JP2019043146A - Laminate for packaging product having biomass-derived resin layer - Google Patents

Abstract

To provide a laminate for packaging product which has a paper board substrate, a polyethylene resin layer that is positioned on one surface side of the paper board substrate and is derived from a fossil fuel, and a biomass polyolefin resin layer positioned on the other surface side of the paper board substrate.SOLUTION: The laminate for packaging product comprises: a paper board substrate having a basis weight of 100-700 g/m; a polyethylene resin layer that is positioned on one surface side of the paper board substrate and is derived from a fossil fuel; and a biomass polyolefin resin layer positioned on the other surface side of the paper board substrate, where the biomass polyolefin resin layer contains biomass-derived polyethylene obtained by polymerization monomers containing biomass-derived ethylene.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminate provided with a resin layer derived from biomass, and more specifically to a paperboard substrate, a polyethylene resin layer derived from fossil fuel located on one side of the paperboard substrate, and a paperboard substrate. The present invention relates to a laminate for a packaged product comprising a biomass polyolefin resin layer located on the other side.

  In recent years, along with a growing demand for the construction of a recycling society, in the field of materials as well as energy, it is desired to break away from fossil fuels, and the use of biomass is attracting attention. Biomass is a so-called carbon neutral renewable energy, which is an organic compound photosynthesized from carbon dioxide and water, and converted to carbon dioxide and water by using it. In recent years, commercialization of biomass plastic using such biomass as raw materials has been rapidly advanced, and attempts have been made to produce various resins from biomass raw materials.

  As a resin derived from biomass, polylactic acid (PLA) produced via lactic acid fermentation preceded commercial production, but it is biodegradable, and its performance as a plastic is currently general-purpose plastic However, there is a limit to product applications and product manufacturing methods, and they have not been widely used. In addition, life cycle assessment (LCA) evaluation is performed for PLA, and discussions are being made on energy consumption at the time of PLA production and equivalence when replacing general-purpose plastics.

  Here, as the general purpose plastic, various types such as polyethylene, polypropylene, polyvinyl chloride, polystyrene and the like are used. In particular, polyethylene is formed into a film, a sheet, a bottle and the like, used for various applications such as packaging materials, and used in large quantities all over the world. Therefore, using conventional fossil fuel-derived polyethylene has a large environmental impact.

  Therefore, it is desirable to reduce the amount of fossil fuel used by using biomass-derived materials for the production of polyethylene. For example, to date, it has been studied to produce ethylene and butylene, which are raw materials of polyolefin resins, from renewable natural raw materials (see, for example, Patent Document 1).

JP 2011-506628 gazette

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

  Therefore, an object of the present invention is to use a paperboard base, a polyethylene resin layer derived from fossil fuel located on one side of the paperboard base, and ethylene derived from biomass located on the other side of the paperboard base A laminate for a packaging product comprising a biomass polyolefin resin layer comprising a biomass polyolefin resin composition containing carbon neutral polyethylene, and providing a laminate for a packaging product, wherein the raw material is obtained from conventional fossil fuel It is an object of the present invention to provide a laminate for a packaging product of a biomass polyolefin resin which is not inferior in physical properties such as mechanical properties to the laminate having a resin layer manufactured from the above.

That is, according to one aspect of the present invention,
A paperboard substrate having a basis weight of 100 to 700 g / m ² ;
A fossil fuel-derived polyethylene resin layer located on one side of the paperboard substrate;
A biomass polyolefin resin layer located on the other side of the paperboard substrate;
Have
There is provided a laminate for a packaging product, wherein the biomass polyolefin resin layer comprises biomass-derived polyethylene obtained by polymerizing a monomer containing biomass-derived ethylene.
In an aspect of the present invention, the biomass polyolefin resin layer further comprises a fossil fuel-derived polyethylene obtained by polymerizing ethylene of a fossil fuel and a monomer of ethylene and / or an α-olefin derived from a fossil fuel. preferable.
In the aspect of this invention, it is preferable that the said biomass polyolefin resin layer contains 5 mass% or more with respect to the whole biomass polyolefin resin layer of ethylene derived from the said biomass.
In the aspect of the present invention, it is preferable to further have a barrier layer containing an inorganic substance.
In the aspect of this invention, it is preferable that the said biomass polyolefin resin layer is an extrusion coating layer.
In the aspect of this invention, it is preferable that the polyethylene resin layer derived from the said fossil fuel is an extrusion coating layer.
In another aspect of the present invention, there is provided a packaged product comprising the above laminate for a packaged product.

  The laminate for a packaged product according to the present invention comprises a paperboard substrate, a polyethylene resin layer derived from fossil fuel located on one side of the paperboard substrate, and biomass derived from the other side of the paperboard substrate. By having the biomass polyolefin resin layer which consists of a biomass polyolefin resin composition which contains the biomass origin polyethylene which the monomer containing ethylene of above is polymerized, the laminated body for packaging products of carbon neutral polyolefin resin is realizable. Therefore, the amount of fossil fuel used can be significantly reduced as compared with the prior art, and the environmental impact can be reduced. In addition, the laminate for a packaging product according to the present invention is comparable to the polyolefin laminate manufactured from the raw material obtained from the conventional fossil fuel in terms of physical properties such as mechanical properties. It can be substituted.

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 materials using at least a part of biomass-derived material as the material, and all of the materials are biomass-derived Does not mean.

