JP6827892B2 - Polyolefin resin film - Google Patents

Description

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

In recent years, with the growing demand for the construction of a recycling-oriented society, there is a desire to break away from fossil fuels in the material field as well as energy, and the use of biomass is drawing attention. Biomass is an organic compound photosynthesized from carbon dioxide and water, and by using it, it becomes carbon dioxide and water again, so-called carbon-neutral renewable energy. In recent years, the practical use of biomass plastics made from these biomass raw materials is rapidly progressing, and attempts are being made to produce various resins from the biomass raw materials.

As a biomass-derived resin, polylactic acid (PLA), which is produced via lactic acid fermentation, has started commercial production in advance, but its biodegradable performance and other general-purpose plastics are currently available. Because it is very different from the above, there are limits to the product applications and product manufacturing methods, and it has not been widely used. In addition, a life cycle assessment (LCA) evaluation is being conducted for PLA, and discussions are being held on energy consumption during PLA manufacturing and equivalence when replacing general-purpose plastics.

Here, as the general-purpose plastic, various types such as polyethylene, polyvinyl chloride, polystyrene, and ABS resin are used. In particular, polyethylene is molded into films, sheets, bottles and the like, and is used for various purposes such as packaging materials, and is widely used all over the world. Therefore, the use of conventional fossil fuel-derived polyethylene has a large environmental load.

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

Japanese Patent Publication No. 2011-506628

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 a raw material was obtained from a conventional fossil fuel. It was found that a polyolefin resin film produced using ethylene can be obtained that is comparable in physical properties such as mechanical properties. The present invention is based on such findings.

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

In the bag made of the single-layer polyolefin resin film for packaging material according to the present invention, the single-layer polyolefin resin film for packaging material is derived from high-density polyethylene derived from biomass in which a monomer containing ethylene derived from biomass is polymerized, and fossil fuel. It is composed of a resin composition composed of two types of resins, low-density polyethylene derived from fossil fuel obtained by polymerizing a monomer containing ethylene.
The resin composition contains 5% by mass or more of the high-density polyethylene derived from the biomass with respect to the entire resin composition, and the biomass degree of the resin composition is 48% or less. The resin composition is characterized by having a density of 0.91 to 0.96 g / cm ³ .
In the aspect of the present invention, the above resin composition is 1 to 30 g / 10 when measured by the method A under the conditions of a temperature of 190 ° C. and a load of 21.18 N in the method specified in JIS K7210-1995. It is preferable to have a melt flow rate of minutes.
In the aspect of the present invention, the above resin composition may contain 5 to 95% by mass of the above biomass-derived high-density polyethylene with respect to the whole of the above resin composition.
The method for producing a bag made of the single-layer polyolefin resin film for packaging materials according to the present invention is characterized in that the resin composition is extruded.
In the aspect of the present invention, it is preferable that the extrusion molding is performed by the T-die method or the inflation method.

According to the present invention, the polyolefin resin film has a low density derived from fossil fuel obtained by polymerizing a monomer containing ethylene derived from biomass and a high density polyethylene derived from biomass obtained by polymerizing a monomer containing ethylene derived from fossil fuel. A carbon-neutral polyolefin resin film can be realized by comprising a resin composition composed of two types of resins with polyethylene and containing 5% by mass or more of high-density polyethylene 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 conventional case, and the environmental load can be reduced.
Further, the polyolefin resin film of the present invention is comparable to the polyolefin resin film produced from the raw material obtained from the conventional fossil fuel in terms of physical properties such as mechanical properties, and therefore replaces the conventional polyolefin resin film. be able to.

Biomass-Derived Ethylene In the present invention, the method for producing biomass-derived ethylene, which is a raw material for biomass-derived polyolefin, is not particularly limited and can be obtained by a conventionally known method. Hereinafter, an example of a method for producing ethylene-derived 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 fermented ethanol derived from biomass obtained from plant raw materials. The plant 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, the fermented ethanol derived from biomass refers to ethanol purified by contacting a culture solution containing a carbon source obtained from a plant raw material with a microorganism that produces ethanol or a product derived from a crushed product thereof. Conventionally known methods such as distillation, membrane separation, and extraction can be applied to the purification of ethanol from the culture broth. For example, a method of adding benzene, cyclohexane or the like and azeotropically boiling the mixture, or removing water by membrane separation or the like can be mentioned.

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

A catalyst is usually used when ethylene is obtained by a dehydration reaction of ethanol, but the 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, and for example, γ-alumina is preferable.

