JP6738568B2 - Polyethylene resin film - Google Patents

Description

The present invention relates to a resin film containing a biomass-derived polyethylene, and more particularly to a polyethylene resin film comprising a resin composition containing a biomass-derived polyethylene obtained by polymerizing a biomass-derived ethylene-containing monomer.

In recent years, with the increasing demand for building a recycling-based society, there is a demand in the materials field to escape from fossil fuels as well as energy, and the use of biomass is drawing attention. Biomass is an organic compound photosynthesized from carbon dioxide and water, and by utilizing it, it becomes carbon dioxide and water again, so-called carbon-neutral renewable energy. In recent years, the practical use of biomass plastics using these biomasses as raw materials has progressed rapidly, and attempts have been made to produce various resins from biomass raw materials.

As a biomass-derived resin, polylactic acid (PLA), which is produced through lactic acid fermentation, preceded commercial production, but its performance as a plastic, including its biodegradability, is the current general-purpose plastic. Therefore, it is not widely used because there are limits to product applications and product manufacturing methods. Further, life cycle assessment (LCA) evaluation is performed on PLA, and energy consumption during PLA production and equivalence during replacement of general-purpose plastics are discussed.

Here, various types of general-purpose plastics such as polyethylene, polyvinyl chloride, polystyrene, and ABS resin are used. In particular, polyethylene is formed 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. Therefore, the use of conventional fossil fuel-derived polyethylene has a large environmental load.

Therefore, it is desired to reduce the amount of fossil fuel used by using a raw material derived from biomass for the production of polyethylene. For example, up to now, research has been conducted on producing ethylene or butylene, which is a raw material of a polyolefin resin, from a renewable natural raw material (for example, see Patent Document 1).

Japanese Patent Publication No. 2011-506628

The present inventors focused on ethylene as a raw material of a polyethylene resin film, and instead of ethylene obtained from a conventional fossil fuel, a polyethylene resin film obtained by using biomass-derived ethylene as a raw material was obtained from a conventional fossil fuel. It was found that a polyethylene resin film produced by using such ethylene can be obtained in terms of physical properties such as mechanical properties. The present invention is based on this finding.

Therefore, an object of the present invention is to provide a resin film made of a resin composition containing carbon-neutral polyethylene using biomass-derived ethylene, which is a resin film produced from a raw material obtained from a conventional fossil fuel. Another object of the present invention is to provide a polyethylene resin film which is comparable in physical properties such as mechanical properties.

According to an aspect of the present invention, a resin containing biomass-derived high-density polyethylene obtained by polymerizing biomass-derived ethylene-containing monomers, and fossil fuel-derived polyethylene obtained by polymerizing fossil fuel-derived ethylene-containing monomers A polyethylene resin film for a single-layer packaging material comprising a composition,
For the single-layer packaging material, wherein the resin composition contains 5% by mass or more of the biomass-derived high-density polyethylene with respect to the entire resin composition, and the biomass content of the resin composition is 48% or less. A polyethylene resin film is provided.

In the aspect of the present invention, the resin composition may have a density of 0.91 to 0.96 g/cm ³ .

In an aspect of the present invention, the resin composition has a temperature of 190° C. and a load of 21.18 N in a method defined by JIS K7210-1995, when measured by a method A of 1 to 30 g/10 min. May have a melt flow rate of

In the aspect of the present invention, the resin composition is a plasticizer, an ultraviolet stabilizer, an anti-coloring agent, a matting agent, a deodorant, a flame retardant, a weathering agent, an antistatic agent, a yarn friction reducing agent, a slip agent. , A release agent, an antioxidant, an ion exchanger, and one or more additives selected from coloring pigments.

In the aspect of the present invention, the resin composition may be composed of 5 to 50% by mass of the biomass-derived high-density polyethylene and 10 to 50% by mass of the fossil fuel-derived low-density polyethylene.

In an aspect of the present invention, a method for producing the polyethylene resin film for packaging material,
Provided is a method for producing, which comprises extruding the resin composition.

In the aspect of the present invention, the extrusion molding may be performed by a T-die method or an inflation method.

In an aspect of the present invention, there is provided a packaged product including the polyethylene resin film for packaging material.

