JP2017193722A - Polyolefin resin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin film comprising a resin composition that includes polyolefin of carbon neutral that uses ethylene of a biomass origin.MEANS: The resin film comprises the resin composition that includes the polyolefin of a biomass origin in which a monomer including ethylene of a biomass origin is polymerized. The resin composition includes at least 5 mass% of the ethylene of a biomass origin based on the total of the resin composition. 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 comprising a biomass-derived polyolefin obtained by polymerizing a monomer containing biomass-derived ethylene.

  In recent years, with the growing demand for the establishment of a recycling-oriented society, the use of biomass has been attracting attention in the materials field, as it is desired to move away from fossil fuels as well as energy. Biomass is an organic compound photo-synthesized from carbon dioxide and water, and by using it, it is so-called carbon neutral renewable energy that becomes carbon dioxide and water again. In recent years, biomass plastics using these biomasses as raw materials have been rapidly put into practical use, and attempts have been made to produce various resins from biomass raw materials.

  As a biomass-derived resin, commercial production of polylactic acid (PLA) produced via lactic acid fermentation has begun, but it is biodegradable, and its performance as a plastic is now a general-purpose plastic. Therefore, it has not been widely used due to its limitations in product applications and product manufacturing methods. Moreover, life cycle assessment (LCA) evaluation is performed for PLA, and discussion is made on energy consumption at the time of PLA production, equivalence at the time of replacement of general-purpose plastics, and the like.

  Here, various types such as polyethylene, polyvinyl chloride, polystyrene, and ABS resin are used as the general-purpose plastic. In particular, polyethylene is molded into films, sheets, bottles, etc., and is used for various applications such as packaging materials, and is used in large amounts all over the world. For this reason, the use of conventional fossil fuel-derived polyethylene has a large environmental impact.

  Therefore, it is desired to reduce the amount of fossil fuel used by using raw materials derived from biomass for the production of polyethylene. For example, until now, it has been studied to produce ethylene and butylene as raw materials for polyolefin resin from renewable natural raw materials (see, for example, Patent Document 1).

Special table 2011-506628 gazette

  The present inventors have focused on ethylene, which is a raw material for polyolefin resin films, and instead of ethylene obtained from conventional fossil fuels, polyolefin resin films using biomass-derived ethylene as raw materials are obtained from conventional fossil fuels. The present inventors have obtained the knowledge that a polyolefin resin film produced using ethylene can be obtained, and a film inferior in physical properties such as mechanical properties can be obtained. The present invention is based on this finding.

  Accordingly, an object of the present invention is to provide a resin film comprising a resin composition containing carbon-neutral polyolefin using biomass-derived ethylene, and the resin film manufactured from a raw material obtained from a conventional fossil fuel Another object is to provide a polyolefin resin film that is inferior in terms of physical properties such as mechanical properties.

The resin film according to the present invention comprises a resin composition comprising a biomass-derived polyolefin formed by polymerizing monomers containing biomass-derived ethylene,
Said resin composition contains 5 mass% or more of said biomass-derived ethylene with respect to said whole resin composition, and said resin composition has a density of 0.91-0.96 g / cm < ³ >. It is characterized by having.

  In the embodiment of the present invention, the resin composition preferably has a melt flow rate of 1 to 30 g / 10 minutes.

  In the embodiment of the present invention, the resin composition may include 5 to 95% by mass of the biomass-derived ethylene with respect to the entire resin composition.

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

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

  In an embodiment of the present invention, the resin composition may further include 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. Good.

  In the embodiment of the present invention, the resin composition may include 5 to 90% by mass of the biomass-derived polyolefin and 10 to 95% by mass of the fossil fuel-derived polyolefin. .

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

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

  In the embodiment of the present invention, the resin composition is preferably a resin film obtained by extrusion molding.

  In the embodiment of the present invention, it is preferable that the extrusion molding is performed by a T-die method or an inflation method.

  In the aspect of this invention, it is preferable that it is a packaging product which consists of said resin film.

  In the aspect of this invention, it is preferable that it is a sheet molded product which consists of said resin film.

