JP6635355B2 - Laminate for packaging products with biomass-derived resin layer - Google Patents

Description

  The present invention relates to a laminate having a biomass-derived resin layer, and more particularly, a biomass polyolefin resin composition comprising a paper base and a biomass-derived polyolefin obtained by polymerizing a monomer containing biomass-derived ethylene. The present invention relates to a laminated product for a packaging product, comprising a biomass polyolefin resin layer made of a product and a non-biomass polyolefin resin layer in this order.

  In recent years, with the increasing demand for the establishment of a recycling-based society, in the materials field as well, there has been a desire to break away from fossil fuels as well as energy, and the use of biomass has attracted attention. Biomass is an organic compound that is photosynthesized from carbon dioxide and water, and is a so-called carbon-neutral renewable energy that is converted into carbon dioxide and water again by using it. Recently, biomass plastics using biomass as a raw material have been rapidly commercialized, and attempts have been made to produce various resins from biomass raw materials.

  As a biomass-derived resin, commercial production of polylactic acid (PLA), which is manufactured via lactic acid fermentation, has begun, but its performance as a plastic, including its biodegradability, is the current general-purpose plastic. Therefore, there is a limit in the product use and the method of manufacturing the product, and the product has not been widely used. In addition, a life cycle assessment (LCA) evaluation is performed on the PLA, and the energy consumption at the time of manufacturing the PLA and the equivalence at the time of replacing the general-purpose plastic are discussed.

  Here, as the general-purpose plastic, various types such as polyethylene, polypropylene, polyvinyl chloride, and polystyrene are used. In particular, polyethylene is formed into films, sheets, bottles, and the like, and is used for various uses such as packaging materials, and is widely used worldwide. Therefore, using polyethylene derived from the conventional fossil fuel has a large environmental load.

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

JP 2011-506628 A

  The present inventors have focused on ethylene which is a raw material of a polyolefin laminate, and in place of ethylene obtained from a conventional fossil fuel, a laminate having a biomass polyolefin resin layer of a polyolefin using ethylene derived from biomass as its raw material is It has been found that a laminate of a polyolefin resin produced using ethylene obtained from a conventional fossil fuel and a laminate having physical properties such as mechanical properties can be obtained. The present invention is based on such findings.

  Accordingly, an object of the present invention is to have a paper base, a biomass polyolefin resin layer composed of a biomass polyolefin resin composition containing a carbon neutral polyolefin using biomass-derived ethylene, and a non-biomass polyolefin resin layer in this order. The present invention provides a laminate for a packaging product comprising: a laminate having a resin layer produced from a raw material obtained from a conventional fossil fuel; and packaging of a biomass polyolefin resin which is comparable in physical properties such as mechanical properties. It is to provide a laminate for a product.

That is, according to one aspect of the present invention,
Paper base material,
Biomass polyolefin resin layer comprising a biomass polyolefin resin composition comprising a biomass-derived polyolefin obtained by polymerizing a monomer containing biomass-derived ethylene,
A non-biomass polyolefin resin layer made of a resin material containing a fossil fuel-derived raw material,
Are provided in this order, and a laminate for packaging products is provided.
In the aspect of the present invention, it is preferable that the biomass polyolefin resin layer contains biomass-derived polyethylene obtained by polymerizing a monomer containing biomass-derived ethylene.
In an embodiment of the present invention, the biomass polyolefin resin layer may further include fossil fuel-derived polyethylene obtained by polymerizing fossil fuel-derived ethylene and fossil fuel-derived ethylene and / or α-olefin monomer. preferable.
In an embodiment of the present invention, it is preferable that the biomass polyolefin resin layer contains 5% by mass or more of the biomass-derived ethylene based on the entire biomass polyolefin resin layer.
In the aspect of the present invention, it is preferable that the image forming apparatus further includes a barrier layer containing an inorganic substance.
In another aspect of the present invention, there is provided a packaged product comprising the laminate for a packaged product described above.

  The laminate for packaging products according to the present invention is a paper base, a biomass polyolefin resin layer composed of a biomass polyolefin resin composition containing a biomass-derived polyolefin obtained by polymerizing a monomer containing biomass-derived ethylene, and a non-biomass. By having a polyolefin resin layer in this order, a carbon-neutral polyolefin resin laminate for packaging products can be realized. Therefore, the amount of fossil fuel used can be significantly reduced as compared with the related art, and the environmental load can be reduced. In addition, the laminated product for packaging products according to the present invention is not inferior in physical properties such as mechanical properties as compared with a polyolefin laminated product manufactured from a raw material obtained from a conventional fossil fuel. Can be replaced.

FIG. 2 is a schematic cross-sectional view showing one example of a laminate according to the present invention. FIG. 2 is a schematic cross-sectional view showing one example of a laminate according to the present invention.

  In the present invention, the "biomass polyolefin resin composition" and the "biomass polyolefin resin layer" are those in which raw materials derived from biomass are used at least in part as raw materials, and all of the raw materials are derived from biomass. It does not mean.

Laminate The laminate according to the present invention comprises a paperboard substrate and a biomass polyolefin resin layer. By having the biomass polyolefin resin layer, the laminate can realize a carbon-neutral polyolefin resin laminate. Therefore, the amount of fossil fuel used can be significantly reduced as compared with the related art, and the environmental load can be reduced. In addition, the laminate according to the present invention is not inferior in physical properties such as mechanical properties as compared with a laminate of a polyolefin resin manufactured from a raw material obtained from a conventional fossil fuel, and thus a laminate of a conventional polyolefin resin is used. Can be substituted.

  FIGS. 1 and 2 show schematic cross-sectional views of an example of the laminate according to the present invention. The laminate 10 shown in FIG. 1 has a paperboard substrate 11 and a biomass polyolefin resin layer 12 formed on the paperboard substrate 11. The laminate 20 shown in FIG. 2 includes a paperboard substrate 21, a first biomass polyolefin resin layer 22 formed on the paperboard substrate 21, and a second biomass polyolefin resin layer 22 formed on the first biomass polyolefin resin layer 22. And a biomass polyolefin resin layer 23 in this order. Hereinafter, each layer constituting the laminate will be described.

Paperboard Substrate In the present invention, the paperboard substrate functions as a substrate layer, and needs to have strength enough to withstand the step of laminating a biomass polyolefin resin layer by extrusion. Paper used as paperboard substrate, 100~700g / ^{m 2,} preferably not 150~600g / ^{m 2,} more preferably those having a basis weight of 200-500 g / ^{m 2.} As the paperboard substrate, white paperboard is generally used, 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. Is also good. It is also possible to make a paper in the neutral region of pH 6 to 9 using a sulfuric acid band. In addition, if necessary, in addition to the above-mentioned sizing agent, other than the fixing agent, various fillers for papermaking, a retention enhancer, a dry paper strength enhancer, a wet paper strength enhancer, a binder, a dispersant, a flocculant, a plasticizer. Agents and adhesives may be appropriately contained.