In an aspect of the present invention, a sheet molded article provided with the polyethylene resin film for packaging material is provided.

In an aspect of the present invention, a label material including the polyethylene resin film for packaging material is provided.

In an aspect of the present invention, a lid member provided with the polyethylene resin film for packaging material is provided.

In an aspect of the present invention, a laminate tube provided with the polyethylene resin film for packaging material is provided.

In an aspect of the present invention, a bag including the polyethylene resin film for packaging material is provided.

According to the present invention, the polyethylene resin film comprises a resin composition containing a biomass-derived polyethylene obtained by polymerizing a monomer containing a biomass-derived ethylene, and the biomass-derived ethylene is added to the resin composition in an amount of 5% or less. A carbon-neutral polyethylene resin film can be realized by containing at least mass%. Therefore, the amount of fossil fuel used can be significantly reduced as compared with the conventional one, and the environmental load can be reduced. Further, the polyethylene resin film of the present invention is comparable to the polyethylene resin film produced from the raw material obtained from the conventional fossil fuel in terms of physical properties such as mechanical properties, and thus replaces the conventional polyethylene resin film. be able to.

Biomass-Derived Ethylene In the present invention, the method for producing biomass-derived ethylene, which is a raw material for the biomass-derived polyolefin, is not particularly limited and can be obtained by a conventionally known method. Hereinafter, an example of a method for producing ethylene derived from biomass 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, beets, and manioc can be mentioned.

In the present invention, the biomass-derived fermented ethanol refers to ethanol purified after the ethanol-producing microorganism or its crushed product-derived product is brought into contact with a culture solution containing a carbon source obtained from a plant raw material. 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 to carry out azeotropic distillation, or removing water by membrane separation or the like can be mentioned.

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

A catalyst is usually used when ethylene is obtained by the dehydration reaction of ethanol, but this catalyst is not particularly limited, and a conventionally known catalyst can be used. What is advantageous in the process is a fixed bed flow reaction in which the catalyst and the product can be easily separated, and for example, γ-alumina and the like are preferable.

Since this dehydration reaction is an endothermic reaction, it is usually performed under heating conditions. The heating temperature is not limited as long as the reaction proceeds at a commercially useful reaction rate, but a temperature of 100°C or higher, preferably 250°C or higher, more preferably 300°C or higher is suitable. The upper limit is also not particularly limited, but from the viewpoint of energy balance and equipment, it is preferably 500°C or lower, more preferably 400°C or lower.

The reaction pressure is also not particularly limited, but a pressure equal to or higher than normal pressure is preferable in order to facilitate the subsequent gas-liquid separation. Industrially, a fixed bed flow reaction in which the catalyst can be easily separated is preferable, 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. In general, when performing a dehydration reaction, it is preferable that there is no water in view of the removal efficiency of water. However, in the case of ethanol dehydration reaction using a solid catalyst, it was found that the amount of other olefins, especially butene, tends to increase in the absence of water. It is speculated that ethylene dimerization after dehydration cannot be suppressed unless a small amount of water is present. The lower limit of the permissible water content is 0.1% or more, preferably 0.5% or more. The upper limit is not particularly limited, but from the viewpoint of mass balance and heat balance, it is preferably 50% by weight or less, more preferably 30% or less, still more preferably 20% or less.

By carrying out the dehydration reaction of ethanol in this way, a mixed part of ethylene, water and a small amount of unreacted ethanol can be obtained. However, since ethylene is a gas at room temperature below about 5 MPa, gas-liquid separation is performed from these mixed parts. Ethylene can be obtained by removing water and ethanol. This method may be a known method.

Ethylene obtained by gas-liquid separation is further distilled, and the distillation method, operating temperature, residence time and the like are not particularly limited, except that the operating pressure at this time is atmospheric pressure or higher.

When the raw material is ethanol derived from biomass, the obtained ethylene includes carbon dioxide gas which is a carbonyl compound such as ketones, aldehydes and esters which are impurities mixed in the ethanol fermentation process and carbon dioxide which is a decomposition product thereof, and a decomposition product of an enzyme. A minute amount of impurities such as nitrogen-containing compounds such as amines and amino acids and decomposition products thereof such as ammonia are contained. These trace amounts of impurities may pose a problem depending on the use of ethylene, and may be removed by purification. The purification method is not particularly limited and can be performed 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 a conventionally known adsorbent can be used. For example, a material having a high surface area is preferable, and the type of the adsorbent is selected according to the type and amount of impurities in ethylene obtained by the dehydration reaction of ethanol derived from biomass.