According to the present invention, the polyolefin resin film comprises a resin composition comprising a biomass-derived polyolefin formed by polymerizing a monomer containing ethylene derived from biomass, and the ethylene derived from biomass is 5 to the entire resin composition. By including at least mass%, a carbon neutral polyolefin resin film can be realized. Therefore, the amount of fossil fuel used can be greatly reduced compared to the conventional case, and the environmental load can be reduced.
In addition, the polyolefin resin film of the present invention is not inferior in terms of physical properties such as mechanical properties as compared to a polyolefin resin film produced from a raw material obtained from a conventional fossil fuel, and therefore substitutes for a conventional polyolefin resin film. be able to.

Biomass-derived ethylene In the present invention, a method for producing biomass-derived ethylene that is a raw material for biomass-derived polyolefin is not particularly limited, and can be obtained by a conventionally known method. Hereinafter, an example of a method for producing biomass-derived ethylene will be described.

  Biomass-derived ethylene can be produced using biomass-derived ethanol as a raw material. In particular, it is preferable to use biomass-derived fermented ethanol obtained from plant raw materials. A plant raw material is not specifically limited, A conventionally well-known plant can be used. For example, corn, sugar cane, beet, and manioc can be mentioned.

  In the present invention, biomass-derived fermented ethanol refers to ethanol that has been purified after contacting a microorganism-producing product or a crushed product thereof with a culture solution containing a carbon source obtained from plant raw materials. For the purification of ethanol from the culture solution, conventionally known methods such as distillation, membrane separation, and extraction can be applied. For example, a method of adding benzene, cyclohexane or the like and azeotropically or removing water by membrane separation or the like can be mentioned.

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

  When ethylene is obtained by a dehydration reaction of ethanol, a catalyst is usually used, but this catalyst is not particularly limited, and a conventionally known catalyst can be used. Advantageous in the process is a fixed bed flow reaction in which the catalyst and the product can be easily separated. For example, γ-alumina is preferable.

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

  The reaction pressure is not particularly limited, but a pressure equal to or higher than normal pressure is preferable in order to facilitate subsequent gas-liquid separation. Industrially, a fixed bed flow reaction in which separation of the catalyst is easy is suitable, but a liquid phase suspension bed, a fluidized bed, or the like may be used.

  In the dehydration reaction of ethanol, the yield of the reaction depends on the amount of water contained in ethanol supplied as a raw material. Generally, when performing a dehydration reaction, it is preferable that there is no water in view of water removal efficiency. However, in the case of ethanol dehydration reaction using a solid catalyst, it has been found that in the absence of water, the production of other olefins, particularly butene, tends to increase. It is presumed that ethylene dimerization after dehydration cannot be suppressed unless a small amount of water is present. The lower limit of the allowable water content is 0.1% or more, preferably 0.5% or more. The upper limit is not particularly limited, but is preferably 50% by 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 performing a dehydration reaction of ethanol in this way, a mixed part of ethylene, water and a small amount of unreacted ethanol can be obtained. Ethylene can be obtained except water and ethanol. This method may be performed by a known method.

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

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

  In addition, you may use caustic water treatment together as a refinement | purification method of the impurity in ethylene. In the case of performing caustic water treatment, it is desirable to perform it before adsorption purification. In that case, it is necessary to perform a water removal treatment after the caustic treatment and before the adsorption purification.

Polyolefin In the present invention, biomass-derived polyolefin is obtained by polymerizing monomers containing ethylene derived from biomass. It is preferable to use what was obtained by said manufacturing method for ethylene derived from biomass. Since ethylene derived from biomass is used as a monomer as a raw material, the polymerized polyolefin is derived from biomass. In addition, the raw material monomer of polyolefin does not need to contain 100 mass% of ethylene derived from biomass.

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

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

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

The biomass-derived ethylene concentration in the polyolefin (hereinafter sometimes referred to as “biomass degree”) is a value obtained by measuring the content of biomass-derived carbon by measurement of radioactive carbon (C14). Since carbon dioxide in the atmosphere contains C14 at a constant rate (105.5 pMC), the C14 content in plants that grow by incorporating carbon dioxide in the atmosphere, for example, corn, is also about 105.5 pMC. It is known. It is also known that fossil fuel contains almost no C14. Therefore, the proportion of carbon derived from biomass can be calculated by measuring the proportion of C14 contained in all carbon atoms in the polyolefin. In the present invention, in the case where the content of C14 in the polyolefin was P _C14, the content P _{bio Bio} carbon from biomass, can be obtained as follows.
P _bio (%) = P _C14 /105.5×100

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

  In the present invention, the biomass-derived polyolefin and the biomass-derived resin film need not have a biomass degree of 100%. This is because, if a biomass-derived raw material is used even for a part of the resin film, the amount of the fossil fuel used is reduced as compared with the conventional case.