Biomass polyolefin resin layer In the present invention, the biomass polyolefin resin layer is preferably composed of the following biomass-derived ethylene in an amount of preferably 5% by mass or more, more preferably 5 to 95% by mass, and still more preferably 25 to 95% by mass based on the entire biomass polyolefin resin layer. It comprises 75% by mass. The biomass polyolefin resin layer may be composed of at least two or more layers. For example, the biomass polyolefin resin layer includes a first biomass polyolefin resin layer and a second biomass polyolefin resin layer in order from the paperboard substrate side. Both the seal layer and the core layer of the laminate may be a biomass polyolefin resin layer, or only one of them may be a biomass polyolefin resin layer.

First Biomass Polyolefin Resin Layer In the present invention, the first biomass polyolefin resin layer may function as a core layer of the laminate. By having the core layer, the laminate does not break and can exhibit excellent flexibility.

  In the first biomass polyolefin resin layer, the biomass-derived ethylene is preferably at least 5% by mass, more preferably 5 to 95% by mass, still more preferably 25 to 75% by mass, based on the entire first biomass polyolefin resin layer, Most preferably, it comprises 40 to 75%. If the concentration of biomass-derived ethylene in the first biomass polyolefin resin layer is 5% by mass or more, the amount of fossil fuel used can be reduced as compared with the conventional case, and a carbon-neutral polyolefin resin laminate is realized. it can.

The first biomass polyolefin resin layer preferably has a thickness of 0.915 to 0.96 g / cm ³ , more preferably 0.92 to 0.955 g / cm ³ , and still more preferably 0.93 to 0.955 g / cm ³ . It has a density. The density of the first biomass polyolefin resin layer is a value measured according to the method specified in the method A in JIS K7112-1980 after performing the annealing described in JIS K6760-1995. When the density of the first biomass polyolefin resin layer is 0.915 g / cm ³ or more, the rigidity of the first biomass polyolefin resin layer can be increased. When the density of the first biomass polyolefin resin layer is 0.96 g / cm ³ or less, the transparency and mechanical strength of the first biomass polyolefin resin layer can be increased.

  The first biomass polyolefin resin layer has a melt flow rate (MFR) of 1 to 30 g / 10 min, preferably 3 to 25 g / 10 min, more preferably 4 to 20 g / 10 min. The melt flow rate is a value measured by the method A at a temperature of 190 ° C. and a load of 21.18 N in a method specified in JIS K7210-1995. If the MFR of the first biomass polyolefin resin layer is 1 g / 10 minutes or more, the extrusion load during molding can be reduced. When the MFR of the biomass polyolefin resin composition is 30 g / 10 minutes or less, the mechanical strength of the first biomass polyolefin resin layer can be increased.

  The first biomass polyolefin resin layer has a thickness of 10 to 100 μm, preferably 10 to 50 μm, and more preferably 15 to 30 μm.

Second biomass polyolefin resin layer In the present invention, the second biomass polyolefin resin layer may function as a seal layer of the laminate. Since the laminate has the heat seal layer, the laminate can be firmly bonded without using an adhesive or the like when laminated on another resin film.

  The second biomass polyolefin resin layer preferably contains biomass-derived ethylene in an amount of preferably 5% by mass or more, more preferably 5 to 95% by mass, and still more preferably 25 to 75% by mass, based on the entire second biomass polyolefin resin layer. It consists of If the concentration of ethylene derived from biomass in the second biomass polyolefin resin layer is 5% by mass or more, the amount of fossil fuel used can be reduced as compared with the conventional case, and a carbon-neutral polyolefin laminate can be realized.

The second biomass polyolefin resin layer has a density of 0.90 to 0.925 g / cm ³ , preferably 0.905 to 0.925 g / cm ³ . The density of the second biomass polyolefin resin layer is a value measured according to the method specified in the method A of JIS K7112-1980 after performing the annealing described in JIS K6760-1995. If the density of the second biomass polyolefin resin layer is 0.90 g / cm ³ or more, the rigidity of the second biomass polyolefin resin layer can be increased. When the density of the second biomass polyolefin resin layer is 0.925 g / cm ³ or less, the transparency and mechanical strength of the second biomass polyolefin resin layer can be increased.

  The second biomass polyolefin resin layer has a melt flow rate (MFR) of 1 to 30 g / 10 min, preferably 3 to 25 g / 10 min, more preferably 4 to 20 g / 10 min. The melt flow rate is a value measured by the method A at a temperature of 190 ° C. and a load of 21.18 N in a method specified in JIS K7210-1995. If the MFR of the second biomass polyolefin resin layer is 1 g / 10 minutes or more, the extrusion load during molding can be reduced. When the MFR of the biomass polyolefin resin composition is 30 g / 10 minutes or less, the mechanical strength of the second biomass polyolefin resin layer can be increased.

  The second biomass polyolefin resin layer has a thickness of 1 to 50 μm, preferably 1 to 20 μm, more preferably 1 to 10 μm.

  In the present invention, the first biomass polyolefin resin layer and the second biomass polyolefin resin layer satisfy the following specific relationship with respect to density, thickness, MFR, and biomass degree (concentration of biomass-derived ethylene). Preferably, there is.

In the present invention, the density d ₂ between the density d ₁ of the first biomass polyolefin resin layer second biomass polyolefin resin layer preferably satisfy d _1> d _2. This is because the first biomass polyolefin resin layer functions as a core layer and thus requires rigidity, and the second biomass polyolefin resin layer functions as a heat seal layer and requires flexibility.

In the present invention, the thickness t ₂ of the first and the thickness t ₁ of the biomass polyolefin resin layer second biomass polyolefin resin layer preferably satisfy t _1> t _2. This is because the first biomass polyolefin resin layer functions as a core layer and thus needs a thickness, and the second biomass polyolefin resin layer functions as a heat seal layer, so that the thickness is not required as large as the core layer.

In the present invention, MFR ₂ of MFR ₁ of the first biomass polyolefin resin layer second biomass polyolefin resin layer _preferably satisfy the MFR 1> MFR _2. This is because the first biomass polyolefin resin layer functions as a core layer and thus requires rigidity, and the second biomass polyolefin resin layer functions as a heat seal layer and requires flexibility.