Note that caustic water treatment may be used in combination as a method for purifying impurities in ethylene. When treating with caustic water, 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.

Polyolefin In the present invention, the biomass-derived polyolefin is obtained by polymerizing a biomass-derived ethylene-containing monomer. As the biomass-derived ethylene, it is preferable to use the one obtained by the above production method. Since biomass-derived ethylene is used as the raw material monomer, the polymerized polyolefin is derived from biomass. The raw material monomer of the polyolefin does not have to contain 100% by mass of biomass-derived ethylene.

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

The above-mentioned α-olefin is not particularly limited in carbon number, but normally, one having 3 to 20 carbon atoms can be used, and butylene, hexene, or octene is preferable. This is because if butylene, hexene, or octene can be produced by polymerizing ethylene, which is a raw material derived from biomass. Further, by including such an α-olefin, the polymerized polyolefin has an alkyl group as a branched structure, so that it can be made more flexible than a simple linear one.

The above-mentioned polyolefin is preferably polyethylene. This is because it is theoretically possible to produce 100% biomass-derived components by using ethylene, which is a biomass-derived raw material.

The concentration of ethylene derived from biomass in the above-mentioned polyolefin (hereinafter sometimes referred to as “biomass degree”) is a value obtained by measuring the content of carbon derived from biomass by measuring radioactive carbon (C14). Since carbon dioxide in the atmosphere contains C14 at a constant rate (105.5 pMC), the amount of C14 in plants that grow by taking in carbon dioxide in the atmosphere, such as 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, when the content of C14 in the polyolefin is P _C14 , the content P _bio of carbon derived 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 the raw material of the polyolefin, the biomass-derived ethylene concentration is 100%, and the biomass-derived polyolefin has a biomass degree of 100%. Further, the concentration of ethylene 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 biomass-derived resin film do not have to have a biomass degree of 100%. This is because if the biomass-derived raw material is used even in a part of the resin film, it is in line with the gist of the present invention that the amount of fossil fuel used is reduced compared to the conventional case.

In the present invention, the method for polymerizing the monomer containing biomass-derived ethylene is not particularly limited, and a conventionally known method can be used. The polymerization temperature and the polymerization pressure may be appropriately adjusted depending on the polymerization method and the polymerization apparatus. The polymerization device is also not particularly limited, and a conventionally known device can be used. Hereinafter, an example of a method for polymerizing a monomer containing ethylene will be described.

The method for polymerizing a polyolefin, particularly an ethylene polymer or a copolymer of ethylene and an α-olefin, is carried out according to the type of the target polyethylene such as high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE) ), and linear low-density polyethylene (LLDPE), etc., can be appropriately selected depending on the difference in density and branching. For example, as a polymerization catalyst, using a multi-site catalyst such as Ziegler-Natta catalyst, or a single-site catalyst such as a metallocene catalyst, by any one of gas phase polymerization, slurry polymerization, solution polymerization, and high pressure ionic polymerization, It is preferable to carry out in one step or in multiple steps of two or more steps.

The above single-site catalyst is a catalyst that can form a uniform active species, and is usually prepared by contacting a metallocene-based transition metal compound or a nonmetallocene-based transition metal compound with an activating cocatalyst. .. The single-site catalyst is preferable since it has a more active site structure than the multi-site catalyst and can polymerize a polymer having a high molecular weight and a high degree of uniformity. As the single-site catalyst, it is particularly preferable to use a metallocene catalyst. The metallocene catalyst is a catalyst including a transition metal compound of Group IV of the periodic table containing 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 containing a ligand having the cyclopentadienyl skeleton, the cyclopentadienyl skeleton is a cyclopentadienyl group, a substituted cyclopentadienyl group, or the like. .. Examples of the substituted cyclopentadienyl group include a hydrocarbon group having 1 to 30 carbon atoms, a silyl group, a silyl-substituted alkyl group, a silyl-substituted aryl group, a cyano group, a cyanoalkyl group, a cyanoaryl group, a halogen group, a haloalkyl group, and a halosilyl group. It has at least one kind of substituent selected from groups and the like. The substituted cyclopentadienyl group may have two or more substituents, and the substituents are bonded to each other to form a ring, and an indenyl ring, a fluorenyl ring, an azulenyl ring, a hydrogenated product thereof or the like can be formed. It may be formed. The ring formed by bonding the substituents to each other may further have a substituent to each other.

