JP6136272B2 - Laminate with a resin layer derived from biomass - Google Patents

Description

  The present invention relates to a laminate having a biomass-derived resin layer, and more specifically, a biomass polyolefin resin composition comprising a paperboard substrate and a biomass-derived polyolefin formed by polymerizing a monomer containing ethylene derived from biomass. It is related with the laminated body which has a biomass polyolefin resin layer which consists of a thing.

  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 inventors focused on ethylene, which is a raw material for polyolefin laminates, and instead of ethylene obtained from conventional fossil fuels, a laminate having a polyolefin polyolefin polyolefin resin layer of polyolefin using biomass-derived ethylene as its raw material is The present inventors have obtained the knowledge that a laminate of polyolefin resin produced using ethylene obtained from a conventional fossil fuel and a product inferior in 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 paperboard substrate and a biomass polyolefin resin layer comprising a biomass polyolefin resin composition containing carbon neutral polyolefin using biomass-derived ethylene. Then, it is providing the laminated body of the biomass polyolefin resin which is inferior in terms of physical properties, such as the laminated body which has the resin layer manufactured from the raw material obtained from the conventional fossil fuel, and a mechanical characteristic.

In an embodiment of the present invention,
A paperboard substrate having a basis weight of 100-700 g / m ² ;
There is provided a laminate comprising a biomass polyolefin resin layer comprising a biomass polyolefin resin composition comprising a biomass-derived polyolefin obtained by polymerizing a monomer containing ethylene derived from biomass.

  In the aspect of this invention, it is preferable that the said biomass polyolefin resin layer contains 5 mass% or more of said biomass-derived ethylene with respect to the said biomass polyolefin resin layer whole.

  In an aspect of the present invention, 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, and the first biomass polyolefin resin layer Comprises 5% by mass or more of the biomass-derived ethylene with respect to the entire first biomass polyolefin resin layer, and the second biomass polyolefin resin layer contains the biomass-derived ethylene in the entire second biomass polyolefin resin layer. It is preferable that 5% by mass or more is contained.

In the embodiment of the present invention, the biomass-derived ethylene concentration C ₁ in the first biomass polyolefin resin layer and the biomass-derived ethylene concentration C _{2 in} the second biomass polyolefin resin layer satisfy C ₁ > C _2. Is preferred.

  In an embodiment of the present invention, the monomer may further contain ethylene and / or α-olefin derived from fossil fuel.

  In the aspect of the present invention, the monomer may further contain an α-olefin derived from biomass.

  In an aspect of the present invention, the biomass polyolefin resin composition further includes a fossil fuel-derived polyolefin obtained by polymerizing a fossil fuel-derived ethylene and a fossil-fuel-derived ethylene and / or α-olefin monomer. But you can.

  In the aspect 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 the aspect of the present invention, the α-olefin is preferably butylene, hexene, or octene.

In the embodiment of the present invention, the polyolefin is preferably polyethylene.

  In the 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 raw material.

  In the aspect of this invention, the said laminated body may further have a barrier layer which consists of an inorganic substance and / or an inorganic oxide.

  In the aspect of the present invention, it is preferable that the biomass polyolefin resin layer is formed on the paperboard substrate by extrusion molding.

  In the aspect of the present invention, the biomass polyolefin resin layer is preferably formed by coextrusion molding.

  In the aspect of the present invention, the coextrusion molding is preferably performed by a T-die method or an inflation method.

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

  The laminate according to the present invention comprises a paperboard substrate and a 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 laminate of neutral polyolefin resin can be realized. Therefore, the amount of fossil fuel used can be greatly reduced compared to the conventional case, 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 laminate produced from a raw material obtained from a conventional fossil fuel. Can do.

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.

  In the present invention, the “biomass polyolefin resin composition” and the “biomass polyolefin resin layer” are those using a raw material derived from biomass at least in part as a raw material, and all the raw materials are derived from biomass. Does not mean.

Laminate The laminate according to the present invention comprises a paperboard substrate and a biomass polyolefin resin layer. By having a biomass polyolefin resin layer, the laminate can realize a laminate of a carbon neutral polyolefin resin. Therefore, the amount of fossil fuel used can be greatly reduced compared to the conventional case, 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.

  A schematic cross-sectional view of an example of a laminate according to the present invention is shown in FIGS. A 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 laminated body 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 the biomass polyolefin resin layer 23 in this order. Hereinafter, each layer which comprises a laminated body is demonstrated.