In the present invention, the first ethylene concentration C ₁ of biomass-derived biomass polyolefin resin layer and the second ethylene concentration C ₂ of the biomass-derived biomass polyolefin resin layer, it is preferable to satisfy the C _1> C _2. Since the first biomass polyolefin resin layer functions as a core layer, since the thickness is large and the amount of ethylene used is large, the amount of fossil fuel used can be further reduced by increasing the biomass degree of the first biomass polyolefin resin layer. It is.

Biomass-Derived Ethylene In the present invention, a method for producing biomass-derived ethylene which is a raw material of a biomass-derived 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 fermented ethanol derived from biomass obtained from plant raw materials. The plant material is not particularly limited, and conventionally known plants can be used. For example, corn, sugar cane, beet, and manioc can be mentioned.

  In the present invention, the biomass-derived fermented ethanol refers to purified ethanol obtained by contacting a culture solution containing a carbon source obtained from a plant material with a microorganism-producing microorganism or a product derived from a crushed product thereof and producing the ethanol. For 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 causing azeotropic distillation, or removing water by membrane separation or the like can be mentioned.

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

  When ethylene is obtained by a dehydration reaction of ethanol, a catalyst is usually used. However, the catalyst is not particularly limited, and a conventionally known catalyst can be used. The process is advantageous in 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 performed under heating conditions. As long as the reaction proceeds at a commercially useful reaction rate, the heating temperature is not limited, but a temperature of preferably 100 ° C. or higher, more preferably 250 ° C. or higher, and still more preferably 300 ° C. or higher is appropriate. Although the upper limit is not particularly limited, it 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 is preferably a pressure equal to or higher than normal pressure to facilitate subsequent gas-liquid separation. Industrially, a fixed bed flow reaction in which the catalyst can be easily separated 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 the ethanol supplied as a raw material. Generally, when performing a dehydration reaction, it is preferable that there is no water in consideration of the water removal efficiency. However, in the case of ethanol dehydration reaction using a solid catalyst, it has been found that the production of other olefins, especially butene, tends to increase in the absence of water. Presumably, it is because the ethylene dimerization after dehydration cannot be suppressed unless a small amount of water is present. The lower limit of the allowable water content needs to be 0.1% or more, preferably 0.5% or more. The upper limit is not particularly limited, but is preferably 50% by mass or less, more preferably 30% or less, and still more preferably 20% or less, from the viewpoint of material balance and heat balance.

  By performing the dehydration reaction of ethanol in this manner, a mixed portion of ethylene, water and a small amount of unreacted ethanol is obtained, but ethylene is a gas at about 5 MPa or less at room temperature. 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, and the like are not particularly limited, except that the operating pressure at this time is equal to or higher than normal pressure.

  When the raw material is biomass-derived ethanol, the obtained ethylene contains carbonyl compounds such as ketones, aldehydes, and esters, which are impurities mixed in the ethanol fermentation step, and carbon dioxide, which is a decomposition product thereof, and a decomposition product of an enzyme. Nitrogen-containing compounds such as amines and amino acids, which are contaminants, and ammonia, which is a decomposition product thereof, are contained in trace amounts. Depending on the use of ethylene, these very small 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. Suitable purification operations include, for example, an adsorption purification method. The adsorbent to be used is not particularly limited, and a conventionally known adsorbent can be used. For example, a material having a high surface area is preferable, and the type of the adsorbent is selected according to the type and amount of impurities in ethylene obtained by a dehydration reaction of biomass-derived ethanol.

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

Biomass Polyolefin In the present invention, biomass-derived polyolefin is obtained by polymerizing a monomer containing biomass-derived ethylene. As the biomass-derived ethylene, it is preferable to use ethylene obtained by the above-described production method. Since ethylene derived from biomass is used as the 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 the raw material of the biomass-derived polyolefin may further contain fossil fuel-derived ethylene and / or α-olefin, or may further contain biomass-derived α-olefin.

  The α-olefin is not particularly limited in the number of carbon atoms, but usually one having 3 to 20 carbon atoms can be used, and is preferably butylene, hexene, or octene. This is because butylene, hexene, or octene can be produced by polymerizing ethylene, which is a raw material derived from biomass. In addition, by containing 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.

  Preferably, the polyolefin is polyethylene. This is because, by using ethylene, which is a biomass-derived raw material, it is theoretically possible to produce from 100% biomass-derived components.

The concentration of biomass-derived ethylene in the polyolefin (hereinafter, sometimes referred to as “biomass degree”) is a value obtained by measuring the content of biomass-derived carbon by radiocarbon (C14) measurement. Since C14 is contained in the carbon dioxide in the atmosphere at a constant rate (105.5 pMC), the C14 content in plants growing by taking in the carbon dioxide in the atmosphere, for example, corn, is also about 105.5 pMC. It is known. It is also known that C14 is hardly contained in fossil fuels. Therefore, by measuring the ratio of C14 contained in all the carbon atoms in the polyolefin, the ratio of carbon derived from biomass can be calculated. In the present invention, when the content of C14 in the polyolefin is defined as _PC14 , the content P _bio of carbon derived from biomass can be determined as follows.
P _bio (%) = P _C14 /105.5×100

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

  In the present invention, the biomass-derived polyolefin or the biomass-derived resin layer does not need to have a biomass degree of 100%. This is because if a biomass-derived raw material is used even in a part of the laminate, the purpose of the present invention is to reduce the amount of fossil fuel used compared to the related art.

  In the present invention, the method of polymerizing a monomer containing ethylene derived from biomass is not particularly limited, and can be performed by a conventionally known method. The polymerization temperature and the polymerization pressure are suitably adjusted according to the polymerization method and the 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 method for polymerizing polyolefins, especially ethylene polymers and copolymers of ethylene and α-olefins, is based on the type of the target polyethylene, for example, high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE). ) And linear low-density polyethylene (LLDPE), etc., depending on the density and branching. 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, gas phase polymerization, slurry polymerization, solution polymerization, and any one of high-pressure ionic polymerization, It is preferable to carry out in one stage or in two or more stages.

  The single-site catalyst is a catalyst capable of forming a uniform active species, and is usually adjusted by contacting a metallocene-based transition metal compound or a non-metallocene-based transition metal compound with an activating cocatalyst. . Single-site catalysts are preferable because they have a more uniform active site structure than multi-site catalysts and can polymerize a polymer having a high molecular weight and a highly uniform structure. It is particularly preferable to use a metallocene catalyst as the single-site catalyst. The metallocene catalyst is a catalyst containing a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, a co-catalyst, an organic metal compound as required, and each catalyst component of a carrier. is there.