In the transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, examples of the transition metal include zirconium, titanium and hafnium, and zirconium and hafnium are particularly preferable. The transition metal compound usually has two ligands having a cyclopentadienyl skeleton, and it is preferable that each ligand having a cyclopentadienyl skeleton is bound to each other by a bridging group. Examples of the bridging group include a substituted silylene group such as an alkylene group having 1 to 4 carbon atoms, a silylene group, a dialkylsilylene group, and a diarylsilylene group; A substituted silylene group is preferred.

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

The transition metal compound of Group IV of the periodic table containing the above-mentioned ligand having a cyclopentadienyl skeleton can use one kind or a mixture of two or more kinds as a catalyst component.

The co-catalyst is a co-catalyst that can effectively use the transition metal compound of Group IV of the periodic table as a polymerization catalyst or that can balance the ionic charge in a catalytically activated state. As the co-catalyst, a benzene-soluble aluminoxane of an organoaluminum oxy compound, a benzene-insoluble organoaluminum oxy compound, an ion-exchange layered silicate, a boron compound, a cation with or without an active hydrogen group and a non-coordinating anion are used. And lanthanoid salts such as lanthanum oxide, tin oxide, and a phenoxy compound containing a fluoro group.

The group IV transition metal compound of the periodic table containing a ligand having a cyclopentadienyl skeleton may be used by supporting it on an inorganic or organic compound carrier. As the carrier, an inorganic or organic compound porous oxide is preferable, and 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.

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

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

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

The above resin composition has a density of 0.91 to 0.96 g/cm ³ , preferably 0.915 to 0.955 g/cm ³ , and more preferably 0.92 to 0.95 g/cm ^3. is there. The density of the resin composition is a value measured according to the method defined in the method A of JIS K7112-1980 after performing the annealing described in JIS K6760-1995. When the density of the resin composition is 0.91 g/cm ³ or more, the rigidity of the resin film made of the resin composition can be increased. When the density of the resin composition is 0.96 g/cm ³ or less, the transparency and mechanical strength of the resin film made of the resin composition can be increased.

The resin composition has a melt flow rate (MFR) of 1 to 30 g/10 minutes, preferably 1.5 to 6.0 g/10 minutes by the inflation method and 4 to 20 g/10 minutes by the T-die method. It is a thing. 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. When the MFR of the resin composition is 1 g/10 minutes or more, the extrusion load during molding can be reduced. When the MFR of the resin composition is 30 g/10 minutes or less, the mechanical strength of the resin film made of the resin composition can be increased.

The above resin composition may include two or more kinds of polyolefins having different biomass degrees, and the concentration of ethylene derived from the biomass in the entire resin composition may be within the above range.

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

According to an aspect of the present invention, the resin composition is preferably 5-90 wt%, more preferably 25-75 wt% biomass-derived polyolefin, preferably 10-95 wt%, more preferably 25-75 wt%. It contains a mass% of a fossil fuel-derived polyolefin. Even when the resin composition of such a mixture is used, the concentration of ethylene derived from the biomass may be within the above range for the entire resin composition.

In addition to the polyolefin as the main component, various additives may be added to the above resin composition production process or to the produced resin composition as long as the characteristics are not impaired. Examples of the additives include plasticizers, ultraviolet stabilizers, anti-coloring agents, matting agents, deodorants, flame retardants, weather resistance agents, antistatic agents, thread friction reducing agents, slip agents, release agents, An oxidizing agent, an ion exchange agent, a coloring 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 resin composition.