Paperboard Substrate In the present invention, the paperboard substrate functions as a base material layer, and needs to have a strength that can withstand the process of laminating a biomass polyolefin resin layer by extrusion molding. 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 as a whole is a target, but from the viewpoint of safety, ivory paper using natural pulp, milk carton base paper, cup base paper and the like are preferable.

  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 6-9 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.

Biomass polyolefin resin layer In the present invention, the biomass polyolefin resin layer is preferably 5% by mass or more, more preferably 5 to 95% by mass, more preferably 25 to 95% by mass of the following biomass-derived ethylene with respect to the entire biomass polyolefin resin layer. It contains 75% by mass. The biomass polyolefin resin layer may be composed of at least two 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 sealing 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.

1st biomass polyolefin resin layer In this invention, the 1st biomass polyolefin resin layer may fulfill | perform the function as a core layer of a laminated body. By having the core layer, the laminate can exhibit excellent flexibility without breaking.

  The first biomass polyolefin resin layer is preferably 5% by mass or more, more preferably 5 to 95% by mass, more preferably 25 to 75% by mass, of ethylene derived from biomass with respect to the entire first biomass polyolefin resin layer. Most preferably, it comprises 40 to 75%. If the concentration of ethylene derived from biomass in the first biomass polyolefin resin layer is 5% by mass or more, the amount of fossil fuel used can be reduced compared to the conventional, and a carbon neutral polyolefin resin laminate is realized. it can.

The first biomass polyolefin resin layer is preferably 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 defined in Method A of JIS K7112-1980 after 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. Moreover, if the first biomass polyolefin resin layer density 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 minutes, preferably 3 to 25 g / 10 minutes, more preferably 4 to 20 g / 10 minutes. 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 first biomass polyolefin resin layer is 1 g / 10 min or more, the extrusion load during the molding process can be reduced. Moreover, if MFR of a biomass polyolefin resin composition is 30 g / 10min or less, the mechanical strength of a 1st biomass polyolefin resin layer can be raised.

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

2nd biomass polyolefin resin layer In this invention, the 2nd biomass polyolefin resin layer may fulfill | perform the function as a sealing layer of a laminated body. By having the heat seal layer, the laminate can be firmly bonded without using an adhesive or the like when laminating on another resin film.

  The second biomass polyolefin resin layer preferably contains biomass-derived ethylene in an amount of 5% by mass or more, more preferably 5 to 95% by mass, and even more preferably 25 to 75% by mass with respect to the entire second biomass polyolefin resin layer. It is what. 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 one, 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 defined in Method A of JIS K7112-1980 after 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. Moreover, if the density of a 2nd biomass polyolefin resin layer is 0.925 g / cm < ³ > or less, transparency and mechanical strength of a 2nd biomass polyolefin resin layer can be improved.

  The second biomass polyolefin resin layer has a melt flow rate (MFR) of 1 to 30 g / 10 minutes, preferably 3 to 25 g / 10 minutes, more preferably 4 to 20 g / 10 minutes. 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 second biomass polyolefin resin layer is 1 g / 10 min or more, the extrusion load during the molding process can be reduced. Moreover, if the MFR of the biomass polyolefin resin composition is 30 g / 10 min 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 regarding density, thickness, MFR, and biomass degree (ethylene concentration derived from biomass). Preferably there is.

In the present invention, it is preferable that the density d ₁ of the first biomass polyolefin resin layer and the density d _{2 of} the second biomass polyolefin resin layer satisfy d ₁ > d ₂ . This is because the first biomass polyolefin resin layer functions as a core layer and therefore requires rigidity, and the second biomass polyolefin resin layer functions as a heat seal layer and thus requires flexibility.

In the present invention, it is preferable that the thickness t ₁ of the first biomass polyolefin resin layer and the thickness t _{2 of} the second biomass polyolefin resin layer satisfy t ₁ > t ₂ . This is because the first biomass polyolefin resin layer functions as a core layer and therefore requires a thickness, and the second biomass polyolefin resin layer functions as a heat seal layer, so that the thickness is not 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 therefore requires rigidity, and the second biomass polyolefin resin layer functions as a heat seal layer and thus 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 that is a raw material for 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 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. 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 viewpoints of mass balance and heat balance.