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

  In the transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, examples of the transition metal include zirconium, titanium, and hafnium, with zirconium and hafnium being particularly preferred. The transition metal compound usually has two ligands each having a cyclopentadienyl skeleton, and it is preferable that each ligand having a cyclopentadienyl skeleton be bonded to each other by a crosslinking group. Examples of the crosslinking group include a substituted silylene group such as an alkylene group having 1 to 4 carbon atoms, a silylene group, a dialkylsilylene group and a diarylsilylene group, and a substituted germylene group such as a dialkylgermylene group and a diarylgermylene group. Preferably, it is a substituted silylene group.

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

  As the transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, one kind or a mixture of two or more kinds can be used as a catalyst component.

  The co-catalyst refers to a co-catalyst capable of effectively using the above-mentioned transition metal compound of Group IV of the periodic table as a polymerization catalyst or equalizing ionic charges in a catalytically activated state. As the co-catalyst, benzene-soluble aluminoxane or benzene-insoluble organic aluminum oxy compound of an organic aluminum oxy compound, an ion-exchanged layered silicate, a boron compound, a cation containing or not containing an active hydrogen group and a non-coordinating anion are used. Lanthanide salts such as lanthanum oxide, tin oxide, and phenoxy compounds containing a fluoro group.

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

  Further, examples of the organometallic compound used as necessary include an organic aluminum compound, an organic magnesium compound, an organic zinc compound and the like. Of these, organoaluminum is preferably used.

  Further, as the polyolefin, a polymer of ethylene or a copolymer of ethylene and an α-olefin may be used alone or in combination of two or more.

Biomass polyolefin resin composition In the present invention, the biomass polyolefin resin composition contains the above-mentioned polyolefin as a main component. The biomass polyolefin resin composition preferably contains 5% by mass or more, more preferably 5 to 95% by mass, and still more preferably 25 to 75% by mass of ethylene derived from biomass based on the entire biomass polyolefin resin composition. is there. When the concentration of ethylene derived from biomass in the biomass polyolefin resin composition is 5% by mass or more, the amount of fossil fuel used can be reduced as compared with the conventional case, and a carbon-neutral polyolefin laminate can be realized.

  The biomass polyolefin resin composition may contain two or more types of polyolefins having different biomass degrees. The biomass polyolefin resin composition as a whole may have a concentration of biomass-derived ethylene within the above range.

  The biomass polyolefin resin composition may further include a fossil fuel-derived polyolefin obtained by polymerizing a monomer containing fossil fuel-derived ethylene and fossil fuel-derived ethylene and / or α-olefin. In other words, in the present invention, the biomass polyolefin resin composition may be a mixture of a biomass-derived polyolefin and a fossil fuel-derived polyolefin. The mixing method is not particularly limited, and mixing can be performed by a conventionally known method. For example, a dry blend or a melt blend may be used.

  According to an embodiment of the present invention, the biomass polyolefin resin composition preferably comprises 5 to 90% by weight, more preferably 25 to 75% by weight of biomass-derived polyolefin and preferably 10 to 95% by weight, more preferably 25% by weight. And 75% by mass of a polyolefin derived from a fossil fuel. Even when the biomass polyolefin resin composition of such a mixture is used, the biomass polyolefin resin composition as a whole may have a concentration of ethylene derived from biomass within the above range.

  In the above-mentioned biomass polyolefin resin composition production process, or to the produced biomass polyolefin resin composition, as long as its properties are not impaired, in addition to the main component polyolefin, various additives may be added. Good. Examples of additives include a plasticizer, an ultraviolet stabilizer, a coloring inhibitor, a matting agent, a deodorant, a flame retardant, a weathering agent, an antistatic agent, a yarn friction reducing agent, a slip agent, a release agent, An oxidizing agent, an ion exchange agent, a coloring pigment, and the like can be added. These additives are added in an amount of preferably 1 to 20% by mass, and more preferably 1 to 10% by mass, based on the entire biomass polyolefin resin composition.

Non-biomass polyolefin resin layer The laminate according to the present invention may further have a non-biomass polyolefin resin layer. The non-biomass polyolefin resin layer is a resin layer made of a resin material containing a raw material derived from a fossil fuel, and has a biomass degree of 0%. When only one of the core layer and the seal layer of the laminate is a biomass polyolefin resin layer, the other may be a non-biomass polyolefin resin layer. The non-biomass polyolefin resin layer can be formed using a conventionally known raw material, and the composition and the forming method are not particularly limited. When the laminate further has a non-biomass polyolefin resin layer, heat resistance, pressure resistance, water resistance, heat sealability, pinhole resistance, piercing resistance, and other physical properties can be imparted or improved. The laminate may have two or more non-biomass polyolefin resin layers. When there are two or more non-biomass polyolefin resin layers, each may have the same composition or different compositions.

  As the non-biomass polyolefin resin layer, for example, low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, propylene-ethylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid Resins such as copolymers, ethylene-methacrylic acid copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methyl methacrylate copolymers, and ionomers can be used. These resins may be formed by an extrusion lamination method, or may be previously laminated as a film formed by a T-die method or an inflation method by a dry lamination or extrusion lamination method or the like. .

  Also, stretched polyethylene terephthalate film, silica-deposited stretched polyethylene terephthalate film, alumina-deposited stretched polyethylene terephthalate film, stretched nylon film, silica-deposited stretched nylon film, alumina-deposited stretched nylon film, stretched polypropylene film, polyvinyl alcohol-coated stretched polypropylene film, nylon 6 Either a / co-extended stretch film of / meta-xylylenediamine nylon 6 or a co-extended film of a polypropylene / ethylene-vinyl alcohol copolymer, or a composite film obtained by laminating two or more of these films.

Barrier layer The laminate according to the present invention may further have a barrier layer. The barrier layer is composed of an inorganic substance and / or an inorganic oxide, and is preferably composed of a vapor-deposited film of an inorganic substance or an inorganic oxide or a metal foil. The deposited film can be formed by a conventionally known method using a conventionally known inorganic substance or inorganic oxide, and the composition and the forming method are not particularly limited. When the laminate further includes a barrier layer, a gas barrier property for preventing transmission of oxygen gas and water vapor and a light shielding property for preventing transmission of visible light and ultraviolet light 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 different compositions.

  Examples of the deposited film include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), and titanium (Ti). ), Lead (Pb), zirconium (Zr), yttrium (Y) or the like, or a deposited film of an inorganic oxide can be used. In particular, as a material suitable for a packaging material (bag) or the like, a deposited film of aluminum metal or a deposited film of silicon oxide or aluminum metal or aluminum oxide is preferably used.

