There were no pinholes at the top and bottom, and the performance as a liquid paper container was good.
X: There were pinholes at the top and bottom, and the performance as a liquid paper container was poor.

10, 20, 30 Laminate 11 First polyolefin resin layer 12 Paper base layer 13 Second polyolefin resin layer 14 Adhesive layer 15 Barrier layer 16 Plastic film 40 Liquid paper container 41 Body 42 Bottom 43 Top 44 Inclined plate 45 Insertion section 46

Claims (6)

A laminate comprising at least a first polyolefin resin layer, a paper base material layer, and a second polyolefin resin layer,
The first and second polyolefin resin layers include a biomass polyolefin that is a polymer of monomers containing biomass-derived ethylene,
The degree of biomass in the first and second polyolefin resin layers is 5% or more,
The biomass polyolefin has a density of 0.91 g / cm ³ or more 0.93 g / cm ³ or less, laminate.   The laminate according to claim 1, wherein the first or second polyolefin resin layer further contains a polyolefin derived from fossil fuel.   3. The laminate according to claim 2, wherein the first or second polyolefin resin layer contains 5 to 100 mass% of the biomass polyolefin and 0 to 95 mass% of the polyolefin derived from the fossil fuel. body.   The laminate according to any one of claims 1 to 3, wherein the first or second polyolefin resin layer contains polyethylene.   Packaged product provided with the laminated body as described in any one of Claims 1-4. A liquid paper container comprising the laminate according to any one of claims 1 to 4,
A liquid paper container, wherein the innermost layer of the liquid paper container is the second polyolefin resin layer.

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