Resin film The resin film according to the present invention comprises the above resin composition, and the resin composition contains 5% by mass or more of biomass-derived ethylene with respect to the entire resin composition, thereby forming a carbon-neutral polyolefin resin film. realizable. Therefore, the amount of fossil fuel used can be significantly reduced as compared with the conventional one, and the environmental load can be reduced. Further, the polyolefin resin film of the present invention, as compared with a polyolefin resin film produced from a raw material obtained from a conventional fossil fuel, is comparable to physical properties such as mechanical properties, and thus replaces the conventional polyolefin resin film. be able to.

The method for producing the resin film according to the present invention is not particularly limited and can be produced by a conventionally known method. In the present invention, extrusion molding is preferable, and extrusion molding is more preferably performed by a T-die method or an inflation method.

For example, the resin film can be molded by extrusion molding by the following method. After drying the above-mentioned resin composition, 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 resin composition, for example, a die such as a T-die. A film can be formed by further extruding into a sheet and rapidly 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 according to the purpose.

The thickness of the resin film obtained as described above is arbitrary depending on its application, but is usually about 5 to 500 μm, preferably about 5 to 200 μm. Further, the resin film may be used as a single-layer film, or a plurality of laminated films may be used as a laminated film.

The resin film according to the present invention is used for various applications such as packaging products such as containers and 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 preferably used, and packaging products and sheet molded products are particularly preferred.

Other Embodiments A further object of the present invention is to provide a resin film comprising a resin composition containing a carbon-neutral polyolefin using ethylene derived from biomass, which is produced from a raw material obtained from a conventional fossil fuel. Another object of the present invention is to provide a polyolefin resin film which is comparable to the resin film in physical properties such as mechanical properties.
A resin film according to another aspect of the present invention is composed of a resin composition containing a biomass-derived polyolefin obtained by polymerizing a monomer containing biomass-derived ethylene,
The above resin composition contains 5% by mass or more of the above biomass-derived ethylene with respect to the entire above resin composition, and the above resin composition has a density of 0.91 to 0.96 g/cm ³ . Is to have.
In another aspect of the present invention, the above resin composition may have a melt flow rate of 1 to 30 g/10 minutes.
In another aspect of the present invention, the resin composition may contain the biomass-derived ethylene in an amount of 5 to 95% by mass with respect to the entire resin composition.
In another aspect of the present invention, the above monomer may further include fossil fuel-derived ethylene and/or α-olefin.
In another aspect of the present invention, the above-mentioned monomer may further include a biomass-derived α-olefin.
In another embodiment of the present invention, the resin composition further comprises a fossil fuel-derived polyolefin obtained by polymerizing a fossil fuel-derived ethylene and a monomer containing fossil fuel-derived ethylene and/or α-olefin. May be included.
In another aspect of the present invention, the resin composition contains 5 to 90% by mass of the biomass-derived polyolefin and 10 to 95% by mass of the fossil fuel-derived polyolefin. Good.
In another aspect of the present invention, the α-olefin may be butylene, hexene, or octene.
In another aspect of the invention, the polyolefin may be polyethylene.
In another aspect of the present invention, a resin film formed by extrusion molding the above resin composition may be used.
In another aspect of the present invention, the extrusion molding may be performed by a T-die method or an inflation method.
In another aspect of the present invention, a packaged product comprising the above resin film is provided.
In another aspect of the present invention, there is provided a sheet molded article made of the above resin film.
According to the present invention as described above, the polyolefin resin film is made of a resin composition containing a biomass-derived polyolefin obtained by polymerizing a monomer containing biomass-derived ethylene, and the biomass-derived ethylene is added to the entire resin composition. On the other hand, when the content is 5% by mass or more, a carbon-neutral polyolefin resin film can be realized. Therefore, it is possible to significantly reduce the amount of fossil fuel used as compared with the related art, and it is possible to reduce the environmental load.
Further, the polyolefin resin film of the present invention, as compared with a polyolefin resin film produced from a raw material obtained from a conventional fossil fuel, is comparable to physical properties such as mechanical properties, and thus replaces the conventional polyolefin resin film. be able to.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto.

Measurement/Conditions In the following Examples 1 to 7 and Comparative Examples 1 and 2, the biomass degree is a value of the content of carbon derived from biomass by measurement of radioactive carbon (C14).