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 the 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, Potassium (K) is 0 to 0.5, tin (Sn) is 0 to 2, sodium (Na) is 0 to 0.5, boron (B) is 0 to 1, 5, titanium (Ti). Can take a value in the range of 0 to 2, lead (Pb) takes a value of 0 to 1, zirconium (Zr) takes a value of 0 to 2, and yttrium (Y) takes a value of 0 to 1.5. In the above, when X = 0, it is a complete inorganic simple substance (pure substance), it is not transparent, and the upper limit of the range of X is a completely oxidized value. Silicon (Si) and aluminum (Al) are preferably used for the packaging material. 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 thickness of the deposited film of the inorganic substance or the inorganic oxide as described above varies depending on the kind of the inorganic substance or the inorganic oxide to be used, but is, for example, about 50 to 2000 °, preferably about 100 to 1000 °. It is desirable to arbitrarily select and form within the range. More specifically, in the case of a deposited film of aluminum, the thickness is preferably about 50 to 600 °, more preferably about 100 to 450 °, and in the case of a deposited film of aluminum oxide or silicon oxide, It is desirable that the film thickness is about 50 to 500 °, more preferably about 100 to 300 °.

  Examples of the method for forming the deposited film include a physical vapor deposition method (PVD method) such as a vacuum deposition method, a sputtering method, and an ion plating method, a plasma chemical vapor deposition method, and a thermochemical method. Chemical vapor deposition methods (Chemical Vapor Deposition method, CVD method) such as a vapor deposition method and a photochemical vapor deposition method can be given.

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

Other Layers The laminate according to the present invention may further include at least one other layer in addition to the above-described layers. When two or more other layers are provided, each may have the same composition or different compositions. Other layers can be formed on one or more of the above layers. Examples of other layers include a printing layer and an adhesive layer. The printing layer can be formed using a conventionally known pigment or dye, and the forming method is not particularly limited. Further, the adhesive layer is an adhesive layer or an adhesive resin layer formed to bond any two layers by lamination. Examples of the laminating adhesive include one-component or two-component curable or non-curable vinyl, (meth) acrylic, polyamide, polyester, polyether, polyurethane, epoxy, rubber, and the like. Other laminating adhesives such as a solvent type, an aqueous type, or an emulsion type can be used. As the coating method of the adhesive, for example, a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a Fonten method, a transfer roll coating method, or another method can be used. As the coating ^{amount, 0.1g / m 2 ~10g / m} 2 ( dry state) position are ^{preferred, 1g / m 2 ~5g / m} 2 ( dry state) position is more preferred.

  Further, a resin layer made of a thermoplastic resin layer is used as the adhesive resin layer. Specifically, as the material of the adhesive resin layer, a low-density polyethylene resin, a medium-density polyethylene resin, a high-density polyethylene resin, a linear low-density polyethylene resin, and an ethylene / α-olefin polymerized using a metallocene catalyst are used. Copolymer resin, ethylene / polypropylene copolymer resin, ethylene / vinyl acetate copolymer resin, ethylene / acrylic acid copolymer resin, ethylene / ethyl acrylate copolymer resin, ethylene / methacrylic acid copolymer resin, Graft polymerization of unsaturated carboxylic acid, unsaturated carboxylic acid, unsaturated carboxylic anhydride, ester monomer to ethylene / methyl methacrylate copolymer resin, ethylene / maleic acid copolymer resin, ionomer resin, polyolefin resin, Or graft copolymerized maleic anhydride to polyolefin resin It can be used sexual resin or the like. These materials can be used alone or in combination of two or more.

  The method for producing the laminate according to the present invention is not particularly limited, and the laminate can be produced by a conventionally known method. In the present invention, a biomass polyolefin resin layer is preferably formed on a paper substrate by extrusion, and more preferably a biomass polyolefin resin layer is formed by co-extrusion. More preferably, the co-extrusion is performed by a T-die method or an inflation method.

  For example, a laminate can be formed by extrusion molding in the following manner. After drying the above-mentioned biomass polyolefin resin composition, it is supplied to a melt extruder heated to a temperature of from the melting point of the polyolefin (Tm) to a temperature of Tm + 70 ° C. to melt the biomass polyolefin resin composition. A laminate can be formed by extruding the material into a sheet shape from a die such as a T-die, and rapidly solidifying the extruded sheet material with a rotating cooling drum or the like. As the melt extruder, a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder or the like can be used according to the purpose.

  The thickness of the laminate obtained as described above is arbitrary depending on the application, but is usually about 5 to 500 μm, preferably about 20 to 300 μm.

  The laminate according to the present invention has a chemical function, an electrical function, a magnetic function, a mechanical function, a friction / wear / lubrication function, an optical function, a thermal function, and a surface function such as biocompatibility. For the purpose, secondary processing can be performed. Examples of secondary processing include embossing, painting, bonding, printing, metallizing (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 may be subjected to lamination (dry lamination or extrusion lamination), bag making, and other post-processing to produce a molded product.

Applications The laminate according to the present invention can be used for packaging products such as packaging containers and packaging bags, sheet molded products such as decorative sheets and trays, laminated films, optical films, resin plates, various label materials, lid materials, and laminated tubes. It can be suitably used for applications, and particularly, packaged products are preferable.