  By performing the dehydration reaction of ethanol in this way, a mixed part of ethylene, water and a small amount of unreacted ethanol is obtained. Since ethylene is a gas at a temperature of about 5 MPa or less at normal temperature, gas and liquid separation is performed from these mixed parts. 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.

Biomass polyolefin In the present invention, biomass-derived polyolefin is obtained by polymerizing monomers containing ethylene derived from biomass. It is preferable to use what was obtained by said manufacturing method 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 the raw material of the polyolefin derived from biomass may further contain ethylene and / or α-olefin derived from fossil fuel, or may further include α-olefin derived from biomass.

  The α-olefin is not particularly limited, but can usually be one having 3 to 20 carbon atoms, and is preferably butylene, hexene or octene. This is because if it is butylene, hexene or octene, it can be produced by polymerization of ethylene which is a biomass-derived raw material. In addition, by including such an α-olefin, the polymerized polyolefin has an alkyl group as a branched structure, and therefore can be more flexible than a simple linear one.

  The 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-derived ethylene concentration in the polyolefin (hereinafter sometimes referred to as “biomass degree”) is a value obtained by measuring the content of biomass-derived carbon by measurement of radioactive carbon (C14). Since carbon dioxide in the atmosphere contains C14 at a constant rate (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, if all the biomass-derived ethylene is used as the polyolefin raw material, the biomass-derived ethylene concentration is 100%, and the biomass degree of the biomass-derived polyolefin is 100%. In addition, the biomass-derived ethylene concentration in the fossil fuel-derived polyolefin produced only from the fossil fuel-derived raw material is 0%, and the biomass degree of the fossil fuel-derived polyolefin is 0%.

  In the present invention, the biomass-derived polyolefin and the biomass-derived resin layer need not have a biomass degree of 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.

  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.

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

Biomass polyolefin resin composition In this invention, a biomass polyolefin resin composition contains said polyolefin as a main component. The biomass polyolefin resin composition preferably comprises 5 mass% or more, more preferably 5 to 95 mass%, still more preferably 25 to 75 mass%, of ethylene derived from biomass with respect to the entire biomass polyolefin resin composition. is there. If 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 one, and a carbon neutral polyolefin laminate can be realized.

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

  The biomass polyolefin resin composition may further include a fossil fuel-derived polyolefin obtained by polymerizing a monomer containing ethylene derived from fossil fuel and ethylene derived from fossil fuel and / or α-olefin. That is, in the present invention, the biomass polyolefin resin composition may be a mixture of biomass-derived polyolefin and 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 aspect of the present invention, the biomass polyolefin resin composition is preferably 5 to 90% by mass, more preferably 25 to 75% by mass of polyolefin derived from biomass, preferably 10 to 95% by mass, more preferably 25%. -75 mass% polyolefin derived from fossil fuel. Even when the biomass polyolefin resin composition of such a mixture is used, the concentration of ethylene derived from biomass may be within the above range as the whole biomass polyolefin resin composition.

  In the production process of the above-described biomass polyolefin resin composition, or in the produced biomass polyolefin resin composition, various additives other than the main component polyolefin may be added as long as the characteristics are not impaired. Good. 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 to 20% by mass, preferably 1 to 10% by mass, based on the whole 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 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 formation method thereof 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, puncture resistance, and other physical properties can be imparted or improved. The laminate may have two or more non-biomass polyolefin resin layers. When having two or more non-biomass polyolefin resin layers, each may have the same composition or a different composition.

  Non-biomass polyolefin resin layers include, 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. A resin such as a copolymer, an ethylene-methacrylic acid copolymer, an ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-methyl methacrylate copolymer, or an ionomer can be used. These resins may be formed by an extrusion laminating method, or may be laminated in advance as a film formed by a T-die method or an inflation method by a heat-resistant substrate layer and a dry laminating or extrusion laminating method. .

  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 / Metaxylylenediamine nylon 6 co-extrusion co-stretched film or polypropylene / ethylene-vinyl alcohol copolymer co-extrusion co-stretched film or the like, or a composite film obtained by laminating two or more of these films may be used.

Barrier layer The laminate according to the present invention may further comprise a 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, about 50 to 2000 mm, preferably about 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, a film thickness of about 50 to 600 mm, more preferably about 100 to 450 mm, is desirable, 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.

  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 or the like is preferable from the viewpoint of gas barrier properties that prevent the transmission of oxygen gas, water vapor, and the like, and light shielding properties that prevent the transmission of visible light, ultraviolet light, and the like.