Laminate The laminate according to the present invention comprises a paperboard base and a biomass polyolefin resin layer. A laminated body can implement | achieve the laminated body of carbon neutral polyolefin resin by having a biomass polyolefin resin layer. Therefore, the amount of fossil fuel used can be significantly reduced as compared with the prior art, and the environmental impact can be reduced. In addition, the laminate according to the present invention is comparable to the laminate of polyolefin resin manufactured from the raw material obtained from the conventional fossil fuel in terms of physical properties such as mechanical characteristics, so the laminate of the conventional polyolefin resin Can be substituted.

  A schematic cross-sectional view of an example of a laminate according to the present invention is shown in FIGS. 1 and 2. The laminated body 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 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 fulfills the function as a substrate layer, and it is necessary to have a strength to endure the process of laminating the biomass polyolefin resin layer by extrusion. The paper used as the paperboard substrate has a basis weight of 100 to 700 g / m ² , preferably 150 to 600 g / m ² , more preferably 200 to 500 g / m ² . As the paperboard substrate, white paperboard in general is targeted, but from the viewpoint of safety, it is particularly preferable to use ivory paper, milk carton base paper, cup base paper, etc. using natural pulp.

  The paperboard used in the present invention may use neutral rosin, alkyl ketene dimer or alkenyl succinic anhydride as a sizing agent, and use cationic polyacrylamide or cationic starch as a fixing agent. It is also good. It is also possible to make paper in the neutral region of pH 6 to 9 using a sulfuric acid band. In addition to the sizing agents mentioned above, in addition to fixing agents, various fillers for papermaking, retention aids, dry strength agents, wet strength agents, binders, dispersants, flocculants, plasticizing agents You may contain the agent and the adhesive agent suitably.

Biomass polyolefin resin layer In the present invention, the biomass polyolefin resin layer is preferably 5 mass% or more, more preferably 5 to 95 mass%, still more preferably 25 to 50 mass% of ethylene derived from the following biomass based on the whole 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 has a first biomass polyolefin resin layer and a second biomass polyolefin resin layer in this order from the paperboard substrate side. Both of 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 a laminate. The laminated body can exhibit excellent flexibility without breaking by having the core layer.

  The first biomass polyolefin resin layer 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 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 prior art, 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 , 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 method A of JIS K7112-1980 after annealing described in JIS K6760-1995. If 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 enhanced. 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 enhanced.

  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. Melt flow rate is a value measured by method A under the conditions of a temperature of 190 ° C. and a load of 21.18 N in the method defined in JIS K 7210-1995. If the MFR of the first biomass polyolefin resin layer is 1 g / 10 min or more, the extrusion load during molding can be reduced. Moreover, if MFR of a biomass polyolefin resin composition is 30 g / 10 minutes 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.

Second Biomass Polyolefin Resin Layer In the present invention, the second biomass polyolefin resin layer may function as a sealing layer of a laminate. 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 5% by mass or more, more preferably 5 to 95% by mass, still more preferably 25 to 75% by mass of ethylene derived from biomass with respect to 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 compared to the prior art, 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 K 6760-1995. 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 enhanced. If 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 enhanced.

  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. Melt flow rate is a value measured by method A under the conditions of a temperature of 190 ° C. and a load of 21.18 N in the method defined in JIS K 7210-1995. If the MFR of the second biomass polyolefin resin layer is 1 g / 10 min or more, the extrusion load during molding can be reduced. Moreover, if MFR of a biomass polyolefin resin composition is 30 g / 10 minutes or less, the mechanical strength of a 2nd biomass polyolefin resin layer can be raised.

  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 relationships with respect to density, thickness, MFR, and biomass degree (ethylene concentration derived from biomass): Is preferred.

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. The first biomass polyolefin resin layer functions as a core layer, so rigidity is required, and the second biomass polyolefin resin layer functions as a heat seal layer, so flexibility is required.

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. Since the first biomass polyolefin resin layer functions as a core layer, a thickness is required, and since the second biomass polyolefin resin layer functions as a heat seal layer, a thickness as large as that of the core layer is not necessary.

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. The first biomass polyolefin resin layer functions as a core layer, so rigidity is required, and the second biomass polyolefin resin layer functions as a heat seal layer, so flexibility is required.

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

Ethylene derived from biomass In the present invention, a method of producing ethylene derived from biomass which is a raw material of polyolefin derived from biomass 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. The plant raw 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, biomass-derived fermented ethanol refers to ethanol purified after contacting a culture solution containing a carbon source obtained from a plant material with a microorganism producing ethanol or a product derived from a crushed material thereof to produce. For purification of ethanol from the culture solution, conventionally known methods such as distillation, membrane separation, and extraction can be applied. For example, benzene, cyclohexane and the like are added to make it azeotropic, or water is removed by membrane separation and the like.

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

  When ethylene is obtained by dehydration reaction of ethanol, a catalyst is usually used, but this catalyst is not particularly limited, and conventionally known catalysts can be used. An advantage of the process is a fixed bed flow reaction which facilitates separation of the catalyst and the product, and, for example, γ-alumina and the like are preferable.

  Since this dehydration reaction is an endothermic reaction, it is usually conducted 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 more, more preferably 250 ° C. or more, still more preferably 300 ° C. or more is suitable. The upper limit is also not particularly limited, but is preferably 500 ° C. or less, more preferably 400 ° C. or less from the viewpoint of energy balance and equipment.

