JP2019094509A - Polyolefin resin film - Google Patents

Abstract

To provide a resin film formed of a resin composition containing carbon neutral polyolefin using ethylene derived from biomass.SOLUTION: A resin film is formed of a resin composition containing polyethylene derived from biomass formed by polymerization a monomer containing ethylene derived from biomass and polyethylene derived from a fossil fuel formed by polymerization of a monomer containing ethylene derived from a fossil fuel, in which the resin film contains one or two or more impurities selected from the group consisting of a carbonyl compound and a nitrogen-containing compound of amine and amine acid, the resin composition contains 5 mass% or more of the ethylene derived from the biomass to the whole resin composition, and the resin composition has a density of 0.91-0.96 g/cm.SELECTED DRAWING: None

Description

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

  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, polyvinyl chloride, polystyrene, ABS resin, etc. 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 resin film, and instead of ethylene obtained from a conventional fossil fuel, a polyolefin resin film using ethylene derived from biomass as the raw material is obtained from a conventional fossil fuel We obtained the finding that a polyolefin resin film produced using ethylene and a film 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 provide a resin film comprising a resin composition containing a carbon neutral polyolefin using biomass-derived ethylene, wherein the resin film is produced from raw materials obtained from conventional fossil fuels And providing a polyolefin resin film which is comparable in physical properties such as mechanical properties.

According to an aspect of the present invention, it comprises biomass-derived polyethylene obtained by polymerizing a monomer derived from biomass-derived ethylene, and fossil fuel-derived polyethylene obtained by polymerizing a monomer derived from fossil fuel-derived ethylene. A resin film comprising a resin composition, wherein
The resin film contains one or more impurities selected from the group consisting of carbonyl compounds, amines and nitrogen-containing compounds of amino acids,
The resin, wherein the resin composition contains 5% by mass or more of ethylene derived from the biomass with respect to the entire resin composition, and the resin composition has a density of 0.91 to 0.96 g / cm ³ A film is provided.

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

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

  In an aspect of the present invention, the α-olefin may be butylene, hexene or octene.

  In an aspect of the present invention, there is provided a packaged product comprising the resin film.

  In the aspect of this invention, the sheet | seat molded article provided with the said resin film is provided.

  In the aspect of this invention, the label material provided with the said resin film is provided.

  In the aspect of this invention, the lid material provided with the said resin film is provided.

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

  In the aspect of this invention, the laminated | multilayer film provided with the said resin film are provided.

  In an aspect of the present invention, a bag provided with the resin film is provided.

According to the present invention, the polyolefin resin film comprises: biomass-derived polyethylene obtained by polymerizing monomers containing biomass-derived ethylene; and fossil fuel-derived polyethylene obtained by polymerizing the monomers containing fossil fuel-derived ethylene A carbon neutral polyolefin resin film can be realized by containing a resin composition containing 5% by mass or more of ethylene derived from biomass with respect to the entire resin composition. 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 polyolefin resin film of the present invention substitutes the conventional polyolefin resin film because it is comparable in physical properties such as mechanical properties to the polyolefin resin film produced from the raw material obtained from the conventional fossil fuel. be able to.

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 weight 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 together a caustic water treatment 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.

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 biomass-derived resin film do not have to have a biomass degree of 100%. This is because, in accordance with the present invention, the amount of fossil fuel used can be reduced as compared to the conventional method if the biomass-derived material is used even for a part of the resin film.

  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.

Resin Composition In the present invention, the resin composition contains the above-described polyolefin as a main component. The resin composition comprises 5% by mass or more, preferably 5 to 95% by mass, 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 prior art, 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 , 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 specified in method A of JIS K7112-1980 after annealing described in JIS K6760-1995. If 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 enhanced. 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 enhanced.

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

  The above resin composition may contain two or more types of polyolefins having different degrees of biomass, and the concentration of ethylene derived from biomass may be within the above range as the whole resin composition.

  The above 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 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 embodiment of the present invention, the 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 to 75%. And polyolefins of fossil fuel origin. Even when the resin composition of such a mixture is used, the concentration of ethylene derived from biomass may be within the above range as the entire resin composition.

  Various additives may be added to the above-mentioned resin composition production process or to the produced resin composition, in addition to the main component polyolefin, as long as the characteristics are not impaired. 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 an amount of 1 to 20% by mass, preferably 1 to 10% by mass, based on the entire resin composition.