Other Layers In addition to the above layers, the laminate according to the present invention may further include at least one other layer. When two or more other layers are included, each may have the same composition or a different composition. Other layers can be formed on any one or more of the above layers. Examples of other layers include a printing layer and an adhesive layer. A printing layer can be formed using a conventionally well-known pigment and dye, The formation method is not specifically limited. Further, the adhesive layer is an adhesive layer or an adhesive resin layer formed in order to bond any two layers by lamination. As an adhesive for laminating, for example, one or two-component cured or non-cured vinyl type, (meth) acrylic type, polyamide type, polyester type, polyether type, polyurethane type, epoxy type, rubber type, Other adhesives such as solvent type, aqueous type, and emulsion type can be used. Examples of the coating method for the 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. 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.

  In addition, a resin layer made of a thermoplastic resin layer is used as the adhesive resin layer. Specifically, the material of the adhesive resin layer includes a low density polyethylene resin, a medium density polyethylene resin, a high density polyethylene resin, a linear low density polyethylene resin, and ethylene / α-olefin polymerized using a metallocene catalyst. 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 acid anhydride, ester monomer to ethylene / methyl methacrylate copolymer resin, ethylene / maleic acid copolymer resin, ionomer resin, polyolefin resin, Or graft copolymerized resin, maleic anhydride to polyolefin resin It can be used sexual resin or the like. These materials can be used alone or in combination.

  The manufacturing method of the laminated body by this invention is not specifically limited, It can manufacture by a conventionally well-known method. In the present invention, it is preferable to form a biomass polyolefin resin layer on a paper substrate by extrusion molding, and it is more preferable that the biomass polyolefin resin layer is formed by coextrusion molding. More preferably, the coextrusion is performed by a T-die method or an inflation method.

  For example, the laminate can be formed by extrusion molding according to the following method. After drying the above-described biomass polyolefin resin composition, the biomass polyolefin resin composition is melted by supplying it to a melt extruder heated to a temperature not lower than the melting point of polyolefin (Tm) to Tm + 70 ° C. A laminated body can be formed by extruding a sheet from a die such as a T-die on the material and quenching and solidifying the extruded sheet 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 depending on 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 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.

Applications Laminates according to the present invention are packaged 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 used suitably for a use, and a packaged product is particularly preferable.

  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 / Conditions In the following Reference Examples, Reference Comparative Examples, Examples, and Comparative Examples, the biomass degree 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 type: Full flight L / D: 28
T die: 11S type straight manifold T die effective opening length: 560mm

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

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

Comparative Example 1
As the body and bottom material of the paper cup container, acid-resistant paper (made by Oji Specialty Paper: acid-resistant BYO-500, basis weight 320 g / m ² ) is used for the paperboard substrate, and the corona treatment is applied to the back surface thereof, and then the corona Fossil fuel-derived low density polyethylene resin (manufactured by Nippon Polyethylene Co., Ltd .: Novatec LC520, MFR: 3.6, density: 0.923) is extruded at a resin temperature of 320 ° C. (40 μm), and the line speed is 100 m / min. And non-biomass polyethylene laminate was obtained by extrusion coating. The biomass degree of the extruded layer was 0%.

Comparative Example 2
A cup base paper (manufactured by Nippon Paper Industries Co., Ltd .: basis weight 220 g / m ² ) is used as the base material and bottom material of the paper cup container, and after corona treatment, low fossil fuel-derived surface is applied to the corona treatment surface. Density polyethylene (manufactured by Nippon Polyethylene Co., Ltd .: LC520 (MFR: 3.6, density: 0.923) was extruded at a resin temperature of 320 ° C. (25 μm), extrusion coated at a line speed of 100 m / min, and non-biomass polyethylene A laminate was obtained, and the extruded layer had a biomass degree of 0%.

Preparation of paper cup Next, the laminated body manufactured above was used, and the truncated cone-shaped blank board which makes the trunk | drum of a paper cup was punched out from the laminated body. Next, the blank plate was wound into a cylindrical shape, both end portions thereof were partially overlapped, flame treatment was performed on the polymerization portion, and the low density polyethylene resin layer present in the polymerization portion was heated and melted. Then, it pressed with the hot plate etc. and performed cylinder sticking, the cylinder seal part was formed, and the cylindrical cup trunk part which comprises a paper cup was manufactured.