  The reaction pressure is also not particularly limited, but a pressure of normal pressure or higher is preferable in order to facilitate the subsequent gas-liquid separation. Industrially, a fixed bed flow reaction in which separation of the catalyst is easy is preferable, but a liquid phase suspension bed, a fluidized bed and 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. In general, when the dehydration reaction is carried out, it is preferable that there is no water in view of the water removal efficiency. However, in the case of dehydration reaction of ethanol using a solid catalyst, it has been found that in the absence of water, the production of other olefins, in particular butene, tends to increase. It is speculated that this is probably because ethylene dimerization after dehydration can not 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 viewpoint of mass balance and heat balance.

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

  When the raw material is ethanol derived from biomass, the ethylene obtained may be a carbonyl compound such as a ketone, an aldehyde, or an ester, which is an impurity mixed in the ethanol fermentation process, a carbonic acid gas as a decomposition product thereof, a decomposition product of the enzyme, It contains extremely small amounts of nitrogen-containing compounds such as amines and amino acids which are contaminants, and ammonia which is its decomposition product. Depending on the use of ethylene, these trace impurities may become a problem, and may be removed by purification. The purification method is not particularly limited, and can be carried out by a conventionally known method. As a suitable purification operation, for example, an adsorption purification method can be mentioned. The adsorbent used is not particularly limited, and conventionally known adsorbents can be used. For example, a 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 the dehydration reaction of ethanol derived from biomass.

  In addition, you may use a caustic-water process together as a purification method of the impurity in ethylene. In the case of caustic water treatment, it is desirable to carry out before adsorption purification. In that case, after caustic treatment, it is necessary to carry out water removal treatment before adsorption purification.

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

  The carbon number of the above α-olefin is not particularly limited, but generally, 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 biomass-derived material. Further, by containing such an α-olefin, the polyolefin to be polymerized can be made more flexible than a simple linear one because it has an alkyl group as a branched structure.

  It is preferable that said polyolefin is polyethylene. By using ethylene, which is a biomass-derived material, it is possible to theoretically use 100% biomass-derived components.

The ethylene concentration derived from biomass (hereinafter sometimes referred to as “biomass degree”) in the above-mentioned polyolefin is a value obtained by measuring the content of carbon derived from biomass by the 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 take in carbon dioxide in the atmosphere, such as corn, is 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 biomass-derived ethylene is used as a raw material of polyolefin, the ethylene concentration derived from biomass is 100%, and the biomass degree of biomass-derived polyolefin is 100%. Moreover, the ethylene concentration derived from biomass 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 resin layer derived from biomass do not have to have a biomass degree of 100%. This is because if the biomass-derived raw material is used even in part of the laminate, the present invention is in line with the purpose of the present invention to reduce the amount of fossil fuel used as compared with the prior art.

  In the present invention, the method for polymerizing ethylene-containing monomers derived from biomass is not particularly limited, and can be carried out by a conventionally known method. The polymerization temperature and the polymerization pressure may be appropriately adjusted according to the polymerization method and the polymerization apparatus. The polymerization apparatus is also not particularly limited, and a conventionally known apparatus can be used. Hereinafter, an example of the polymerization method of the monomer containing ethylene is demonstrated.

  Methods of polymerizing polyolefins, in particular ethylene polymers and copolymers of ethylene and α-olefins, include the types of polyethylenes targeted, eg high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE) And linear low density polyethylene (LLDPE) and the like, depending on the difference in density and branching. For example, by using a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene-based catalyst as a polymerization catalyst, any method of gas phase polymerization, slurry polymerization, solution polymerization, and high pressure ion polymerization can be used. It is preferable to carry out in one or two or more stages.

  The above single-site catalyst is a catalyst capable of forming homogeneous active species, and is usually prepared by contacting a metallocene transition metal compound or a nonmetallocene transition metal compound with an activation cocatalyst. . A single site catalyst is preferable because it can polymerize a polymer having a high molecular weight and a high degree of uniformity since the active site structure is uniform as compared with a multisite catalyst. It is particularly preferable to use a metallocene catalyst as the single site catalyst. The metallocene catalyst is a catalyst comprising a transition metal compound of Group IV of the periodic table including a ligand having a cyclopentadienyl skeleton, a cocatalyst, an organometallic compound if necessary, and each catalyst component of a carrier. is there.

  In the transition metal compound of Group IV of the periodic table including a ligand having a cyclopentadienyl skeleton as described above, the cyclopentadienyl skeleton is a cyclopentadienyl group, a substituted cyclopentadienyl group, etc. . The substituted cyclopentadienyl group is a hydrocarbon group having 1 to 30 carbon atoms, silyl group, silyl substituted alkyl group, silyl substituted aryl group, cyano group, cyanoalkyl group, cyanoaryl group, halogen group, haloalkyl group, halosilyl It has at least one kind of substituent selected from groups and the like. The substituted cyclopentadienyl group may have two or more substituents, and the substituents combine with each other to form a ring, and an indenyl ring, a fluorenyl ring, an azulenyl ring, a hydrogenated product thereof, etc. You may form. The rings formed by bonding the substituents to each other may further have substituents each other.

  In the transition metal compound of Group IV of the periodic table including a ligand having a cyclopentadienyl skeleton, examples of the transition metal include zirconium, titanium, hafnium and the like, with zirconium and hafnium being particularly preferable. The transition metal compound generally has two as a ligand having a cyclopentadienyl skeleton, and it is preferable that the ligands having each cyclopentadienyl skeleton are bonded to each other by a crosslinking group. Examples of the crosslinking group include substituted silylene groups such as alkylene groups having 1 to 4 carbon atoms, silylene groups, dialkyl silylene groups and diaryl silylene groups, and substituted germylene groups such as dialkyl germylene groups and diaryl germylene groups. Preferably, it is a substituted silylene group.