Since this dehydration reaction is an endothermic reaction, it is usually carried out under heating conditions. As long as the reaction proceeds at a commercially useful reaction rate, the heating temperature is not limited, but a temperature of 100 ° C. or higher, more preferably 250 ° C. or higher, still more preferably 300 ° C. or higher is suitable. 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 also not particularly limited, but a pressure higher than normal pressure is preferable in order to facilitate subsequent gas-liquid separation. Industrially, a fixed bed flow reaction in which the catalyst can be easily separated is preferable, but a liquid phase suspension bed, a fluidized bed, or the like may also be used.

In the dehydration reaction of ethanol, the yield of the reaction depends on the amount of water contained in the ethanol supplied as a raw material. Generally, when a dehydration reaction is carried out, it is preferable that there is no water in consideration of the efficiency of removing water. However, in the case of the dehydration reaction of ethanol using a solid catalyst, it was found that the amount of other olefins, especially butene, tends to increase in the absence of water. It is presumed that it is not possible to suppress ethylene dimerization after dehydration without the presence of a small amount of water. The lower limit of the allowable water content needs to be 0.1% or more, preferably 0.5% or more. The upper limit is not particularly limited, but from the viewpoint of mass balance and heat balance, it is preferably 50% by weight or less, more preferably 30% or less, still more preferably 20% or less.

By performing the ethanol dehydration reaction in this way, a mixed portion of ethylene, water and a small amount of unreacted ethanol can be obtained, but since ethylene is a gas at about 5 MPa or less at room temperature, it is separated from these mixed portions by gas-liquid separation. Ethylene can be obtained except for 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, and the like 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 ammonia, the obtained ethylene contains carbonyl compounds such as ketones, aldehydes, and esters, which are impurities mixed in the ethanol fermentation process, carbon dioxide gas, which is a decomposition product thereof, and decomposition products of enzymes. It contains a very small amount 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. 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 material having a high surface area 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, caustic water treatment may be used in combination as a method for purifying impurities in ethylene. When caustic water treatment is performed, it is desirable to perform it before adsorption purification. In that case, it is necessary to perform a water removal treatment after the caustic treatment and before the adsorption purification.

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

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

The above-mentioned α-olefin has no particular limitation on the number of carbon atoms, but usually one having 3 to 20 carbon atoms can be used, and it is preferably butylene, hexene, or octene. This is because butylene, hexene, or octene can be produced by polymerization of ethylene, which is a raw material derived from biomass. Further, by including such an α-olefin, the polymerized polyolefin has an alkyl group as a branched structure, so that it can be made more flexible than a simple linear one.

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

The biomass-derived ethylene concentration in the above-mentioned polyolefin (hereinafter, may be referred to as “biomass degree”) is a value obtained by measuring the content of biomass-derived carbon by measuring radioactive carbon (C14). Since carbon dioxide in the atmosphere contains C14 at a fixed ratio (105.5 pMC), the C14 content in plants that grow by taking in carbon dioxide in the atmosphere, such as corn, is also about 105.5 pMC. It is known. It is also known that fossil fuels contain almost no C14. Therefore, the proportion of biomass-derived carbon can be calculated by measuring the proportion of C14 contained in all carbon atoms in 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 the raw material for the polyolefin, the biomass-derived ethylene concentration is 100%, and the biomass degree of the biomass-derived polyolefin is 100%. Further, 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 do not need to have a biomass degree of 100%. This is because if a raw material derived from biomass is used even in a part of the resin film, the purpose of the present invention is to reduce the amount of fossil fuel used as compared with the conventional case.

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

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

The above-mentioned single-site catalyst is a catalyst capable of forming a uniform active species, and is usually prepared by contacting a metallocene-based transition metal compound or a non-metallocene-based transition metal compound with an activation co-catalyst. .. Compared with the multisite catalyst, the single-site catalyst is preferable because it has a uniform active site structure and can polymerize a polymer having a high molecular weight and a high uniformity structure. As the single-site catalyst, it is particularly preferable to use a metallocene-based catalyst. The metallocene-based catalyst is a catalyst containing a transition metal compound of Group IV of the Periodic Table, which contains a ligand having a cyclopentadienyl skeleton, a cocatalyst, an organometallic compound if necessary, and each catalyst component of the carrier. is there.

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

In the transition metal compound of Group IV of the Periodic Table containing a ligand having a cyclopentadienyl skeleton, examples of the transition metal include zirconium, titanium and hafnium, and zirconium and hafnium are particularly preferable. The transition metal compound usually has two ligands having a cyclopentadienyl skeleton, and the ligands having each cyclopentadienyl skeleton are preferably bonded to each other by a cross-linking group. Examples of the cross-linking group include a substituted silylene group such as an alkylene group having 1 to 4 carbon atoms, a silylene group, a dialkyl silylene group and a diaryl silylene group, a substituted gel millene group such as a dialkyl gel millene group and a diaryl gel millene group. It is preferably a substituted silylene group.