  On the other hand, similarly to the above, the laminate manufactured above is used, and this is punched into a circular shape to manufacture a disk constituting the bottom, and then the outer periphery of the disk is raised up in a cylindrical shape. Molded to produce a bottom with an upright molded part. Next, after inserting the bottom paper manufactured in the same manner into the cylindrical cup body manufactured above, the cylindrical cup body and the bottom paper are blown with hot air or the like on the joint portion. The resin layer present at the joint was melted by heating. Subsequently, the tip of the cylindrical cup body is bent inward by a curling die and placed on the upright molding part constituting the bottom, so that the tip and the bottom of the cylindrical cup body are By knurling the overlapping part with the upright molded part from the inner diameter side by knurling, the cylindrical cup body part and the bottom part are closely bonded to form a joint part, and a steam cylindrical cup body part And a bottom of the paper cup was formed.

  After that, the bottom end of the cylindrical cup barrel is tightly bonded, and the tip short part opposite to the side where the joint is formed is curled outwardly by the curling die in the same manner as above, and the upper end A paper cup having a full capacity of 353 cc was manufactured by forming an outward curl portion.

  In both Examples 1 and 2 and Comparative Examples 1 and 2, cup molding could be carried out without problems. Moreover, when these paper cups were destructively inspected and visually checked for seal abnormality, paper peeling phenomenon was confirmed in both cases, and it was confirmed that sufficient seal strength was obtained.

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

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

Evaluation of Film From the laminates obtained in Reference Example 1 and Reference Example 2, the PET film as a base material was peeled to obtain film samples A and B, respectively. Each of the obtained film samples was cut into a width of 15 mm and a length of 200 mm from each of the MD direction and the CD direction to obtain a test piece, and the temperature was 23 ° C. using a tensile tester (Tensilon RTC-125A, manufactured by Orientec Corp.). Under the environment of humidity 50RH%, the strength of the test piece was measured. In addition, each film sample was heat sealed at a seal temperature of 150 ° C., a seal pressure of 30 N / cm ² , and a seal time of 1 second, and using a tensile tester (Tensilon RTC-125A, manufactured by Orientec), the seal strength (N / 15 mm).

The evaluation results were as shown in Table 1. Film samples A and B were not significantly different in all evaluation items. That is, the biomass resin film (A) was not inferior in terms of physical properties such as mechanical properties compared to the non-biomass resin film (B).

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

Comparative Example 3
A milk carton base paper (made by Clearwater: basis weight 320 g / m ² ) was used for the paperboard substrate, and the surface side was subjected to frame treatment, and then low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd .: LC520 ( (MFR: 3.6, density: 0.923) was extruded at a resin temperature of 320 ° C. (20 μm) Subsequently, the frame processing was performed on the back surface side, and then this frame processing surface (back surface side) Linear low density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd .: NH745 (MFR: 8.0, density: 0.913, 20 μm) in the first layer of coextrusion, and low in fossil fuel derived from the second layer. Density polyethylene (manufactured by Nippon Polyethylene Co., Ltd .: LC520 (MFR: 3.6, density: 0.923, 20 μm) was extruded at a resin temperature of 300 ° C. (line speed 100 m / min), non- It was obtained ion mass polyethylene laminate.

Example 4
Mainly used for normal temperature long-term storage type liquid paper containers such as sake, etc. Frame processing is applied to the non-laminated surface of base paper (clear water 400 g / m ² printed surface and low density polyethylene 20 g / m ² extruded laminated) went. On this frame treated surface, an aluminum foil (Toyo Aluminum Co., Ltd., 7 μm) and a fossil fuel-derived PET film (Toyobo Co., Ltd .: E5100, 12 μm) are dry-laminated (DIC manufactured: main agent LX-703A / curing agent KR-90). ) Was laminated by extrusion laminating an ethylene-acrylic acid copolymer (Mitsui DuPont Polychemical Co., Ltd .: Nucleel N0908C, 20 μm). Then, after coating the PET surface of the dry laminate film with a polyester polyol / isocyanate two-component curable anchor agent (Mitsui Takeda Polychemical Co., Ltd .: A3210 / AT3075), low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd .: LC520 (MFR: 3.6, density: 0.923) 50 parts by mass and biomass-derived linear low density polyethylene (manufactured by Braskem: SLL318, MFR: 2.7, density: 0.918, biomass degree: 87) %) 50 parts by mass dry-blended, extruded at a resin temperature of 320 ° C. (20 μm), and at a line speed of 100 m / min, a low-density polyethylene film (Dai Nippon Printing Co., Ltd .: SKL, density: 0.923). , 40 μm) to obtain a biomass polyethylene laminate. The biomass degree of the whole laminated body excluding was 6%.