  In the present invention, the polymerization method of the monomer containing ethylene derived from biomass is not particularly limited, and can be performed by a conventionally known method. The polymerization temperature and polymerization pressure are preferably adjusted as appropriate according to the polymerization method and polymerization apparatus. The polymerization apparatus is not particularly limited, and a conventionally known apparatus can be used. Hereinafter, an example of a method for polymerizing a monomer containing ethylene will be described.

  The polymerization method of polyolefins, particularly ethylene polymers and copolymers of ethylene and α-olefins, is the type of polyethylene of interest, such as high density polyethylene (HDPE), medium density polyethylene (MDPE), and low density polyethylene (LDPE). ), And linear low density polyethylene (LLDPE), etc. For example, as a polymerization catalyst, using a multi-site catalyst such as a Ziegler-Natta catalyst or a single site catalyst such as a metallocene catalyst, by any of gas phase polymerization, slurry polymerization, solution polymerization, and high-pressure ion polymerization, It is preferable to carry out by one stage or two or more stages.

  The above single-site catalyst is a catalyst that can form a uniform active species, and is usually adjusted by bringing a metallocene transition metal compound or a nonmetallocene transition metal compound into contact with an activation cocatalyst. . The single site catalyst is preferable because the active site structure is uniform as compared with the multisite catalyst, and a polymer having a high molecular weight and a high degree of uniformity can be polymerized. As the single site catalyst, it is particularly preferable to use a metallocene catalyst. The metallocene-based catalyst is a catalyst containing a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, a cocatalyst, and if necessary, an organometallic compound, and each catalyst component of the support. is there.

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

  In the group IV transition metal compound containing a ligand having a cyclopentadienyl skeleton, examples of the transition metal include zirconium, titanium, hafnium, and zirconium and hafnium are particularly preferable. The transition metal compound usually has two ligands having a cyclopentadienyl skeleton, and each ligand having a cyclopentadienyl skeleton is preferably bonded to each other via a bridging group. Examples of the crosslinking group include substituted alkylene groups such as C1-C4 alkylene groups, silylene groups, dialkylsilylene groups, and diarylsilylene groups, dialkylgermylene groups, and diarylgermylene groups. Preferably, it is a substituted silylene group.

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

  The transition metal compound of Group IV of the Periodic Table containing a ligand having a cyclopentadienyl skeleton can use one or a mixture of two or more as a catalyst component.

  The co-catalyst is one that can effectively make the above-mentioned group IV transition metal compound as a polymerization catalyst, or can neutralize ionic charges in a catalytically activated state. Co-catalysts include benzene-soluble aluminoxanes of organoaluminum oxy compounds, benzene-insoluble organoaluminum oxy compounds, ion-exchange layered silicates, boron compounds, active hydrogen group-containing or non-containing cations and non-coordinating anions. Ionic compounds, lanthanoid salts such as lanthanum oxide, tin oxide, phenoxy compounds containing a fluoro group, and the like.

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

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

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

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

The 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 a resin composition is a value measured according to the method prescribed | regulated to A method among JISK7112-1980, after performing annealing as described in JISK6760-1995. 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. Moreover, if the density of a resin composition is 0.96 g / cm < ³ > or less, the transparency and mechanical strength of the resin film which consist of this resin composition can be improved.

  The resin composition has a melt flow rate (MFR) of 1 to 30 g / 10 min, preferably 1.5 to 6.0 g / 10 min in the inflation method, and 4 to 20 g / 10 min in the T-die method. Is. The melt flow rate is a value measured by the method A under the conditions of a temperature of 190 ° C. and a load of 21.18 N in the method defined in JIS K7210-1995. If the MFR of the resin composition is 1 g / 10 min or more, the extrusion load during the molding process can be reduced. Moreover, if MFR of a resin composition is 30 g / 10min or less, the mechanical strength of the resin film which consists of this resin composition can be raised.