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

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

The co-catalyst is one in which the transition metal compound of Group IV of the Periodic Table can be effectively used as a polymerization catalyst, or the ionic charge in a catalytically activated state can be equalized. As co-catalysts, benzene-soluble organoxane of organoaluminum oxy compounds, benzene-insoluble organoaluminum oxy compounds, ion-exchange layered silicates, boron compounds, cations containing or not containing active hydrogen groups and non-coordinating anions are used. Examples thereof include ionic compounds, lanthanoid 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, which contains a ligand having a cyclopentadienyl skeleton, may be used by supporting it on a carrier of an inorganic or organic compound. As the carrier, a porous oxide of an inorganic or organic compound is preferable, and specifically, an ion-exchangeable 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, etc. or a mixture thereof can be mentioned.

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

Further, as the polyolefin, a polymer of ethylene or a copolymer of ethylene and α-olefin may be used alone, or two or more kinds may be mixed and used.

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

The above resin composition has a density of 0.91 to 0.96 g / cm ³ , preferably 0.915 to 0.955 g / cm ³ , and more preferably 0.92 to 0.95 g / cm ^3. is there. The density of the resin composition is a value measured according to the method specified in the method A of JIS K7112-1980 after performing the annealing described in JIS K6760-1980. 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. Further, 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 minutes, preferably 1.5 to 6.0 g / 10 minutes in the inflation method, and 4 to 20 g / 10 minutes in the T-die method. It is a thing. The melt flow rate is a value measured by the method A under the conditions of a temperature of 190 ° C. and a load of 21.18 N in the method specified in JIS K7210-1995. When the MFR of the resin composition is 1 g / 10 minutes or more, the extrusion load during molding can be reduced. Further, when the MFR of the resin composition is 30 g / 10 minutes or less, the mechanical strength of the resin film made of the resin composition can be increased.

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

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

According to the aspect of the present invention, the resin composition preferably contains 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% by mass. It contains a mass% of fossil fuel-derived polyolefin. Even when the resin composition of such a mixture is used, the concentration of ethylene derived from biomass as a whole of the resin composition may be within the above range.

In addition to the polyolefin as the main component, various additives may be added to the resin composition produced in the above-mentioned production process of the resin composition or to the produced resin composition as long as its characteristics are not impaired. Additives include, for example, plasticizers, UV stabilizers, color inhibitors, matting agents, deodorants, flame retardants, weatherproofing agents, antistatic agents, thread friction reducing agents, slipping agents, mold release agents, anti-corrosion agents. Excipients, ion exchangers, coloring pigments and the like can be added. These additives are preferably added in the range of 1 to 20% by mass, preferably 1 to 10% by mass, based on the entire resin composition.

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

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

For example, the resin film can be molded by extrusion molding by the following method. After the above resin composition is dried, it is supplied to a melt extruder heated to a temperature (Tm) to Tm + 70 ° C. higher than the melting point of polyolefin to melt the resin composition, for example, a die such as a T die. A film can be formed by extruding the extruded sheet into a sheet and quenching and solidifying the extruded sheet with a rotating cooling drum or the like. As the melt extruder, a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder and the like can be used depending on the purpose.