Example 5
Mainly used for normal temperature long-term storage type liquid paper containers such as sake, etc. Frame processing is applied to the non-laminated surface of base paper (clear water 400 g / m ² printed surface and low density polyethylene 20 g / m ² extruded laminated) went. On this frame-treated surface, an aluminum foil (Toyo Aluminum Co., 7 μm) and a biomass-derived PET film (Toyobo Co., Ltd .: DE024, 12 μm) are dry-laminated (DIC manufactured: main agent LX-703A / curing agent KR-90). The resulting film was laminated by extrusion lamination of an ethylene-acrylic acid copolymer (Mitsui DuPont Polychemical Co., Ltd .: Nucleel N0908C, 20 μm). Then, after coating the PET surface of the dry laminate film with a polyester polyol / isocyanate two-component curable anchor agent (Mitsui Takeda Polychemical Co., Ltd .: A3210 / AT3075), low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd .: LC520 (MFR: 3.6, density: 0.923) 50 parts by mass and biomass-derived linear low density polyethylene (manufactured by Braskem: SLL318, MFR: 2.7, density: 0.918, biomass degree: 87) %) 50 parts by mass dry-blended, extruded at a resin temperature of 320 ° C. (20 μm), and at a line speed of 100 m / min, a low-density polyethylene film (Dai Nippon Printing Co., Ltd .: SKL, density: 0.923). , 40 μm) to obtain a biomass polyethylene laminate. The biomass degree of the whole laminated body excluding was 9%.

Comparative Example 4
Mainly used for normal temperature long-term storage type liquid paper containers such as sake, etc. Frame processing is applied to the non-laminated surface of base paper (clear water 400 g / m ² printed surface and low density polyethylene 20 g / m ² extruded laminated) went. On this frame treated surface, an aluminum foil (Toyo Aluminum Co., Ltd., 7 μm) and a fossil fuel-derived PET film (Toyobo Co., Ltd .: E5100, 12 μm) are dry-laminated (DIC manufactured: main agent LX-703A / curing agent KR-90). ) Was laminated by extrusion laminating an ethylene-acrylic acid copolymer (Mitsui DuPont Polychemical Co., Ltd .: Nucleel N0908C, 20 μm). Then, after coating the PET surface of the dry laminate film with a polyester polyol / isocyanate two-component curable anchor agent (Mitsui Takeda Polychemical Co., Ltd .: A3210 / AT3075), low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd .: LC520 (MFR: 3.6, density: 0.923) was extruded at a resin temperature of 320 ° C. (20 μm), and at a line speed of 100 m / min, a low density polyethylene film (Dai Nippon Printing Co., Ltd .: SKL, Density: 0.923, 40 μm) to obtain a biomass polyethylene laminate, and the biomass degree of the whole laminate excluding the paper substrate was 0%.

Comparative Example 5
Mainly used for normal temperature long-term storage type liquid paper containers such as sake, etc. With base paper of paper base (clear water 400g / m ² printed surface low density polyethylene 20g / m ² extruded laminated) with non-laminated surface by polyethyleneimine Anchor coating was performed. A film obtained by dry-lamination (manufactured by DIC: main agent LX-703A / curing agent KR-90) of an aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 7 μm) and a biomass-derived PET film (manufactured by Toyobo Co., Ltd .: DE024, 12 μm). Were laminated by extrusion lamination of an ethylene-acrylic acid copolymer (Mitsui DuPont Polychemical Co., Ltd .: Nucleel N0908C, 20 μm). Then, after coating the PET surface of the dry laminate film with a polyester polyol / isocyanate two-component curable anchor agent (Mitsui Takeda Polychemical Co., Ltd .: A3210 / AT3075), low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd .: LC520 (MFR: 3.6, density: 0.923) was extruded at a resin temperature of 320 ° C. (20 μm), and at a line speed of 100 m / min, a low density polyethylene film (Dai Nippon Printing Co., Ltd .: SKL, Density: 0.923, 40 μm) to obtain a biomass polyethylene laminate, and the biomass degree of the whole laminate excluding the paper base was 3%.