  Said resin composition may contain 2 or more types of polyolefin of different biomass degree, and the density | concentration of biomass-derived ethylene should just be in the said range as the whole resin composition.

  The resin composition may further include a fossil fuel-derived polyolefin formed by polymerization of a fossil fuel-derived ethylene and a fossil-fuel-derived ethylene and / or α-olefin monomer. 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 mixing can be performed by a conventionally known method. For example, a dry blend or a melt blend may be used.

  According to an aspect of the present invention, the resin composition is preferably 5 to 90% by mass, more preferably 25 to 75% by mass of biomass-derived polyolefin, and preferably 10 to 95% by mass, more preferably 25 to 75%. And a polyolefin derived from fossil fuel in mass%. 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 whole resin composition.

  Various additives other than the main component polyolefin may be added to the resin composition produced in the above process or to the produced resin composition as long as the characteristics are not impaired. Examples of additives include plasticizers, UV stabilizers, anti-coloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, yarn friction reducing agents, slip agents, mold release agents, An oxidizing agent, an ion exchange agent, a coloring pigment, and the like can be added. These additives are preferably added in an amount of 1 to 20% by mass, preferably 1 to 10% by mass, based on the entire resin composition.

Resin film The resin film according to the present invention comprises the above resin composition, and the resin composition contains 5 mass% or more of biomass-derived ethylene with respect to the entire resin composition, thereby providing a carbon neutral polyolefin resin film. realizable. Therefore, the amount of fossil fuel used can be greatly reduced compared to the conventional case, and the environmental load can be reduced. In addition, the polyolefin resin film of the present invention is not inferior in terms of physical properties such as mechanical properties as compared to a polyolefin resin film produced from a raw material obtained from a conventional fossil fuel, and therefore substitutes for a conventional polyolefin resin film. 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 preferable, and extrusion molding is more preferably performed by a T-die method or an inflation method.

  For example, the resin film can be formed by extrusion molding by the following method. After the above resin composition is dried, the resin composition is supplied to a melt extruder heated to a temperature equal to or higher than the melting point of the polyolefin (Tm) to Tm + 70 ° C. to melt the resin composition, for example, a die such as a T die. The 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 depending on the purpose.

  The thickness of the resin film obtained as described above is arbitrary depending on the 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 may be used as a laminated film by laminating a plurality of sheets.

Applications The resin film according to the present invention is used in 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 used suitably, and a packaged product and a sheet molded product are particularly preferable.

  Hereinafter, although the present invention is explained based on an example, the present invention is not limited to these.

Measurement / Conditions In Examples 1 to 7 and Comparative Examples 1 and 2 below, the degree of biomass is a value of the content of carbon derived from biomass as measured by 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: 90mm
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 min) at a resin temperature of 290 ° C., thickness Extruded onto a 12 μm PET film (trade name: E5100, manufactured by Toyobo Co., Ltd.), a resin film was obtained. The conditions for 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 Resin obtained by dry blending 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 min) (biomass degree: 48%) , Density: 0.937 g / cm ³ , MFR: 17 g / 10 min) at a resin temperature of 290 ° C., and extruded onto a 12 μm thick PET film (trade name: E5100, manufactured by Toyobo Co., Ltd.). Obtained. The conditions for 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 (trade name: SHA7260, biomass degree: 94.5%, density: 0.955 g / cm ³ , MFR: 20 g / 10 min, manufactured by Braskem), low from fossil fuel Resin obtained by dry blending 67 parts by mass of 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 min) (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 (trade name: E5100, manufactured by Toyobo Co., Ltd.) Obtained. The conditions for 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
Low density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., trade name: LC701, biomass degree: 0%, density: 0.919 g / cm ³ , MFR: 14 g / 10 min) at a resin temperature of 290 ° C., thickness Extruded onto a 12 μm PET film (trade name: E5100, manufactured by Toyobo Co., Ltd.), a resin film was obtained. The conditions for 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 composition used in Examples 1 to 3 and Comparative Example 1 above and the properties of the obtained film, the following various evaluations were made: (1) Drawdown, (2 ) Neck-in, (3) Motor load, (4) Resin pressure, (5) Loop stiffness.