Resin Film A resin film according to the present invention comprises the above resin composition, and the resin composition contains 5% by mass or more of ethylene derived from biomass with respect to the entire resin composition, whereby a carbon neutral polyolefin resin film is obtained. 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 polyolefin resin film of the present invention substitutes the conventional polyolefin resin film because it is comparable in physical properties such as mechanical properties to the polyolefin resin film produced from the raw material obtained from the conventional fossil fuel. be able to.

  The manufacturing method of the resin film by this invention is not specifically limited, It can manufacture by a conventionally well-known method. In the present invention, extrusion molding is preferred, and extrusion molding is more preferably performed by a T-die method or inflation method.

  For example, the resin film can be formed by extrusion in the following manner. After drying the resin composition described above, 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 extruding into a sheet-like shape and quenching and solidifying the extruded sheet-like 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 resin film obtained as mentioned above is arbitrary according to the use, it is usually about 5-500 micrometers, Preferably it is about 5-200 micrometers. The resin film may be used as a single layer film or may be used as a laminated film by laminating a plurality of sheets.

Applications The resin film according to the present invention is used for various applications such as packaging products such as containers and bags, sheet molded 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, and in particular, packaged products and sheet-formed articles are preferable.

Other Aspects The object of the present invention is to provide a resin film comprising a resin composition containing a carbon neutral polyolefin using biomass-derived ethylene, wherein the resin is produced from raw materials obtained from conventional fossil fuels It is an object of the present invention to provide a polyolefin resin film which is not inferior to the film in terms of physical properties such as mechanical properties.
A resin film according to another aspect of the present invention comprises a resin composition comprising a biomass-derived polyolefin obtained by polymerization of a monomer derived from biomass-derived ethylene,
The above resin composition contains 5% by mass or more of ethylene derived from the above biomass 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 The
In another aspect of the present invention, the above resin composition may have a melt flow rate of 1 to 30 g / 10 min.
In another aspect of the present invention, the above resin composition may contain 5 to 95% by mass of ethylene derived from the above biomass with respect to the entire above resin composition.
In another aspect of the invention, the above mentioned monomers may further comprise ethylene and / or alpha-olefins derived from fossil fuels.
In another aspect of the present invention, the above-mentioned monomer may further comprise an α-olefin derived from biomass.
In another aspect of the present invention, the resin composition further comprises a polyolefin derived from fossil fuel, which is obtained by polymerizing a monomer containing ethylene derived from fossil fuel and ethylene and / or α-olefin derived from fossil fuel May be included.
In another aspect of the present invention, the above-mentioned resin composition comprises 5-90% by mass of the biomass-derived polyolefin and 10-95% by mass of the fossil fuel-derived polyolefin. It is also good.
In another aspect of the present invention, the above-mentioned α-olefin may be butylene, hexene or octene.
In another aspect of the invention, the polyolefin described above may be polyethylene.
In the other aspect of this invention, the resin film which said resin composition is extrusion-molded may be sufficient.
In another aspect of the present invention, the above-mentioned extrusion may be performed by a T-die method or an inflation method.
In another aspect of the present invention, there is provided a packaged product comprising the above-mentioned resin film.
In another aspect of the present invention, there is provided a sheet molded article comprising the above-described resin film.
According to the present invention, the polyolefin resin film is made of a resin composition comprising a polyolefin derived from biomass formed by polymerization of a monomer derived from biomass, and ethylene derived from biomass is used in the entire resin composition. On the other hand, by containing 5% by mass or more, a carbon neutral polyolefin resin film 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 polyolefin resin film of the present invention substitutes the conventional polyolefin resin film because it is comparable in physical properties such as mechanical properties to the polyolefin resin film produced from the raw material obtained from the conventional fossil fuel. be able to.

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

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

Production of Resin Film The conditions of the extrusion film-forming machine used in the following Examples 1 to 7 and Comparative Examples 1 and 2 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
Thickness of high density polyethylene derived from biomass (Braskem, trade name: SHA7260, degree of biomass: 94.5%, density: 0.955 g / cm ³ , MFR: 20 g / 10 min) at a resin temperature of 290 ° C. It was extruded on a 12 μm PET film (Toyobo Co., Ltd., trade name: E5100) to obtain a laminated film. The extrusion conditions were set to an effective width of 560 mm, an extrusion thickness of 30 μm, and an extrusion speed of 100 m / min.