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

  The transition metal compound of Group IV of the periodic table including the above-described ligand having a cyclopentadienyl skeleton can have one or a mixture of two or more as a catalyst component.

  As the co-catalyst is meant one that can effectively make the transition metal compound of Group IV of the periodic table as a polymerization catalyst, or can make the ionic charge in a catalytically activated state be balanced. As a co-catalyst, benzene-soluble aluminoxanes of organoaluminum oxy compounds, benzene-insoluble organoaluminum oxy compounds, ion exchangeable layered silicates, boron compounds, active hydrogen group-containing or non-containing cations and non-coordinating anions And 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 including a ligand having a cyclopentadienyl skeleton may be used by being supported on an inorganic or organic compound carrier. As the carrier, porous oxides of inorganic or organic compounds are preferable, and specifically, ion exchange layered silicates such as montmorillonite, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ CaO, ZnO, BaO, ThO ₂ etc. or mixtures thereof.

  Furthermore, as an organic metal compound used as needed, an organic aluminum compound, an organic magnesium compound, an organic zinc compound etc. are illustrated. Among these, organic aluminum is preferably used.

  In addition, 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-described polyolefin as a main component. The biomass polyolefin resin composition preferably comprises 5% by mass or more, more preferably 5 to 95% by mass, still more preferably 25 to 75% by 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 prior art, 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, and the concentration of ethylene derived from biomass may be within the above range as the whole biomass polyolefin resin composition.

  The biomass polyolefin resin composition may further include a fossil fuel-derived polyolefin obtained by polymerizing a monomer containing ethylene of a fossil fuel and ethylene and / or an α-olefin derived from a fossil fuel. 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 may be mixed by a conventionally known method. For example, it may be a dry blend or a melt blend.

  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 a biomass-derived polyolefin and preferably 10 to 95% by mass, more preferably 25 It contains -75 mass% of 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 biomass polyolefin resin composition described above, or in the produced biomass polyolefin resin composition, various additives may be added in addition to the main component polyolefin, as long as the characteristics are not impaired. Good. Additives include, for example, plasticizers, UV stabilizers, color inhibitors, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, yarn friction reducing agents, slip agents, mold release agents, An oxidant, an ion exchange agent, a color pigment, etc. can be added. These additives are preferably added in the range of 1 to 20% by mass, 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 fossil fuel-derived material, 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. A non-biomass polyolefin resin layer can form a non-biomass polyolefin resin layer using a conventionally well-known raw material, The composition and formation method are not specifically 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 it has 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 Copolymers, ethylene-methacrylic acid copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methyl methacrylate copolymers or ionomer resins can be used. These resins may be formed by an extrusion laminating method, or may be laminated with a heat resistant substrate layer by a dry lamination or an extrusion laminating method as a film previously formed by T-die method or inflation method. .

  In addition, 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 It may be a composite film obtained by laminating any one of a / metaxylylene diamine nylon 6 co-pressed co-stretched film, a polypropylene / ethylene-vinyl alcohol copolymer co-pressed co-stretched film, or the like, or two or more films of these.

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 preferably made of a vapor-deposited film of an inorganic substance or an inorganic oxide or a metal foil. The vapor deposition film can be formed by a conventionally known method using a conventionally known inorganic substance or inorganic oxide, and the composition and the formation method thereof are not particularly limited. When the laminate further includes a barrier layer, gas barrier properties to block transmission of oxygen gas, water vapor and the like, and light shielding properties to block transmission of visible light and ultraviolet light can be imparted or improved. The laminate may have two or more barrier layers. When two or more barrier layers are provided, they may have the same composition or different compositions.

  As a vapor deposition film, for example, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti) Vapor deposited films of inorganic substances or inorganic oxides such as lead (Pb), zirconium (Zr), yttrium (Y) and the like can be used. In particular, as a material suitable for packaging materials (bags) etc., it is preferable to use a vapor-deposited film of aluminum metal or a vapor-deposited film of silicon oxide or aluminum metal or aluminum oxide.

The notation of the inorganic oxide is, for example, SiO _x , AlO _x, etc., where M _x (wherein M represents an inorganic element, and the value of X varies depending on the inorganic element). 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 0-0.5, tin (Sn) is 0-2, sodium (Na) is 0-0.5, boron (B) is 0-1, 5, titanium (Ti) Is 0 to 2, lead (Pb) is 0 to 1, zirconium (Zr) is 0 to 2, and yttrium (Y) is a value of 0 to 1.5. In the above, in the case of X = 0, it is a perfect inorganic simple substance (pure substance) and is not transparent, and the upper limit of the range of X is a value which is completely oxidized. As the packaging material, silicon (Si) and aluminum (Al) are suitably used, and 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. The value of can be used.

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

  As a method of forming a deposited film, for example, physical vapor deposition (Physical Vapor Deposition, PVD) such as vacuum deposition, sputtering, and ion plating, or plasma chemical vapor deposition, thermochemical Examples thereof include a chemical vapor deposition method such as a vapor phase growth method and a photochemical vapor deposition method (Chemical Vapor Deposition method, CVD method).

  In addition, according to another aspect, the barrier layer may be a metal foil obtained by rolling a metal. As metal foil, conventionally well-known metal foil can be used. An aluminum foil or the like is preferable from the viewpoint of the gas barrier property to block transmission of oxygen gas and water vapor and the like and the light shielding property to block transmission of visible light and ultraviolet light and the like.