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

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

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

(5) Loop stiffness The resin films obtained in Examples 1 to 3 and Comparative Example 1 were cut into a width of 15 mm and a length of 150 mm, and a stiffness tester (trade name: Loop Stiffness Tester, manufactured by Toyo Seiki Seisakusho Co., 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 min) at a resin temperature of 320 ° C. Then, it was extruded onto a 12 μm thick PET film (trade name: E5100, manufactured by Toyobo Co., Ltd.) to obtain a resin film. The conditions for 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 biomass-derived linear low-density polyethylene (manufactured by Braskem: SLL318, biomass degree: 87%, density: 0.918 g / cm ³ , MFR: 2.7 g / 10 min) and low fossil fuel-derived Resin blended with 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 min) (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 12 μm thick PET film (trade name: E5100, manufactured by Toyobo Co., Ltd.) A film was obtained. The conditions for 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 linear low density polyethylene derived from biomass (manufactured by Braskem, trade name: SLL318, biomass degree: 87%, density: 0.918 g / cm ³ , MFR: 2.7 g / 10 min), fossil fuel 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 min) and 37 parts by mass, linear from fossil fuel Low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: KC573, biomass degree: 0%, density: 0.910 g / cm ³ , MFR: 15 g / 10 minutes) and 30 parts by mass of a resin (biomass degree: 29) %, Density: 0.916 g / cm ³ , MFR: 8.4 g / 10 min) at a resin temperature of 320 ° C. and a 12 μm thick PET film (east The resin film was obtained by extruding onto a product of Yobo Co., Ltd. (trade name: E5100). The conditions for 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 linear low density polyethylene derived from biomass (manufactured by Braskem, trade name: SLL318, biomass degree: 87%, density: 0.918 g / cm ³ , MFR: 2.7 g / 10 min), fossil fuel 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 min) and 37 parts by mass, linear from fossil fuel Low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: KS560T, biomass degree: 0%, density: 0.898 g / cm ³ , MFR: 16 g / 10 minutes) 30 parts by mass of a resin (biomass degree is 29) %, Density is 0.912 g / cm ³ , MFR is 8.7 g / 10 min) at a resin temperature of 320 ° C. and a PET film having a thickness of 12 μm ( Extruded onto Toyobo Co., Ltd., trade name: E5100) to obtain a resin film. The conditions for 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
Low density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., trade name: LC600A, biomass degree: 0%, density: 0.919 g / cm ³ , MFR: 7 g / 10 min) at a resin temperature of 320 ° C., thickness Extruded onto a 12 μm PET film (trade name: E5100, manufactured by Toyobo Co., Ltd.), a resin film was obtained. The conditions for 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 composition used in Examples 4 to 7 and Comparative Example 2 above and the properties of the obtained film, the following various evaluations were made: (6) Drawdown, (7 ) Neck-in, (8) Motor load, (9) Resin pressure, (10) Seal start temperature.

(6) Drawdown The resin compositions used in Examples 4 to 7 and Comparative Example 2 described above were subjected to 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 extrusion film forming machine. Then, the maximum take-off speed (m / min) at which the extrusion coating film was cut 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 taken out under the conditions of a T-die width of 560 mm and a screw rotation speed of 105 rpm using the above-described extrusion film forming machine. The binaural neck-in (mm) at an air gap of 140 m / min and an air gap of 120 mm was measured. 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) when a resin film was produced using the extrusion film forming machine was measured. The measurement results were as shown in Table 2 below.

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

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

Measurement / Conditions In the following Reference Examples 1 to 3, Reference Comparative Example 1, Examples 1 to 2 and Comparative Examples 1 to 3 , the degree of biomass is the value of the content of carbon derived from biomass by radioactive carbon (C14) measurement. It is.

Production of Laminated Film The conditions of the extrusion film forming machine used in Reference Examples 1 to 3, Reference Comparative Example 1, Examples 1 and 2 and Comparative Examples 1 to 3 below were as follows.
Screw diameter: 90mm
Screw type: Full flight L / D: 28
T die: 11S type straight manifold T die effective opening length: 560mm

Reference 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 min) at a resin temperature of 290 ° C., thickness Extruded onto a 12 μm PET film (trade name: E5100, manufactured by Toyobo Co., Ltd.), a laminated film was obtained. The conditions for 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.