Example 2
50 parts by mass of high-density polyethylene derived from biomass (manufactured by Braskem, trade name: SHA7260, degree of biomass: 94.5%, density: 0.955 g / cm ³ , MFR: 20 g / 10 min) and fossil fuel-derived low Resin (dry weight: 48%) dry blended with 50 parts by weight of high density polyethylene (trade name: LC 701, biomass degree: 0%, density: 0.919 g / cm ³ , MFR: 14 g / 10 min) , 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 (Toyobo Co., Ltd., trade name: E5100) to form a laminated film Obtained.
The extrusion conditions were set to an effective width of 560 mm, an extrusion thickness of 30 μm, and an extrusion speed of 100 m / min.

Example 3
33 parts by mass of high-density polyethylene derived from biomass (manufactured by Braskem, trade name: SHA7260, degree of biomass: 94.5%, density: 0.955 g / cm ³ , MFR: 20 g / 10 min) and fossil fuel-derived low Resin (biomass degree: 32%) dry-blended with density polyethylene (trade name: LC701, biomass degree: 0%, density: 0.919 g / cm ³ , MFR: 14 g / 10 min) manufactured by Japan Polyethylene Corporation and 67 parts by mass , 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 (Toyobo Co., Ltd., trade name: E5100) to form a laminated film Obtained.
The extrusion conditions were set to an effective width of 560 mm, an extrusion thickness of 30 μm, and an extrusion speed of 100 m / min.

Comparative Example 1
Low-density polyethylene derived from fossil fuel (manufactured by Japan Polyethylene Corporation, trade name: LC 701, biomass degree: 0%, density: 0.919 g / cm ³ , MFR: 14 g / 10 min) at a resin temperature of 290 ° C. It was extruded on a 12 μm PET film (Toyobo Co., Ltd., trade name: E5100) to obtain a laminated film. The extrusion conditions were set to an effective width of 560 mm, an extrusion thickness of 30 μm, and an extrusion speed of 100 m / min.

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

(1) Drawdown The conditions of T die width 560 mm, resin temperature 290 ° C., screw rotation speed 34 rpm, using the above-described extrusion film forming machine, for the resin composition used in Examples 1 to 3 and Comparative Example 1 above. The maximum draw speed (m / min) at which the extrusion coating film broke 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 drawn using the above-described extrusion film forming machine under conditions of T-die width 560 mm and screw rotation speed 105 rpm. The binaural neck-in (mm) was measured when the air gap was 140 mm and the air gap was 120 mm. The measurement results were as shown in Table 1 below.

(3) Motor Load In Examples 1 to 3 and Comparative Example 1 described above, motor load (A) was measured when a resin film was produced using the above-described extrusion film-forming machine. 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) at the time of producing a resin film 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 are cut into a width of 15 mm and a length of 150 mm, and a stiffness tester (manufactured by Toyo Seiki Seisakusho, trade name: Loop stiffness tester) ) Was used to measure the stiffness (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 (Braskem, trade name: SLL 318, biomass degree: 87%, density: 0.918 g / cm ³ , MFR: 2.7 g / 10 min) at a resin temperature of 320 ° C. The resultant was extruded on a 12 μm thick PET film (manufactured by Toyobo Co., Ltd., trade name: E5100) to obtain a laminated film. The extrusion conditions were set to an effective width of 560 mm, an extrusion thickness of 30 μm, and an extrusion speed of 100 m / min.

Example 5
33 parts by mass of linear low density polyethylene derived from biomass (Braske: SLL 318, degree of biomass: 87%, density: 0.918 g / cm ³ , MFR: 2.7 g / 10 min), and fossil fuel-derived low Resin obtained by melt blending 67 parts by mass of density polyethylene (trade name: LC604, degree of biomass: 0%, density: 0.918 g / cm ³ , MFR: 8 g / 10 min) (manufactured by Japan Polyethylene Corporation) (degree of biomass: 29% , Density: 0.918 g / cm ³ , MFR: 6.3 g / 10 min) at a resin temperature of 320 ° C. onto a 12 μm thick PET film (Toyobo Co., Ltd., trade name: E5100) and laminating I got a film. The extrusion conditions were set to an effective width of 560 mm, an extrusion thickness of 30 μm, and an extrusion speed of 100 m / min.