<Other aspects>
The present invention is to provide a laminate comprising a paperboard substrate and a biomass polyolefin resin layer composed of a biomass polyolefin resin composition containing a carbon neutral polyolefin using biomass-derived ethylene. It is another object of the present invention to provide a laminate having a resin layer produced from a raw material obtained from fossil fuels and a laminate of a biomass polyolefin resin which is comparable in physical properties such as mechanical properties.
According to yet another aspect of the present invention,
A paperboard substrate having a basis weight of 100~700g / ^{m 2,}
A laminate comprising: a biomass polyolefin resin layer comprising a biomass polyolefin resin composition containing a biomass-derived polyolefin obtained by polymerizing a monomer containing biomass-derived ethylene is provided.
In still another embodiment of the present invention, it is preferable that the biomass polyolefin resin layer contains 5% by mass or more of the biomass-derived ethylene based on the entire biomass polyolefin resin layer.
In still another aspect of the present invention, the biomass polyolefin resin layer has a first biomass polyolefin resin layer and a second biomass polyolefin resin layer in order from the paperboard substrate side, The biomass polyolefin resin layer contains 5% by mass or more of the biomass-derived ethylene based on the entire first biomass polyolefin resin layer, and the second biomass polyolefin resin layer contains the biomass-derived ethylene in the second biomass. It is preferable that the content is 5% by mass or more based on the whole polyolefin resin layer.
In yet another aspect of the present invention, the ethylene concentration C ₁ of biomass in the first biomass polyolefin resin layer in the second ethylene concentration C ₂ of the biomass-derived biomass polyolefin resin layer, C _1> C It is preferable to satisfy ₂ .
In still another embodiment of the present invention, the monomer may further include fossil fuel-derived ethylene and / or α-olefin.
In still another embodiment of the present invention, the monomer may further include a biomass-derived α-olefin.
In still another aspect of the present invention, the biomass polyolefin resin composition is derived from a fossil fuel-derived polymer obtained by polymerizing a monomer containing fossil fuel-derived ethylene and fossil fuel-derived ethylene and / or α-olefin. It may further include a polyolefin.
In still another embodiment of the present invention, the biomass polyolefin resin composition may include 5 to 90% by mass of the biomass-derived polyolefin and 10 to 95% by mass of the fossil fuel-derived polyolefin.
In still another aspect of the present invention, the α-olefin is preferably butylene, hexene, or octene.
In still another embodiment of the present invention, it is preferable that the polyolefin is polyethylene.
In still another aspect of the present invention, the laminate may further include a non-biomass polyolefin resin layer made of a resin material containing a fossil fuel-derived material.
In still another embodiment of the present invention, the laminate may further include a barrier layer made of an inorganic substance and / or an inorganic oxide.
In still another aspect of the present invention, it is preferable that the biomass polyolefin resin layer is formed by extrusion on the paperboard substrate.
In still another aspect of the present invention, it is preferable that the biomass polyolefin resin layer is formed by co-extrusion.
In still another embodiment of the present invention, it is preferable that the co-extrusion is performed by a T-die method or an inflation method.
In still another aspect of the present invention, there is provided a packaged product comprising the laminate.
A laminate according to still another embodiment of the present invention, a paperboard substrate, a biomass polyolefin resin layer comprising a biomass polyolefin resin composition containing a biomass-derived polyolefin obtained by polymerizing a monomer containing biomass-derived ethylene. , It is possible to realize a carbon-neutral polyolefin resin laminate. Therefore, the amount of fossil fuel used can be significantly reduced as compared with the related art, and the environmental load can be reduced. In addition, the laminate according to still another embodiment of the present invention is comparable to a polyolefin laminate manufactured from a raw material obtained from a conventional fossil fuel in terms of physical properties such as mechanical properties. Laminates can be substituted.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention should not be construed as being limited to the following Examples.

Measurement / Conditions In the following Reference Examples, Reference Comparative Examples, Examples, and Comparative Examples, the degree of biomass is the value of the content of carbon derived from biomass as measured by radioactive carbon (C14).

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

Example 1
Acid-resistant paper (Oji Specialty Paper: acid-resistant BYO-500, basis weight 320 g / m ² ) was used for the paperboard substrate as the body material and bottom material of the paper cup container, and the back surface thereof was subjected to corona treatment. Next, as the core layer on the paperboard substrate side, low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd .: LC701, MFR: 14, density: 0.919) and linear low-density polyethylene derived from biomass (Braskem Co., Ltd.) Resin: SLL3180, MFR: 2.7, density: 0.918, biomass degree: 87%) were dry-blended at 50:50. In addition, a fossil fuel-derived low-density polyethylene resin (manufactured by Nippon Polyethylene Corporation: Novatec LC520, MFR: 3.6, density: 0.923) was prepared as a seal layer. The above-mentioned resin is co-pressed on the corona-treated surface of the paperboard substrate at resin temperatures of 290 ° C. and 320 ° C. (core layer: 20 μm, seal layer: 20 μm), and extrusion-coated at a line speed of 100 m / min. A polyethylene laminate was obtained. The biomass degree of the extruded layer was 22%.

Example 2
As a base material and a bottom material of a paper cup container, a cup base paper (manufactured by Nippon Paper Industries Co., Ltd .: basis weight 220 g / m ² ) is used as a paperboard substrate, and is subjected to corona treatment. 55 parts by mass of density polyethylene (manufactured by Nippon Polyethylene: LC520 (MFR: 3.6, density: 0.923)) and biomass-derived linear low-density polyethylene (manufactured by Braskem: SLL318, MFR: 2.7, density: 0.918, biomass degree: 87%) A resin obtained by dry blending with 45 parts by mass was extruded (25 μm) at a resin temperature of 320 ° C. and extruded and coated at a line speed of 100 m / min to obtain a biomass polyethylene laminate. The biomass degree of the extruded layer was 41%.

Comparative Example 1
An acid-resistant paper (Oji Specialty Paper: acid-resistant BYO-500, basis weight 320 g / m ² ) is used as a paperboard substrate as a body material and a bottom material of the paper cup container, and the back surface is subjected to corona treatment, and then the corona treatment is performed. A fossil fuel-derived low-density polyethylene resin (manufactured by Nippon Polyethylene Corporation: Novatec LC520, MFR: 3.6, density: 0.923) is extruded (40 μm) at a resin temperature of 320 ° C. on a treated surface at a line speed of 100 m / min. Extrusion coating to obtain a non-biomass polyethylene laminate. The biomass degree of the extruded layer was 0%.

Comparative Example 2
As a base material and a bottom material of a paper cup container, a cup base paper (manufactured by Nippon Paper Industries Co., Ltd .: basis weight 220 g / m ² ) is used as a paperboard substrate, and is subjected to corona treatment. Non-biomass polyethylene is extruded at a resin temperature of 320 ° C. (25 μm), extruded at a line speed of 100 m / min, and coated with high density polyethylene (manufactured by Nippon Polyethylene: LC520 (MFR: 3.6, density: 0.923)). The extruded layer had a biomass degree of 0%.

Production of Paper Cup Next, using the laminate produced above, a frusto-conical blank plate for forming the body of the paper cup was punched from the laminate. Next, the above-mentioned blank plate was wound into a cylindrical shape, its both ends were partially overlapped, a frame treatment was performed on the polymerized portion, and the low-density polyethylene resin layer present in the polymerized portion was heated and melted. Subsequently, the body was adhered by pressing with a hot plate or the like to form a body seal portion, and a cylindrical cup body constituting the paper cup was manufactured.