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

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 products such as decorative sheets and trays, laminated films, optical films, resin plates, various label materials, lid materials, and laminated tubes. It can be preferably used, and in particular, packaged products and sheet-molded products are preferable.
Other aspects
An object of the present invention is to provide a resin film made of a resin composition containing a carbon-neutral polyolefin using ethylene derived from biomass, and a resin film and a machine produced from a raw material obtained from a conventional fossil fuel. It is an object of the present invention to provide a polyolefin resin film that is comparable in physical properties such as physical properties.
The resin film according to the present invention comprises a resin composition containing a biomass-derived polyolefin obtained by polymerizing a biomass-derived ethylene-containing monomer.
The above resin composition contains 5% by mass or more of the above biomass-derived ethylene with respect to the whole of the above resin composition, and the above resin composition has a density of 0.91 to 0.96 g / cm ³ . It is characterized by having.
In the aspect of the present invention, it is preferable that the above resin composition has a melt flow rate of 1 to 30 g / 10 minutes.
In the aspect of the present invention, the above-mentioned resin composition may contain 5 to 95% by mass of the above-mentioned biomass-derived ethylene with respect to the whole of the above-mentioned resin composition.
In aspects of the invention, the monomer may further comprise fossil fuel-derived ethylene and / or α-olefin.
In aspects of the invention, the monomer may further comprise a biomass-derived α-olefin.
In the embodiment of the present invention, the above resin composition may further contain a fossil fuel-derived polyolefin obtained by polymerizing a fossil fuel-derived ethylene and a fossil fuel-derived ethylene and / or α-olefin-containing monomer. Good.
In the aspect of the present invention, the resin composition may contain 5 to 90% by mass of the above-mentioned biomass-derived polyolefin and 10 to 95% by mass of the above-mentioned fossil fuel-derived polyolefin. ..
In aspects of the present invention, the α-olefin is preferably butylene, hexene, or octene.
In the aspect of the present invention, it is preferable that the above-mentioned polyolefin is polyethylene.
In the aspect of the present invention, it is preferable that the resin composition is a resin film obtained by extrusion molding.
In the aspect of the present invention, it is preferable that the above extrusion molding is performed by the T-die method or the inflation method.
In the aspect of the present invention, it is preferable that the packaged product is made of the above resin film.
In the aspect of the present invention, it is preferable that the sheet molded product is made of the above resin film.
According to the present invention, the polyolefin resin film comprises a resin composition containing a biomass-derived polyolefin obtained by polymerizing a monomer containing a biomass-derived ethylene, and the biomass-derived ethylene is added to the entire resin composition 5 A carbon-neutral polyolefin resin film can be realized by containing a mass% or more. Therefore, the amount of fossil fuel used can be significantly reduced as compared with the conventional case, and the environmental load can be reduced. Further, the polyolefin resin film of the present invention is comparable to the polyolefin resin film produced from the raw material obtained from the conventional fossil fuel in terms of physical properties such as mechanical properties, and therefore replaces the conventional polyolefin resin film. be able to.

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

Measurement / Conditions In Examples 1 and 2 , Comparative Examples 1 and 2, Reference Examples 1 to 4, and Reference Comparative Example 1 below, the degree of biomass is the value of the carbon content derived from biomass as measured by radiocarbon (C14). Is.

Production of Laminated Film The conditions of the extruder used in Examples 1 and 2 , Comparative Examples 1 and 2, Reference Examples 1 to 4, and Reference Comparative Example 1 were as follows.
Screw diameter: 90 mm
Screw model: Full flight L / D: 28
T-die: 11S type straight manifold T-die effective opening length: 560mm

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

Example 1
Biomass-derived high-density polyethylene (manufactured by Braskem, trade name: SHA7260, biomass degree: 94.5%, density: 0.955 g / cm ³ , MFR: 20 g / 10 minutes) 50 parts by mass and low fossil fuel-derived Density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: LC701, biomass degree: 0%, density: 0.919 g / cm ³ , MFR: 14 g / 10 minutes) A resin obtained by dry blending 50 parts by mass (biomass degree: 48%) , Density: 0.937 g / cm ³ , MFR: 17 g / 10 minutes) is extruded onto a 12 μm-thick PET film (manufactured by Toyo Boseki Co., Ltd., trade name: E5100) at a resin temperature of 290 ° C. to form a laminated film. Obtained. The conditions for extrusion molding 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
Biomass-derived high-density polyethylene (manufactured by Braskem, trade name: SHA7260, biomass degree: 94.5%, density: 0.955 g / cm ³ , MFR: 20 g / 10 minutes) 33 parts by mass and low fossil fuel-derived Density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: LC701, biomass degree: 0%, density: 0.919 g / cm ³ , MFR: 14 g / 10 minutes) 67 parts by mass and a resin (biomass degree: 32%) , Density: 0.931 g / cm ³ , MFR: 16 g / 10 minutes) is extruded onto a 12 μm-thick PET film (manufactured by Toyo Boseki Co., Ltd., trade name: E5100) at a resin temperature of 290 ° C. to form a laminated film. Obtained. The conditions for extrusion molding 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 Corporation, trade name: LC701, biomass degree: 0%, density: 0.919 g / cm ³ , MFR: 14 g / 10 minutes) at a resin temperature of 290 ° C. A laminated film was obtained by extruding onto a 12 μm PET film (manufactured by Toyobo Corporation, trade name: E5100). The conditions for extrusion molding were set to an effective width of 560 mm, an extrusion thickness of 30 μm, and an extrusion speed of 100 m / min.