Production of Resin Film The conditions of the extrusion film forming machine used in Examples 1 to 7 and Comparative Examples 1 and 2 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: 560mm

Example 1
Biomass-derived high-density polyethylene (manufactured by Braskem, trade name: SHA7260, biomass degree: 94.5%, density: 0.955 g/cm ³ , MFR: 20 g/10 minutes) at a resin temperature of 290° C. A resin film was obtained by extrusion onto a 12 μm PET film (manufactured by Toyobo Co., Ltd., trade name: E5100). The conditions of the extrusion molding were set such that the effective width was 560 mm, the extrusion thickness was 30 μm, and the extrusion speed was 100 m/min.

Example 2
50 parts by mass of biomass-derived high-density polyethylene (manufactured by Braskem, trade name: SHA7260, biomass degree: 94.5%, density: 0.955 g/cm ³ , MFR: 20 g/10 min) and low fossil fuel-derived low A resin dry-blended with 50 parts by mass of density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: LC701, biomass degree: 0%, density: 0.919 g/cm ³ , MFR: 14 g/10 minutes) (biomass degree: 48% , Density: 0.937 g/cm ³ , MFR: 17 g/10 min) at a resin temperature of 290° C. onto a 12 μm-thick PET film (manufactured by Toyobo Co., Ltd., trade name: E5100) to form a resin film. Obtained.
The conditions of the extrusion molding were set such that the effective width was 560 mm, the extrusion thickness was 30 μm, and the extrusion speed was 100 m/min.

Example 3
33 parts by mass of biomass-derived high-density polyethylene (manufactured by Braskem, trade name: SHA7260, biomass degree: 94.5%, density: 0.955 g/cm ³ , MFR: 20 g/10 min), and low fossil fuel-derived low A resin dry-blended with 67 parts by mass of density polyethylene (manufactured by Nippon Polyethylene, trade name: LC701, biomass degree: 0%, density: 0.919 g/cm ³ , MFR: 14 g/10 minutes) (biomass degree: 32% , Density: 0.931 g/cm ³ , MFR: 16 g/10 min) at a resin temperature of 290° C. onto a 12 μm-thick PET film (manufactured by Toyobo Co., Ltd., trade name: E5100) to form a resin film. Obtained.
The conditions of the extrusion molding were set such that the effective width was 560 mm, the extrusion thickness was 30 μm, and the extrusion speed was 100 m/min.

Comparative Example 1
Fossil fuel-derived low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: LC701, degree of biomass: 0%, density: 0.919 g/cm ³ , MFR: 14 g/10 minutes) at a resin temperature of 290° C. A resin film was obtained by extrusion onto a 12 μm PET film (manufactured by Toyobo Co., Ltd., trade name: E5100). The conditions of the extrusion molding were set such that the effective width was 560 mm, the extrusion thickness was 30 μm, and the extrusion speed was 100 m/min.

Evaluation of Resin Composition and Resin Film Regarding the processability of the resin compositions used in Examples 1 to 3 and Comparative Example 1 and the properties of the obtained film, the following various evaluations were performed: (1) drawdown, (2) ) Neck-in, (3) motor load, (4) resin pressure, and (5) loop stiffness were performed.

(1) Drawdown The resin compositions used in Examples 1 to 3 and Comparative Example 1 were processed under the conditions of a T die width of 560 mm, a resin temperature of 290° C., and a screw rotation speed of 34 rpm using the above extrusion film forming machine. Then, the maximum take-up speed (m/min) at which the extrusion coating film was broken or surging was measured.
The measurement results were as shown in Table 1 below.

(2) Neck-in The resin composition used in the above Examples 1 to 3 and Comparative Example 1 was subjected to a take-up speed using the above extrusion film forming machine under the conditions of T die width of 560 mm and screw rotation speed of 105 rpm. The binaural neck-in (mm) was measured at 140 m/min and an air gap of 120 mm. The measurement results were as shown in Table 1 below.

(3) Motor Load In each of Examples 1 to 3 and Comparative Example 1 described above, the motor load (A) when the resin film was manufactured using the extrusion film forming machine was measured. The measurement results were as shown in Table 1 below.

(4) Resin Pressure In the above Examples 1 to 3 and Comparative Example 1, the resin pressure (MPa) when the resin film was manufactured using the above extrusion film forming machine was measured. The measurement results were as shown in Table 1 below.