  On the other hand, in the same manner as described above, the laminated body produced above is used, and this is punched into a circular shape to produce a disk constituting the bottom portion, and then the outer peripheral portion of the disk is raised into a cylindrical shape. It was molded to produce a bottom having an upright molded part. Next, after inserting the bottom paper also manufactured in the upper part into the cylindrical cup body manufactured above, the cylindrical cup body and the bottom paper are blown with hot air or the like to the joint portion thereof. The resin layer present at the joint was melted by heating. Subsequently, the tip of the cylindrical cup body is bent inward by the curling mold, and is placed over the upright forming part forming the bottom, and the tip and bottom of the cylindrical cup body are bent. By knurling the overlapping portion with the upright forming portion from the inner diameter side by knurling, the above-mentioned tubular cup body and the bottom are tightly adhered to form a joint, and the tubular cup body of steam is formed. And the bottom of the paper cup.

  Then, the bottom end of the cylindrical cup body is tightly adhered, and the short end on the side opposite to the side on which the joint is formed is curled while bending outward with a curling mold in the same manner as described above. An outward curl was formed to produce a paper cup with a full capacity of 353 cc.

  In Examples 1 and 2 and Comparative Examples 1 and 2, cup molding could be performed without any problem. In addition, these paper cups were destructively inspected and visually checked for any seal abnormality. Both of them confirmed that the paper was peeled off, and that sufficient sealing strength was obtained.

Reference Example 1
On a PET film as a base material, 50 parts by mass of a linear low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Corporation: NH745 (MFR: 8.0, density: 0.913)) as a first layer of co-extrusion, Two layers of resin (20 μm) obtained by dry blending 50 parts by mass of biomass-derived linear low-density polyethylene (manufactured by Braskem: SLL318, MFR: 2.7, density: 0.918, biomass degree: 87%) A low-density polyethylene (LC520 (MFR: 3.6, density: 0.923, 20 μm) manufactured by Nippon Polyethylene Co., Ltd.) derived from fossil fuel was extruded at a resin temperature of 320 ° C. (line speed 100 m / min). A biomass polyethylene laminate was obtained.

Reference Example 2
On a PET film as a base material, a linear low-density polyethylene derived from fossil fuel (NH745 (MFR: 8.0, density: 0.913, 20 μm) manufactured by Nippon Polyethylene Co., Ltd.) In the layer, low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Corporation: LC520 (MFR: 3.6, density: 0.923, 20 μm)) is extruded together at a resin temperature of 300 ° C. (line speed 100 m / min), A non-biomass polyethylene laminate was obtained.

Evaluation of Film From the laminate obtained in Reference Example 1 and Reference Example 2, the PET film as the substrate was peeled off, and film samples A and B were obtained, respectively. From each of the MD direction and the CD direction of each of the obtained film samples, a test piece was cut out to a width of 15 mm and a length of 200 mm, and was subjected to a tensile tester (Tensilon RTC-125A, manufactured by Orientec) at a temperature of 23 ° C. The strength and elongation of the test piece were measured in an environment with a humidity of 50 RH%. Further, each film sample was heat-sealed at a sealing temperature of 150 ° C., a sealing pressure of 30 N / cm ² , and a sealing time of 1 second, and the sealing strength (N / N) was measured using a tensile tester (Tensilon RTC-125A, manufactured by Orientec). 15 mm).

The above evaluation results were as shown in Table 1. The film samples A and B did not show any significant difference in all evaluation items. That is, the biomass resin film (A) was comparable to the non-biomass resin film (B) in physical properties such as mechanical properties.

Example 3
For liquid paper container applications, milk carton base paper (Clearwater: basis weight 320 g / m ² ) is used as the paper base material, the surface of which is subjected to a frame treatment, and low density polyethylene derived from fossil fuel (Japan). Polyethylene Co., Ltd .: LC520 (MFR: 3.6, density: 0.923) was extruded (20 μm) at a resin temperature of 320 ° C. Subsequently, the back side was subjected to a frame treatment, and then the frame-treated surface On the (back side), 50 parts by mass of linear low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Corporation: NH745 (MFR: 8.0, density: 0.913)) and biomass-derived first layer in the first layer of co-extrusion A tree obtained by dry blending 50 parts by mass of a linear low-density polyethylene (manufactured by Braskem: SLL318, MFR: 2.7, density: 0.918, biomass degree: 87%). In the second layer, low-density polyethylene (LC520 (MFR: 3.6, density: 0.923, 20 μm) manufactured by Nippon Polyethylene Co., Ltd.) is extruded into the second layer at a resin temperature of 300 ° C. ( (Line speed: 100 m / min) to obtain a biomass polyethylene laminate.The biomass degree of the entire laminate excluding the paper substrate was 15%.

Comparative Example 3
Milk carton base paper (clearwater: 320 g / m ² ) is used as the paperboard substrate, and the surface of the paperboard is subjected to a frame treatment. Then, low-density polyethylene derived from fossil fuel (LC520 (manufactured by Nippon Polyethylene): (MFR: 3.6, density: 0.923) was extruded (20 μm) at a resin temperature of 320 ° C. Subsequently, a frame treatment was also performed on the back surface side. The first layer of co-extrusion is a linear low-density polyethylene derived from fossil fuel (NH745 (MFR: 8.0, density: 0.913, 20 μm) manufactured by Nippon Polyethylene Co., Ltd.), and the second layer is a low-density polyethylene derived from fossil fuel. Both density polyethylene (manufactured by Nippon Polyethylene Corporation: LC520 (MFR: 3.6, density: 0.923, 20 μm)) was extruded at a resin temperature of 300 ° C. (line speed 100 m / min) It was obtained ion mass polyethylene laminate.

Example 4
As cold long-term storage type liquid feeding container applications such as mainly sake, the frame processing in the non-laminate surface of the base paper of the paper substrate (Clearwater Inc. 400 g / m ² low density polyethylene 20 g / m already ² extrusion laminating the printed surface) went. An aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 7 μm) and a PET film derived from fossil fuel (manufactured by Toyobo Co., Ltd .: E5100, 12 μm) are dry-laminated (manufactured by DIC: main agent LX-703A / curing agent KR-90) on this frame treated surface. The resulting film was extrusion-laminated with an ethylene-acrylic acid copolymer (manufactured by Du Pont-Mitsui Polychemicals Ltd .: Nuclell N0908C, 20 μm) and bonded together. Thereafter, a polyester polyol / isocyanate two-liquid curing type anchor agent (A3210 / AT3075, manufactured by Mitsui Takeda Polychemicals) is coated on the PET surface of the dry laminate film, and then low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Corporation: 50 parts by mass of LC520 (MFR: 3.6, density: 0.923) and biomass-derived linear low-density polyethylene (manufactured by Braskem: SLL318, MFR: 2.7, density: 0.918, biomass degree: 87) %) And a low-density polyethylene film (manufactured by Dainippon Printing: SKL, density: 0.923) at a line speed of 100 m / min. , 40 μm) to obtain a biomass polyethylene laminate. The biomass degree of the entire laminate except for was 6%.