Reference 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 Resin obtained by dry blending 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 min) (biomass degree: 48%) , ^{density: 0.937g} / cm 3, ^MFR: a 17 g / 10 min), at 290 ° C. of resin temperature, PET film (Toyobo Co., Ltd. having a thickness of 12 [mu] m, trade name: E5100) extruded onto the laminate film Obtained. The conditions for 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.

Reference example 3
33 parts by mass of biomass-derived high-density polyethylene (trade name: SHA7260, biomass degree: 94.5%, density: 0.955 g / cm ³ , MFR: 20 g / 10 min, manufactured by Braskem), low from fossil fuel Resin obtained by dry blending 67 parts by mass of 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 min) (biomass degree: 32% , ^{density: 0.931g / cm 3, MFR:} 16g / 10 min), at 290 ° C. of resin temperature, PET film (Toyobo Co., Ltd. having a thickness of 12 [mu] m, trade name: E5100) extruded onto the laminate film Obtained. The conditions for 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.

Reference Comparative Example 1
Low density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., trade name: LC701, biomass degree: 0%, density: 0.919 g / cm ³ , MFR: 14 g / 10 min) at a resin temperature of 290 ° C., thickness Extruded onto a 12 μm PET film (trade name: E5100, manufactured by Toyobo Co., Ltd.), a laminated film was obtained. The conditions for 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 Laminated Film Regarding the processability of the resin composition used in Reference Examples 1 to 3 and Reference Comparative Example 1 above and the properties of the obtained film, the following various evaluations were made: 2) Neck-in, (3) Motor load, (4) Resin pressure, (5) Loop stiffness were performed.

(1) Drawdown The resin compositions used in the above Reference Examples 1 to 3 and Reference Comparative Example 1 were subjected to 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. Under the conditions, the maximum take-off speed (m / min) at which the extruded coating film was cut or surging was measured.
The measurement results were as shown in Table 1 below.

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

(3) Motor load In the above Reference Examples 1 to 3 and Reference Comparative Example 1, the motor load (A) when a laminated film was produced using the above-mentioned extrusion film forming machine was measured. The measurement results were as shown in Table 1 below.

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

(5) The laminated film obtained in loop stiffness above Examples 1 to 3 and Reference Comparative Example 1, cut into a width 15 mm, length 150 mm, stiffness tester (Toyo Seiki Seisakusho Co., Ltd., trade name: Loop Steph Ness The rigidity (N) of the film was measured using a tester. The length of the loop was 60 mm. The measurement results were as shown in Table 1 below.

Comparative Example 1
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) at a resin temperature of 320 ° C. Then, the film was extruded onto a PET film having a thickness of 12 μm (trade name: E5100 manufactured by Toyobo Co., Ltd.) to obtain a laminated film. The conditions for 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
33 parts by mass of biomass-derived linear low-density polyethylene (manufactured by Braskem: SLL318, biomass degree: 87%, density: 0.918 g / cm ³ , MFR: 2.7 g / 10 min) and low fossil fuel-derived Resin blended with 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 min) (biomass degree: 29%) , ^{density: 0.918g / cm 3, MFR:} 6.3g / 10 minutes), at 320 ° C. of resin temperature, PET film (Toyobo Co., Ltd. having a thickness of 12 [mu] m, trade name: E5100) extruded on, laminated A film was obtained. The conditions for 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 1
33 parts by mass of linear low density polyethylene derived from biomass (manufactured by Braskem, trade name: SLL318, biomass degree: 87%, density: 0.918 g / cm ³ , MFR: 2.7 g / 10 min), fossil fuel 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 min) and 37 parts by mass, linear from fossil fuel Low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: KC573, biomass degree: 0%, density: 0.910 g / cm ³ , MFR: 15 g / 10 minutes) and 30 parts by mass of a resin (biomass degree: 29) %, Density: 0.916 g / cm ³ , MFR: 8.4 g / 10 min) at a resin temperature of 320 ° C. and a 12 μm thick PET film (east The laminated film was obtained by extruding onto Yobo Co., Ltd., trade name: E5100). The conditions for 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
33 parts by mass of linear low density polyethylene derived from biomass (manufactured by Braskem, trade name: SLL318, biomass degree: 87%, density: 0.918 g / cm ³ , MFR: 2.7 g / 10 min), fossil fuel 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 min) and 37 parts by mass, linear from fossil fuel Low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: KS560T, biomass degree: 0%, density: 0.898 g / cm ³ , MFR: 16 g / 10 minutes) 30 parts by mass of a resin (biomass degree is 29) %, Density is 0.912 g / cm ³ , MFR is 8.7 g / 10 min) at a resin temperature of 320 ° C. and a PET film having a thickness of 12 μm ( Extruded onto Toyobo Co., Ltd., trade name: E5100) to obtain a laminated film. The conditions for 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 3
Low density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., trade name: LC600A, biomass degree: 0%, density: 0.919 g / cm ³ , MFR: 7 g / 10 min) at a resin temperature of 320 ° C., thickness Extruded onto a 12 μm PET film (trade name: E5100, manufactured by Toyobo Co., Ltd.), a laminated film was obtained. The conditions for 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 Laminated Film Regarding the processability of the resin compositions used in Examples 1 to 2 and Comparative Examples 1 to 3 and the properties of the obtained films, the following various evaluations were made: (7) Neck-in, (8) Motor load, (9) Resin pressure, (10) Seal start temperature were performed.