(5) Loop Stiffness The resin films obtained in the above Examples 1 to 3 and Comparative Example 1 were cut into a piece having a width of 15 mm and a length of 150 mm, and a rigidity tester (trade name: Loop Stephen Tester manufactured by Toyo Seiki Seisaku-sho, Ltd. ) Was used to measure the rigidity (N) of the film. The length of the loop was 60 mm. The measurement results were as shown in Table 1 below.

Example 4
Biomass-derived linear low-density polyethylene (manufactured by Braskem, trade name: SLL318, biomass degree: 87%, density: 0.918 g/cm ³ , MFR: 2.7 g/10 minutes) was added to a resin temperature of 320°C. Then, a 12 μm thick PET film (manufactured by Toyobo Co., Ltd., trade name: E5100) was extruded to obtain a resin film. The conditions of the extrusion molding were set such that the effective width was 560 mm, the extrusion thickness was 30 μm, and the extrusion speed was 100 m/min.

Example 5
33 parts by mass of linear low-density polyethylene derived from biomass (Blaskem: SLL318, biomass degree: 87%, density: 0.918 g/cm ³ , MFR: 2.7 g/10 min), and low fossil fuel-derived low 67 parts by mass of density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: LC604, biomass degree: 0%, density: 0.918 g/cm ³ , MFR: 8 g/10 minutes) was melt-blended (biomass degree: 29% , Density: 0.918 g/cm ³ , MFR: 6.3 g/10 min) at a resin temperature of 320° C. and extruded onto a PET film (manufactured by Toyobo Co., Ltd., trade name: E5100) having a thickness of 12 μm. I got a film. The conditions of the extrusion molding were set such that the effective width was 560 mm, the extrusion thickness was 30 μm, and the extrusion speed was 100 m/min.

Example 6
33 parts by mass of biomass-derived linear low-density polyethylene (manufactured by Braskem, trade name: SLL318, biomass degree: 87%, density: 0.918 g/cm ³ , MFR: 2.7 g/10 min), and fossil fuel 37 parts by mass of low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: LC604, biomass degree: 0%, density: 0.918 g/cm ³ , MFR: 8 g/10 minutes) and a straight chain derived from fossil fuel 30 parts by mass of low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: KC573, degree of biomass: 0%, density: 0.910 g/cm ³ , MFR: 15 g/10 minutes) was melt-blended (degree of biomass: 29 %, density: 0.916 g/cm ³ , MFR: 8.4 g/10 minutes) at a resin temperature of 320° C. onto a 12 μm-thick PET film (manufactured by Toyobo Co., Ltd., trade name: E5100), A resin film was obtained. The conditions of the extrusion molding were set such that the effective width was 560 mm, the extrusion thickness was 30 μm, and the extrusion speed was 100 m/min.

Example 7
33 parts by mass of biomass-derived linear low-density polyethylene (manufactured by Braskem, trade name: SLL318, biomass degree: 87%, density: 0.918 g/cm ³ , MFR: 2.7 g/10 min), and fossil fuel 37 parts by mass of low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: LC604, biomass degree: 0%, density: 0.918 g/cm ³ , MFR: 8 g/10 minutes) and a straight chain derived from fossil fuel 30 parts by mass of low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: KS560T, degree of biomass: 0%, density: 0.898 g/cm ³ , MFR: 16 g/10 minutes) was melt-blended (the degree of biomass was 29. %, density 0.912 g/cm ³ , MFR 8.7 g/10 min) at a resin temperature of 320° C. and extruded onto a PET film (manufactured by Toyobo Co., Ltd., trade name: E5100) having a thickness of 12 μm. A resin film was obtained. The conditions of the extrusion molding were set such that the effective width was 560 mm, the extrusion thickness was 30 μm, and the extrusion speed was 100 m/min.

Comparative example 2
Fossil fuel-derived low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: LC600A, degree of biomass: 0%, density: 0.919 g/cm ³ , MFR: 7 g/10 minutes) at a resin temperature of 320° C. A resin film was obtained by extrusion onto a 12 μm PET film (manufactured by Toyobo Co., Ltd., trade name: E5100). The conditions of the extrusion molding were set such that the effective width was 560 mm, the extrusion thickness was 30 μm, and the extrusion speed was 100 m/min.