Example 5
As cold long-term storage type liquid feeding container applications such as mainly sake, the frame processing in the non-laminate surface of the base paper of the paper substrate (Clearwater Inc. 400 g / m ² low density polyethylene 20 g / m already ² extrusion laminating the printed surface) went. A dry laminate (manufactured by DIC: main agent LX-703A / curing agent KR-90) of an aluminum foil (manufactured by TOYO ALUMINUM, 7 μm) and a PET film derived from biomass (manufactured by TOYOBO: DE024, 12 μm) was applied to the frame treated surface. The resulting film was extrusion-laminated with an ethylene-acrylic acid copolymer (manufactured by Du Pont-Mitsui Polychemicals, Inc .: Nuclell N0908C, 20 μm) and bonded together. Thereafter, a polyester polyol / isocyanate two-liquid curing type anchor agent (A3210 / AT3075, manufactured by Mitsui Takeda Polychemicals) is coated on the PET surface of the dry laminate film, and then low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Corporation: 50 parts by mass of LC520 (MFR: 3.6, density: 0.923) and biomass-derived linear low-density polyethylene (manufactured by Braskem: SLL318, MFR: 2.7, density: 0.918, biomass degree: 87) %) And a low-density polyethylene film (manufactured by Dainippon Printing: SKL, density: 0.923) at a line speed of 100 m / min. , 40 μm) to obtain a biomass polyethylene laminate. The biomass degree of the whole laminate except for was 9%.

Comparative Example 4
As cold long-term storage type liquid feeding container applications such as mainly sake, the frame processing in the non-laminate surface of the base paper of the paper substrate (Clearwater Inc. 400 g / m ² low density polyethylene 20 g / m already ² extrusion laminating the printed surface) went. An aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 7 μm) and a PET film derived from fossil fuel (manufactured by Toyobo Co., Ltd .: E5100, 12 μm) are dry-laminated (manufactured by DIC: main agent LX-703A / curing agent KR-90) on this frame treated surface. The resulting film was extrusion-laminated with an ethylene-acrylic acid copolymer (manufactured by Du Pont-Mitsui Polychemicals Ltd .: Nuclell N0908C, 20 μm) and bonded together. Thereafter, a polyester polyol / isocyanate two-liquid curing type anchor agent (A3210 / AT3075, manufactured by Mitsui Takeda Polychemicals) is coated on the PET surface of the dry laminate film, and then low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Corporation: LC520 (MFR: 3.6, density: 0.923) is extruded (20 μm) at a resin temperature of 320 ° C., and a low density polyethylene film (manufactured by Dainippon Printing: SKL, (Density: 0.923, 40 μm) to obtain a biomass polyethylene laminate.The biomass degree of the entire laminate excluding the paper base was 0%.

Comparative Example 5
Mainly used for long-term storage at room temperature such as sake, etc. for liquid paper containers at room temperature. Polyethylene imine is used for the non-laminated surface of the base paper (clear water, 400 g / m ² printed surface, low density polyethylene 20 g / m ² extruded and laminated) An anchor coat was performed. A film in which an aluminum foil (manufactured by Toyo Aluminum Co., 7 μm) and a PET film derived from biomass (manufactured by Toyobo Co., DE024, 12 μm) are dry-laminated (manufactured by DIC: main agent LX-703A / hardener KR-90). Was extruded and laminated with an ethylene-acrylic acid copolymer (manufactured by Du Pont-Mitsui Polychemicals Ltd .: Nuclell N0908C, 20 μm). Thereafter, a polyester polyol / isocyanate two-liquid curing type anchor agent (A3210 / AT3075, manufactured by Mitsui Takeda Polychemicals) is coated on the PET surface of the dry laminate film, and then low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Corporation: LC520 (MFR: 3.6, density: 0.923) is extruded (20 μm) at a resin temperature of 320 ° C., and a low density polyethylene film (manufactured by Dainippon Printing: SKL, (Density: 0.923, 40 μm) to obtain a biomass polyethylene laminate.The biomass degree of the entire laminate excluding the paper base was 3%.

Container strength evaluation
Using the cartons prepared in Example 4 and Comparative Example 4, water was filled and molded using a liquid paper container filling machine (DR-10) manufactured by Dai Nippon Printing Co., Ltd. Single compression strength measurement was performed in two directions (all sideways). As shown in Table 2, no significant difference was found between the biomass-derived product and the fossil fuel-derived product.

Sealability evaluation (filling machine verification)
Using the cartons prepared in Example 4 and Comparative Example 4, after filling with water using a liquid paper container filling machine (DR-10) manufactured by Dai Nippon Printing Co., Ltd., the sealing performance of the top and the bottom was compared. . The sealability was evaluated by enclosing a permeate and visually observing the following criteria. As shown in Table 3, no significant difference was found between the biomass-derived product and the fossil fuel-derived product.
Sealability evaluation criteria ：: Good.
Δ: There was no sealing loss, but there was a tendency to come off.
×: A state in which seal missing was confirmed.

DESCRIPTION OF SYMBOLS 10 Laminated body 11 Paper base material 12 Biomass polyolefin resin layer 20 Laminated body 21 Paperboard base material 22 First biomass polyolefin resin layer 23 Second biomass polyolefin resin layer

Claims (6)

Paper base material,
Biomass polyolefin resin layer comprising a biomass polyolefin resin composition comprising a biomass-derived polyolefin obtained by polymerizing a monomer containing biomass-derived ethylene,
A non-biomass polyolefin resin layer made of a resin material containing a fossil fuel-derived raw material,
, In this order, a laminate for packaging products.   The laminate for a packaging product according to claim 1, wherein the biomass polyolefin resin layer contains biomass-derived polyethylene obtained by polymerizing a monomer containing biomass-derived ethylene.   3. The biomass polyolefin resin layer according to claim 1, wherein the fossil fuel-derived ethylene and the fossil fuel-derived polyethylene obtained by polymerizing a fossil fuel-derived ethylene and / or an α-olefin monomer are further included in the biomass polyolefin resin layer. 4. Laminates for packaging products.   The laminate for a packaging product according to any one of claims 1 to 3, wherein the biomass polyolefin resin layer contains 5% by mass or more of ethylene derived from the biomass based on the entire biomass polyolefin resin layer.   The packaged product laminate according to any one of claims 1 to 4, further comprising a barrier layer containing an inorganic substance.   A packaged product comprising the packaged product laminate according to any one of claims 1 to 5.

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