Other Layers The laminate according to the present invention may further have at least one other layer in addition to the above layers. When two or more other layers are provided, each may have the same composition or different compositions. Other layers can be formed on any one or more of the above layers. As other layers, for example, printed layers and adhesive layers can be mentioned. A printing layer can be formed using a conventionally well-known pigment and dye, and the formation method is not specifically limited. In addition, the adhesive layer is an adhesive layer or an adhesive resin layer which is formed to laminate any two layers by lamination. The adhesive for laminating includes, for example, one-component or two-component cured or non-cured vinyl-based, (meth) acrylic, polyamide-based, polyester-based, polyether-based, polyurethane-based, epoxy-based, rubber-based, Other solvent-based, water-based or emulsion-type laminating adhesives may be used. As a coating method of said adhesive agent, it can apply by the direct gravure roll coat method, the gravure roll coat method, the kiss coat method, the reverse roll coat method, the Fonten method, the transfer roll coat method, and other methods, for example. 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, as the adhesive resin layer, a resin layer formed of a thermoplastic resin layer is used. Specifically, as the material of the adhesive resin layer, low density polyethylene resin, medium density polyethylene resin, high density polyethylene resin, linear low density polyethylene resin, 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 ethylene / methyl methacrylate copolymer resin, ethylene / maleic acid copolymer resin, ionomer resin, polyolefin resin with unsaturated carboxylic acid, unsaturated carboxylic acid, unsaturated carboxylic anhydride, ester monomer, Or graft copolymerized resin, maleic anhydride to polyolefin resin It can be used sexual resin or the like. These materials can be used in combination of one or more.

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

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

  Although the thickness of the laminated body obtained as mentioned above is arbitrary according to the use, it is about 5-500 micrometers normally, Preferably it is about 20-300 micrometers.

  The laminate according to the present invention is provided with surface functions such as chemical function, electric function, magnetic function, mechanical function, friction / wear / lubrication function, optical function, thermal function, biocompatibility etc. For the purpose, it is also possible to apply secondary processing. Examples of secondary processing include embossing, painting, adhesion, printing, metallization (plating, etc.), mechanical processing, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromic treatment, physical vapor deposition, chemical vapor deposition, Coating etc. etc. are mentioned. In addition, the laminate according to the present invention may be subjected to lamination processing (dry lamination or extrusion lamination), bag-making processing, and other post-processing processing to produce a molded article.

Applications The laminate according to the present invention includes various products such as packaging products such as packaging containers and packaging bags, sheet-formed articles such as decorative sheets and trays, laminated films, optical films, resin plates, various label materials, lids, and laminate tubes. It can be suitably used for applications, in particular, packaged products are preferred.

<Other aspects>
The present invention is to provide a laminate comprising a paperboard base and a biomass polyolefin resin layer comprising a biomass polyolefin resin composition containing a carbon neutral polyolefin using ethylene derived from biomass, which comprises: 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 not inferior in physical properties such as mechanical properties.
According to yet another aspect of the invention,
A paperboard substrate having a basis weight of 100 to 700 g / m ² ;
There is provided a laminate having a biomass polyolefin resin layer comprising a biomass polyolefin resin composition comprising a biomass-derived polyolefin obtained by polymerization of a monomer containing biomass-derived ethylene.
In the further another aspect of this invention, it is preferable that the said biomass polyolefin resin layer comprises 5 mass% or more with respect to the whole biomass polyolefin resin layer of ethylene derived from the said biomass.
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 this order from the paperboard substrate side, The biomass polyolefin resin layer contains 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 as a second biomass It is preferable to contain 5 mass% or more with respect to the whole polyolefin resin layer.
In still another aspect of the present invention, the ethylene concentration C ₁ derived from biomass in the first biomass polyolefin resin layer and the ethylene concentration C ₂ derived from biomass in the second biomass polyolefin resin layer are C ₁ > C It is preferable to satisfy ₂ .
In still another aspect of the present invention, the monomer may further include ethylene and / or α-olefin derived from fossil fuel.
In still another aspect of the present invention, the monomer may further include an α-olefin derived from biomass.
In still another aspect of the present invention, the biomass polyolefin resin composition is derived from a fossil fuel obtained by polymerizing a monomer containing ethylene derived from fossil fuel and ethylene and / or α-olefin derived from fossil fuel It may further contain a polyolefin.
In still another aspect of the present invention, the biomass polyolefin resin composition may contain 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 aspect of the present invention, the polyolefin is preferably polyethylene.
In still another aspect of the present invention, the laminate may further have a non-biomass polyolefin resin layer made of a resin material containing a fossil fuel-derived material.
In still another aspect of the present invention, the laminate may further have a barrier layer composed of an inorganic substance and / or an inorganic oxide.
In the further another aspect of this invention, it is preferable that the said biomass polyolefin resin layer is formed by extrusion molding on the said paperboard base material.
In still another aspect of the present invention, the biomass polyolefin resin layer is preferably formed by coextrusion.
In still another aspect of the present invention, the co-extrusion is preferably 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 aspect of the present invention is a biomass polyolefin resin layer comprising a paperboard substrate and a biomass polyolefin resin composition comprising a biomass-derived polyolefin obtained by polymerizing a monomer derived from biomass-derived ethylene. Thus, a carbon neutral polyolefin resin laminate can be realized. Therefore, the amount of fossil fuel used can be significantly reduced as compared with the prior art, and the environmental impact can be reduced. In addition, the laminate according to still another aspect of the present invention is comparable to conventional polyolefins in physical properties such as mechanical properties as compared with polyolefin laminates produced from raw materials obtained from conventional fossil fuels. Laminates can be substituted.