Example 6
33 parts by mass of linear low density polyethylene derived from biomass (Braskem, trade name: SLL 318, biomass degree: 87%, density: 0.918 g / cm ³ , MFR: 2.7 g / 10 min), fossil fuel 37 parts by mass of low density polyethylene derived from Japan (manufactured by Japan Polyethylene, trade name: LC604, biomass degree: 0%, density: 0.918 g / cm ³ , MFR: 8 g / 10 min), linear fossil fuel derived Resin obtained by melt blending 30 parts by mass of low density polyethylene (trade name: KC 573, biomass degree: 0%, density: 0.910 g / cm ³ , MFR: 15 g / 10 min, manufactured by Japan Polyethylene Corporation) (biomass degree: 29 %, Density: 0.916 g / cm ³ , MFR: 8.4 g / 10 min, at a resin temperature of 320 ° C., a PET film of 12 μm thickness (east The laminated film was obtained by extruding onto a product of YOKOSMO CO., LTD., Trade name: E5100). The extrusion conditions were set to an effective width of 560 mm, an extrusion thickness of 30 μm, and an extrusion speed of 100 m / min.

Example 7
33 parts by mass of linear low density polyethylene derived from biomass (Braskem, trade name: SLL 318, biomass degree: 87%, density: 0.918 g / cm ³ , MFR: 2.7 g / 10 min), fossil fuel 37 parts by mass of low density polyethylene derived from Japan (manufactured by Japan Polyethylene, trade name: LC604, biomass degree: 0%, density: 0.918 g / cm ³ , MFR: 8 g / 10 min), linear fossil fuel derived Resin (a biomass degree is 29) obtained by melt-blending 30 parts by mass of low density polyethylene (trade name: KS 560 T, biomass degree: 0%, density: 0.898 g / cm ³ , MFR: 16 g / 10 min) %, Density 0.912 g / cm ³ , MFR 8.7 g / 10 min, at a resin temperature of 320 ° C., a 12 μm thick PET film ( A laminated film was obtained by extruding onto Toyobo Co., Ltd., trade name: E5100). The extrusion conditions were set to an effective width of 560 mm, an extrusion thickness of 30 μm, and an extrusion speed of 100 m / min.

Comparative example 2
Low-density polyethylene derived from fossil fuel (manufactured by Japan Polyethylene, trade name: LC600A, biomass degree: 0%, density: 0.919 g / cm ³ , MFR: 7 g / 10 min) at a resin temperature of 320 ° C. It was extruded on a 12 μm PET film (Toyobo Co., Ltd., trade name: E5100) to obtain a laminated film. The extrusion conditions were set to an effective width of 560 mm, an extrusion thickness of 30 μm, and an extrusion speed of 100 m / min.

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

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

(7) Neck-in The resin composition used in the above Examples 4 to 7 and Comparative Example 2 was drawn using the above-described extrusion film forming machine under the conditions of T die width 560 mm and screw rotational speed 105 rpm. The binaural neck-in (mm) was measured when the air gap was 140 mm and the air gap was 120 mm. The measurement results were as shown in Table 2 below.

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

(9) Resin Pressure In Examples 4 to 7 and Comparative Example 2 described above, the resin pressure (MPa) at the time of producing a resin film using the above-described 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 are cut out to a thickness of 15 mm and a length of 200 mm, the sealing temperature is 90 to 150 ° C., and the sealing pressure is 30 N / cm. ^{2. The} seal time was heat sealed in 1 second to specify the temperature (° C.) at which the seal starts. The measurement results were as shown in Table 2 below.

Claims (11)

A resin film comprising a resin composition comprising a biomass-derived polyethylene formed by polymerization of a biomass-derived ethylene-containing monomer and a fossil fuel-derived polyethylene formed by polymerization of a fossil fuel-derived ethylene There,
The resin film contains one or more impurities selected from the group consisting of carbonyl compounds, amines and nitrogen-containing compounds of amino acids,
The resin, wherein the resin composition contains 5% by mass or more of ethylene derived from the biomass with respect to the entire resin composition, and the resin composition has a density of 0.91 to 0.96 g / cm ³ the film.   The resin film according to claim 1, wherein the biomass-derived ethylene-containing monomer further comprises a fossil fuel-derived ethylene and / or an α-olefin.   The resin film according to claim 1, wherein the monomer containing ethylene derived from biomass further comprises an α-olefin derived from biomass.   The resin film according to claim 2 or 3, wherein the α-olefin is butylene, hexene or octene.   The packaged product provided with the resin film as described in any one of Claims 1-4.   The sheet | seat molded article provided with the resin film as described in any one of Claims 1-4.   The label material provided with the resin film as described in any one of Claims 1-4.   The lid material provided with the resin film as described in any one of Claims 1-4.   The lamination tube provided with the resin film as described in any one of Claims 1-4.   The laminated film provided with the resin film as described in any one of Claims 1-4.   The bag provided with the resin film as described in any one of Claims 1-4.