(6) Drawdown Using the above-described extrusion film forming machine, the resin composition used in Examples 1 to 2 and Comparative Examples 1 to 3 was T-die width 560 mm, resin temperature 290 ° C., screw rotation speed 34 rpm. Under these conditions, the maximum take-off speed (m / min) at which the extruded coating film was cut or surging was measured.
The measurement results were as shown in Table 2 below.

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

(8) In the motor load above Examples 1-2 and Comparative Examples 1 to 3 were motor load at the time of manufacture a laminated film using an extrusion film-forming machine of the above (A) was measured. The measurement results were as shown in Table 2 below.

(9) Resin Pressure In Examples 1 to 2 and Comparative Examples 1 to 3 described above, the resin pressure (MPa) when a laminated film was produced using the extrusion film forming machine was measured. The measurement results were as shown in Table 2 below.

(10) Seal start temperature The laminated films obtained in Examples 1 to 2 and Comparative Examples 1 to 3 are cut into a thickness of 15 mm and a length of 200 mm, the seal temperature is 90 to 150 ° C., and the seal pressure is 30 N. / Cm ² , and sealing time was 1 second, and the temperature (° C.) at which sealing was started was specified. The measurement results were as shown in Table 2 below.

Claims (13)

A resin film comprising a resin composition comprising a biomass-derived polyolefin obtained by polymerizing a monomer containing ethylene derived from biomass,
The resin composition comprises 5% by mass or more of the biomass-derived ethylene with respect to the whole 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 resin composition has a melt flow rate of 1 to 30 g / 10 minutes.   The resin film according to claim 1 or 2, wherein the resin composition comprises 5 to 95 mass% of the biomass-derived ethylene with respect to the entire resin composition.   The resin film according to any one of claims 1 to 3, wherein the monomer further contains fossil fuel-derived ethylene and / or α-olefin.   The resin film as described in any one of Claims 1-3 in which the said monomer further contains the alpha olefin derived from biomass.   6. The resin composition according to claim 1, wherein the resin composition further comprises a fossil fuel-derived polyolefin obtained by polymerizing a fossil fuel-derived ethylene and a fossil fuel-derived ethylene and / or α-olefin monomer. The resin film as described in any one.   The resin film according to claim 6, wherein the resin composition comprises 5 to 90% by mass of the biomass-derived polyolefin and 10 to 95% by mass of the fossil fuel-derived polyolefin.   The resin film according to any one of claims 4 to 7, wherein the α-olefin is butylene, hexene, or octene.   The resin film according to claim 1, wherein the polyolefin is polyethylene.   The resin film according to claim 1, wherein the resin composition is extruded.   The resin film according to claim 10, wherein the extrusion molding is performed by a T-die method or an inflation method.   Packaged product which consists of a resin film as described in any one of Claims 1-11.   The sheet molded product which consists of a resin film as described in any one of Claims 1-11.