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

Measurement / Conditions In the following reference examples, reference comparative examples, examples, and comparative examples, the biomass degree is a value of the content of carbon derived from biomass measured by radioactive carbon (C14).

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

Example 1
An acid resistant paper (made by Oji Specialty Paper: acid resistant BYO-500, basis weight 320 g / m ² ) was used as a base material and a base material of the paper cup container, and the back surface was subjected to a corona treatment. Next, as the core layer on the paperboard substrate side, low density polyethylene derived from fossil fuel (manufactured by Japan Polyethylene Corporation: LC 701, MFR: 14, density: 0.919) and straight chain low density polyethylene derived from biomass (Braskem) Made: SLL3180, MFR: 2.7, density: 0.918, biomass degree: 87%) The resin which carried out dry blending by 50: 50 was prepared. Further, as the seal layer, a low density polyethylene resin derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd .: Novatec LC520, MFR: 3.6, density: 0.923) was prepared. The above resin is co-pressed (core layer: 20 μm, seal layer: 20 μm) on the corona-treated side of the paperboard substrate at resin temperatures of 290 ° C and 320 ° C, respectively, and the line speed is 100 m / min. A polyethylene laminate was obtained. The biomass degree of the extruded layer was 22%.

Example 2
The base material and base material of the paper cup container are subjected to corona treatment using cup base paper (Nippon Paper Industries Co., Ltd .: basis weight 220 g / m ² ) as the paperboard base material, and then the corona treated surface is treated with fossil fuel 55 parts by mass of density polyethylene (manufactured by Japan Polyethylene Corp .: LC 520 (MFR: 3.6, density: 0.923) and linear low density polyethylene derived from biomass (manufactured by Braskem: SLL 318, MFR: 2.7, density: 0.918, Biomass degree: 87%) 45 parts by mass of dry blended resin 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 degree of the extruded layer was 41%.

Comparative Example 1
Acid-resistant paper (made by Oji Specialty Paper: acid-resistant BYO-500, basis weight 320 g / m ² ) is used as the base material and base material of the paper cup container for the paperboard substrate, and the corona treatment is applied to the back surface of the paper cup container. Low-density polyethylene resin derived from fossil fuel (Novatec LC520, MFR: 3.6, density: 0.923) is extruded on the treated side at a resin temperature of 320 ° C (40 μm) to a line speed of 100 m / min. The extrusion coating was carried out to obtain a non-biomass polyethylene laminate. The biomass degree of the extruded layer was 0%.

Comparative example 2
The base material and base material of the paper cup container are subjected to corona treatment using cup base paper (Nippon Paper Industries Co., Ltd .: basis weight 220 g / m ² ) as the paperboard base material, and then the corona treated surface is treated with fossil fuel Density polyethylene (Nippon Polyethylene Co., Ltd .: LC520 (MFR: 3.6, density: 0.923) is extruded at a resin temperature of 320 ° C. (25 μm) and extrusion coated at a line speed of 100 m / min. A laminate was obtained, the biomass degree of the extruded layer was 0%.

Preparation of Paper Cups The laminates prepared above were then used to stamp out a frusto-conical blank plate from which the barrel of the paper cup was made. Next, the above-mentioned blank plate was wound in a cylindrical shape, both ends thereof were partially overlapped, and the polymerizing portion was subjected to a flame treatment to heat and melt the low density polyethylene resin layer present in the polymerizing portion. Subsequently, pressing was performed by a heat plate or the like to perform body sticking to form a body seal portion, and a cylindrical cup body portion forming a paper cup was manufactured.

  On the other hand, in the same manner as described above, the laminate manufactured above is used and punched into a circular shape to manufacture a disk constituting the bottom, and then the outer peripheral portion of the disk is erected into a cylindrical shape. It was molded to produce a bottom with a raised forming. Next, after inserting the bottom paper similarly manufactured in the upper part into the cylindrical cup barrel manufactured above, the cylindrical cup barrel and the bottom paper are blown with hot air or the like at the joint portion thereof The resin layer present at the bonding portion was heated and melted. Subsequently, the tip of the cylindrical cup body is bent inward by the curling mold and covered with the upstanding forming portion that constitutes the bottom, so that the tip and bottom of the cylindrical cup body are covered. By knurling the overlapping portion with the upstanding forming portion from the inner diameter side by knurling from the inner diameter side, the above-mentioned cylindrical cup barrel and the bottom are closely adhered to form a joint portion, and a tubular cup barrel of steam is formed. The bottom of the paper cup was formed.

  After that, the bottom of the above-mentioned cylindrical cup body is closely adhered, and the tip short portion on the opposite side to the side on which the joint portion is formed is curled while being bent outward by the curling mold in the same manner as above. An outward curled portion was formed to produce a paper cup with a full capacity of 353 cc.

  In both of Examples 1 and 2 and Comparative Examples 1 and 2, the cup formation could be carried out without any problem. Further, these paper cups were subjected to a destructive inspection and visually checked if there was a seal abnormality. As a result, the phenomenon of paper peeling was confirmed in both cases, and it was confirmed that a sufficient seal strength was obtained.