Container strength evaluation
Using the carton produced in Example 4 and Comparative Example 4, after filling with water and molding using a liquid paper container filling machine (DR-10) manufactured by Dai Nippon Printing Co., Ltd., these measurement samples were placed vertically and horizontally (in the mouth Single unit compressive strength measurement was performed in two directions (all lateral directions). As shown in Table 2, no significant difference was observed between the biomass-derived product and the fossil fuel-derived product.

Sealability evaluation (verification of filling machine)
Using the cartons prepared in Example 4 and Comparative Example 4, the top and bottom sealing properties were compared after water-filling molding with a liquid paper container filling machine (DR-10) manufactured by Dai Nippon Printing Co., Ltd. . The sealing property was evaluated by enclosing an osmotic solution and visually in accordance with the following criteria. As shown in Table 3, no significant difference was observed between the biomass-derived product and the fossil fuel-derived product.
Sealing evaluation criteria : Good.
(Triangle | delta): It was in the state which has the tendency which falls out, although there is no missing seal.
X: The state where seal omission 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 1st biomass polyolefin resin layer 23 2nd biomass polyolefin resin layer

Claims (18)

A paperboard substrate having a basis weight of 100-700 g / m ² ;
A biomass polyolefin resin layer comprising a biomass polyolefin resin composition comprising a biomass-derived polyolefin formed by polymerization of a monomer containing ethylene derived from biomass;
A non-biomass polyolefin resin layer made of a resin material containing a raw material derived from fossil fuel;
The laminated body for packaged products which has these in this order . The laminate for packaged products according to claim 1, wherein the biomass polyolefin resin layer contains 5 mass% or more of the biomass-derived ethylene with respect to the entire biomass polyolefin resin layer. 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, and the first biomass polyolefin resin layer is ethylene derived from the biomass. 5 mass% or more with respect to the whole first biomass polyolefin resin layer, and the second biomass polyolefin resin layer contains 5 mass% or more of the ethylene derived from the biomass with respect to the whole second biomass polyolefin resin layer. The laminate for packaged products according to claim 1 or 2, comprising the laminate. First biomass polyolefin resin layer ethylene concentration C ₂ of the biomass-derived biomass-derived ethylene concentration C ₁ and the second biomass polyolefin resin layer in satisfies the C _1> C _2, the packaging according to claim 3 Product laminate. The laminate for packaged products according to any one of claims 1 to 4, wherein the monomer containing ethylene derived from biomass further contains ethylene and / or α-olefin derived from fossil fuel. The laminate for packaged products according to any one of claims 1 to 5, wherein the monomer containing ethylene derived from biomass further contains an α-olefin derived from biomass. The biomass polyolefin resin composition further comprises a fossil fuel-derived polyolefin obtained by polymerizing a monomer containing fossil fuel-derived ethylene and fossil fuel-derived ethylene and / or α-olefin. The laminate according to any one of 6 . The laminate for packaged products according to claim 7, wherein the biomass polyolefin resin composition comprises 5 to 90% by mass of the polyolefin derived from the biomass and 10 to 95% by mass of the polyolefin derived from the fossil fuel. . The laminate for packaged products according to any one of claims 5 to 8, wherein the α-olefin is butylene, hexene, or octene. The laminate for packaged products according to any one of claims 1 to 9, wherein the polyolefin is polyethylene. The laminated body for packaged products as described in any one of Claims 1-10 in which the said biomass polyolefin resin layer contains the linear low density polyethylene derived from biomass, and the low density polyethylene derived from a fossil fuel. The laminate for packaged products according to any one of claims 1 to 11, wherein the non-biomass polyolefin resin layer comprises low-density polyethylene derived from fossil fuel. The packaging for products laminate, further comprising comprises a barrier layer comprising an inorganic material, packaging products for laminate according to any one of claims 1 to 12. It is a manufacturing method of the laminated body for packaged products as described in any one of Claims 1-13, Comprising: The said biomass polyolefin resin layer and the said non-biomass polyolefin resin layer are manufacturing methods which co-coat. It is a manufacturing method of the laminated body for packaged products as described in any one of Claims 1-13, Comprising: The manufacturing method of bonding together with the said non-biomass polyolefin resin layer, extruding the said biomass polyolefin resin layer. Comprising a packaging product laminated body according to any one of claims 1 to 13 packaged product. A paper cup provided with the laminated body for packaged products as described in any one of Claims 1-13. A liquid paper container comprising the laminate for packaged product according to any one of claims 1 to 13.

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