Evaluation of Resin Composition and Resin Film Regarding the processability of the resin compositions used in Examples 4 to 7 and Comparative Example 2 and the characteristics of the obtained film, the following various evaluations were performed: (6) drawdown, (7) ) Neck-in, (8) motor load, (9) resin pressure, (10) sealing start temperature were performed.

(6) Drawdown The resin composition used in the above Examples 4 to 7 and Comparative Example 2 was subjected to T die width of 560 mm, resin temperature of 290° C., and screw rotation speed of 34 rpm using the above extrusion film forming machine. Then, the maximum take-up speed (m/min) at which the extrusion coating film was broken or surging was measured. The measurement results were as shown in Table 2 below.

(7) Neck-in The resin compositions used in the above Examples 4 to 7 and Comparative Example 2 were subjected to a take-up speed using the above extrusion film-forming machine under the conditions of a T-die width of 560 mm and a screw rotation speed of 105 rpm. The binaural neck-in (mm) was measured at 140 m/min and an air gap of 120 mm. The measurement results were as shown in Table 2 below.

(8) Motor Load In each of Examples 4 to 7 and Comparative Example 2 described above, the motor load (A) when the resin film was manufactured using the extrusion film forming machine was measured. The measurement results were as shown in Table 2 below.

(9) Resin Pressure In the above Examples 4 to 7 and Comparative Example 2, the resin pressure (MPa) when the resin film was produced using the above extrusion film forming machine was measured. The measurement results were as shown in Table 2 below.

(10) Sealing start temperature The resin films obtained in the above Examples 4 to 7 and Comparative Example 2 were cut into a width of 15 mm and a length of 200 mm, and the sealing temperature was 90 to 150°C and the sealing pressure was 30 N/cm. ^{2. The} sealing time was 1 second, and heat sealing was performed to specify the temperature (° C.) at which the sealing was started. The measurement results were as shown in Table 2 below.

Claims (13)

Single-layer packaging made of a resin composition containing biomass-derived high-density polyethylene obtained by polymerizing biomass-derived ethylene-containing monomers and fossil fuel-derived polyethylene obtained by polymerizing fossil fuel-derived ethylene-containing monomers A polyethylene resin film for wood,
For the single-layer packaging material, wherein the resin composition contains 5% by mass or more of the biomass-derived high-density polyethylene with respect to the entire resin composition, and the biomass content of the resin composition is 48% or less. Polyethylene resin film. The polyethylene resin film for packaging materials according to claim 1, wherein the resin composition has a density of 0.91 to 0.96 g/cm ³ . The resin composition has a melt flow rate of 1 to 30 g/10 minutes when measured by the method A under the conditions of a temperature of 190° C. and a load of 21.18 N in the method specified in JIS K7210-1995. The polyethylene resin film for packaging material according to claim 1 or 2. The resin composition comprises a plasticizer, an ultraviolet stabilizer, a coloring preventing agent, a matting agent, a deodorant, a flame retardant, a weathering agent, an antistatic agent, a yarn friction reducing agent, a slip agent, a release agent, and an antioxidant. The polyethylene resin film for a packaging material according to any one of claims 1 to 3, which comprises one or more additives selected from agents, ion exchangers, and color pigments. 5. The resin composition according to claim 1, wherein the resin composition comprises 5 to 50% by mass of the biomass-derived high-density polyethylene and 10 to 50% by mass of the fossil fuel-derived low-density polyethylene. A polyethylene resin film for the packaging material described. It is a manufacturing method of the polyethylene resin film for packaging materials as described in any one of Claims 1-5,
A method for producing, characterized in that the resin composition is extruded. The manufacturing method according to claim 6, wherein the extrusion molding is performed by a T-die method or an inflation method. A packaged product comprising the polyethylene resin film for packaging material according to claim 1. A sheet molded article, comprising the polyethylene resin film for a packaging material according to claim 1. Label material provided with the polyethylene resin film for packaging materials as described in any one of Claims 1-5. A lid member comprising the polyethylene resin film for a packaging material according to claim 1. A laminated tube comprising the polyethylene resin film for a packaging material according to claim 1. A bag comprising the polyethylene resin film for a packaging material according to claim 1.