Reference Example 1
50 parts by mass of linear low density polyethylene derived from fossil fuel (Nippon Polyethylene Co., Ltd .: NH745 (MFR: 8.0, density: 0.913) in the first layer of coextrusion, as a PET film as a substrate, Two layers of resin (20 μm) dry-blended with 50 parts by mass of linear low density polyethylene derived from biomass (Braske: SLL 318, MFR: 2.7, density: 0.918, degree of biomass: 87%) Low-density polyethylene derived from fossil fuel (manufactured by Japan Polyethylene Corporation: LC520 (MFR: 3.6, density: 0.923, 20 μm) is extruded together at a resin temperature of 320 ° C. (line speed 100 m / min), non- A biomass polyethylene laminate was obtained.

Reference Example 2
In PET film as a base material, linear low density polyethylene derived from fossil fuel (Nippon Polyethylene Co., Ltd .: NH745 (MFR: 8.0, density: 0.913, 20 μm)) in the first layer of co-extrusion, 2 Low density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd .: 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 of the substrate was peeled off to obtain film samples A and B, respectively. Each of the obtained film samples is cut out into a width of 15 mm and a length of 200 mm from each of the MD direction and the CD direction to make a test piece, and a temperature tester (Tensilon RTC-125A, manufactured by Orientec Co., Ltd.) at a temperature of 23 ° C. The strength and elongation of the test pieces were measured in an environment of 50 RH% humidity. In addition, each film sample is 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 seal strength (N / N using a tensile tester (Tensilon RTC-125A, manufactured by Orientec Co., Ltd.) 15 mm) was measured.

The above evaluation results were as shown in Table 1. Film samples A and B showed no significant difference in all evaluation items. That is, the biomass resin film (A) was not inferior to the non-biomass resin film (B) in physical properties such as mechanical characteristics.

Example 3
As a liquid paper container application, using a milk carton base paper (manufactured by Clearwater: basis weight 320 g / m ² ) as the paper base and subjecting the surface side to a flame treatment, 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, a frame was also applied to the back side, and this frame-treated side In the first layer of the coextrusion, 50 parts by mass of linear low density polyethylene derived from fossil fuel (Nippon Polyethylene Co .: NH745 (MFR: 8.0, density: 0.913) and biomass derived A tree obtained by dry blending 50 parts by mass of linear low density polyethylene (manufactured by Braskem: SLL 318, MFR: 2.7, density: 0.918, degree of biomass: 87%) The oil (20 μm) was extruded by extruding low density polyethylene derived from fossil fuel (LC520 (MFR: 3.6, density: 0.923, 20 μm) from the fossil fuel in the second layer at a resin temperature of 300 ° C.) A line speed of 100 m / min), a biomass polyethylene laminate was obtained, and the degree of biomass of the entire laminate excluding the paper substrate was 15%.

Comparative example 3
As a paperboard base material, milk carton base paper (manufactured by Clearwater: basis weight 320 g / m ² ) is subjected to a flame treatment on its surface side, and then low density polyethylene derived from fossil fuel (Japan polyethylene company: LC520 ( MFR: 3.6, density: 0.923) was extruded at a resin temperature of 320 ° C. (20 μm), and after the frame processing was also performed on the back side, this frame treated side (back side) was Linear low density polyethylene derived from fossil fuel (Nippon Polyethylene Co., Ltd .: NH745 (MFR: 8.0, density: 0.913, 20 μm) in the first layer of co-extrusion, low in the second layer from fossil fuel Density polyethylene (Nippon Polyethylene Co., Ltd .: LC520 (MFR: 3.6, density: 0.923, 20 μm) are extruded together at a resin temperature of 300 ° C. (line speed 100 m / min), not 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 (made by Toyo Aluminum Co., 7 μm) and a PET film derived from fossil fuel (made by Toyobo Co., Ltd .: E5100, 12 μm) are dry laminated (made by DIC: main agent LX-703A / hardening agent KR-90) on this frame treated side. ) And ethylene-acrylic acid copolymer (manufactured by Du Pont-Mitsui Polychemicals Co., Ltd .: Nuclerel N0908C, 20 μm) was extrusion laminated and laminated. Thereafter, a polyester polyol / isocyanate two-component curing type anchor agent (Mitsui Takeda Polychemical Co., Ltd .: A3210 / AT3075) is coated on the PET surface of the dry laminated film, and then low density polyethylene derived from fossil fuel (Japan polyethylene company): 50 parts by mass of LC520 (MFR: 3.6, density: 0.923) and linear low density polyethylene derived from biomass (Braske: SLL 318, MFR: 2.7, density: 0.918, biomass degree: 87 Dry blend with 50 parts by mass and extrusion (20 μm) at a resin temperature of 320 ° C., low density polyethylene film (Dainippon Printing Co., Ltd .: SKL, density: 0.923) at a line speed of 100 m / min. , And 40 μm) to obtain a biomass polyethylene laminate. The degree of biomass of the whole laminate excluding 6% 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. Dry-laminate aluminum foil (made by Toyo Aluminum Co., 7 μm) and PET film derived from biomass (made by Toyobo Co., Ltd .: DE 024, 12 μm) on this frame treated side (made by DIC: main agent LX-703A / hardening agent KR-90) The resulting film was laminated by extrusion lamination of an ethylene-acrylic acid copolymer (manufactured by Du Pont-Mitsui Polychemicals Co., Ltd .: Nuclerel N0908C, 20 μm). Thereafter, a polyester polyol / isocyanate two-component curing type anchor agent (Mitsui Takeda Polychemical Co., Ltd .: A3210 / AT3075) is coated on the PET surface of the dry laminated film, and then low density polyethylene derived from fossil fuel (Japan polyethylene company): 50 parts by mass of LC520 (MFR: 3.6, density: 0.923) and linear low density polyethylene derived from biomass (Braske: SLL 318, MFR: 2.7, density: 0.918, biomass degree: 87 Dry blend with 50 parts by mass and extrusion (20 μm) at a resin temperature of 320 ° C., low density polyethylene film (Dainippon Printing Co., Ltd .: SKL, density: 0.923) at a line speed of 100 m / min. , And 40 μm) to obtain a biomass polyethylene laminate. The degree of biomass of the entire laminate excluding 9% 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 (made by Toyo Aluminum Co., 7 μm) and a PET film derived from fossil fuel (made by Toyobo Co., Ltd .: E5100, 12 μm) are dry laminated (made by DIC: main agent LX-703A / hardening agent KR-90) on this frame treated side. ) And ethylene-acrylic acid copolymer (manufactured by Du Pont-Mitsui Polychemicals Co., Ltd .: Nuclerel N0908C, 20 μm) was extrusion laminated and laminated. Thereafter, a polyester polyol / isocyanate two-component curing type anchor agent (Mitsui Takeda Polychemical Co., Ltd .: A3210 / AT3075) is coated on the PET surface of the dry laminated film, and then low density polyethylene derived from fossil fuel (Japan polyethylene company): LC520 (MFR: 3.6, density: 0.923) was extruded (20 μm) at a resin temperature of 320 ° C, and a low density polyethylene film (Dainippon Printing Co., Ltd .: SKL, at a line speed of 100 m / min. A density of 0.923, 40 μm) was laminated to obtain a biomass polyethylene laminate, and the biomass degree of the entire laminate excluding the paper substrate was 0%.

Comparative example 5
Mainly for non-laminated surface of paper base paper (Clear water company 400 g / m ² printed surface low-density polyethylene 20 g / m ² extrusion laminated) as liquid paper container use for normal temperature long-term storage type such as sake etc. I did an anchor coat. A film obtained by dry laminating (made by DIC: main agent LX-703A / hardening agent KR-90) an aluminum foil (made by Toyo Aluminum Co., 7 μm) and a PET film derived from biomass (made by Toyobo Co., Ltd .: DE024, 12 μm) Were laminated by extrusion lamination of an ethylene-acrylic acid copolymer (manufactured by Du Pont-Mitsui Polychemicals Co., Ltd .: Nuclerel N0908C, 20 μm). Thereafter, a polyester polyol / isocyanate two-component curing type anchor agent (Mitsui Takeda Polychemical Co., Ltd .: A3210 / AT3075) is coated on the PET surface of the dry laminated film, and then low density polyethylene derived from fossil fuel (Japan polyethylene company): LC520 (MFR: 3.6, density: 0.923) was extruded (20 μm) at a resin temperature of 320 ° C, and a low density polyethylene film (Dainippon Printing Co., Ltd .: SKL, at a line speed of 100 m / min. A density of 0.923, 40 μm) was laminated to obtain a biomass polyethylene laminate, and the biomass degree of the entire laminate excluding the paper substrate was 3%.

Evaluation of container strength
Using the cartons prepared in Example 4 and Comparative Example 4, after carrying out water filling and molding with a liquid paper container filling machine (DR-10) manufactured by Dainippon Printing Co., Ltd., these measurement samples are vertical and horizontal ( Single compressive strength measurements were carried out in two directions, all across. As shown in Table 2, no significant difference was found between the biomass-derived product and the fossil fuel-derived product.

Sealability evaluation (filler inspection)
Using the cartons prepared in Example 4 and Comparative Example 4, the sealing properties of the top and bottom were compared after water filling molding with a liquid paper container filling machine (DR-10) manufactured by Dainippon Printing Co., Ltd. . The evaluation of the sealability was performed by sealing the penetrant and visually with the following criteria. As the evaluation result is shown in Table 3, no significant difference was found between the biomass-derived product and the fossil fuel-derived product.
Sealability evaluation criteria ○: Good.
Fair: There was no tendency to come off the seal but there was a tendency to come off.
X: It was in the state where seal omission was checked.

DESCRIPTION OF SYMBOLS 10 laminated body 11 paper base 12 biomass polyolefin resin layer 20 laminated body 21 paper board base 22 1st biomass polyolefin resin layer 23 2nd biomass polyolefin resin layer

Claims (7)

A paperboard substrate having a basis weight of 100 to 700 g / m ² ;
A fossil fuel-derived polyethylene resin layer located on one side of the paperboard substrate;
A biomass polyolefin resin layer located on the other side of the paperboard substrate;
Have
The laminated body for packaging products in which the said biomass polyolefin resin layer contains polyethylene derived from biomass which the monomer containing ethylene derived from biomass polymerizes.   The packaged product according to claim 1, wherein the biomass polyolefin resin layer further comprises a fossil fuel-derived polyethylene obtained by polymerizing ethylene of a fossil fuel and a monomer of ethylene and / or α-olefin derived from a fossil fuel. Laminates.   The laminated body for a packaging product according to claim 1 or 2, wherein the biomass polyolefin resin layer contains 5% by mass or more of ethylene derived from the biomass with respect to the entire biomass polyolefin resin layer.   The laminated body for packaged products according to any one of claims 1 to 3, further comprising a barrier layer containing an inorganic substance.   The laminated body for packaged products according to any one of claims 1 to 4, wherein the biomass polyolefin resin layer is an extrusion coating layer.   The laminated body for packaged products according to any one of claims 1 to 5, wherein the fossil fuel-derived polyethylene resin layer is an extrusion coating layer.   A packaged product comprising the laminate for a packaged product according to any one of claims 1 to 6.

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