For workability and properties of the obtained film Evaluation of Examples 1 resin composition used in 2 and Comparative Examples 21 to the resin composition and the laminated 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 resin compositions used in Examples 1 and 2 and Comparative Examples 1 and 2 described above 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-mentioned extrusion film-forming machine. Under the above conditions, the maximum take-up speed (m / min) at which the extruded coating film was cut or surging was measured.
The measurement results are as shown in Table 1 below.

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

(3) Motor load In Examples 1 and 2 and Comparative Examples 1 and 2 described above, the motor load (A) when a laminated film was produced using the extrusion film forming machine was measured. The measurement results are as shown in Table 1 below.

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

(5) The laminated film obtained in loop stiffness above Examples 1-2 and Comparative Examples 21 to cut into a width 15 mm, length 150 mm, stiffness tester (Toyo Seiki Seisakusho Co., Ltd., trade name: Rupusutefu The rigidity (N) of the film was measured using Nestester). The length of the loop was 60 mm. The measurement results are as shown in Table 1 below.

Reference 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 minutes) to a resin temperature of 320 ° C. Then, it was extruded onto a PET film having a thickness of 12 μm (manufactured by Toyobo Co., Ltd., trade name: E5100) to obtain a laminated film. The conditions for extrusion molding were set to an effective width of 560 mm, an extrusion thickness of 30 μm, and an extrusion speed of 100 m / min.

Reference example 2
Biomass-derived linear low-density polyethylene (Brackem: SLL318, biomass degree: 87%, density: 0.918 g / cm ³ , MFR: 2.7 g / 10 minutes) 33 parts by mass, low from fossil fuel Density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: LC604, biomass degree: 0%, density: 0.918 g / cm ³ , MFR: 8 g / 10 minutes) 67 parts by mass and melt-blended resin (biomass degree: 29%) , Density: 0.918 g / cm ³ , MFR: 6.3 g / 10 minutes) is extruded onto a 12 μm thick PET film (manufactured by Toyo Boseki Co., Ltd., trade name: E5100) at a resin temperature of 320 ° C. and laminated. I got a film. The conditions for extrusion molding were set to an effective width of 560 mm, an extrusion thickness of 30 μm, and an extrusion speed of 100 m / min.

Reference example 3
Biomass-derived linear low-density polyethylene (manufactured by Braskem, trade name: SLL318, biomass degree: 87%, density: 0.918 g / cm ³ , MFR: 2.7 g / 10 minutes) 33 parts by mass and fossil fuel Derived low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: LC604, biomass degree: 0%, density: 0.918 g / cm ³ , MFR: 8 g / 10 minutes) 37 parts by mass and linear linear derived from fossil fuel Resin (biomass degree: 29) melt-blended with 30 parts by mass of 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) %, Density: 0.916 g / cm ³ , MFR: 8.4 g / 10 minutes) was extruded onto a 12 μm-thick PET film (manufactured by Toyo Boseki Co., Ltd., trade name: E5100) at a resin temperature of 320 ° C. A laminated film was obtained. The conditions for extrusion molding were set to an effective width of 560 mm, an extrusion thickness of 30 μm, and an extrusion speed of 100 m / min.

Reference example 4
Biomass-derived linear low-density polyethylene (manufactured by Braskem, trade name: SLL318, biomass degree: 87%, density: 0.918 g / cm ³ , MFR: 2.7 g / 10 minutes) 33 parts by mass and fossil fuel Derived low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: LC604, biomass degree: 0%, density: 0.918 g / cm ³ , MFR: 8 g / 10 minutes) 37 parts by mass and linear linear derived from fossil fuel Resin melt-blended with 30 parts by mass of low-density polyethylene (manufactured by Nippon Polyethylene, trade name: KS560T, biomass degree: 0%, density: 0.898 g / cm ³ , MFR: 16 g / 10 minutes) (biomass degree is 29). %, Density 0.912 g / cm ³ , MFR 8.7 g / 10 minutes) was extruded onto a 12 μm thick PET film (manufactured by Toyo Boseki, trade name: E5100) at a resin temperature of 320 ° C. A laminated film was obtained. The conditions for extrusion molding were set to an effective width of 560 mm, an extrusion thickness of 30 μm, and an extrusion speed of 100 m / min.

Reference comparison example 1
Low-density polyethylene derived from fossil fuel (manufactured by Japan Polyethylene Corporation, trade name: LC600A, biomass degree: 0%, density: 0.919 g / cm ³ , MFR: 7 g / 10 minutes) at a resin temperature of 320 ° C. A laminated film was obtained by extruding onto a 12 μm PET film (manufactured by Toyobo Corporation, trade name: E5100). The conditions for extrusion molding 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 Laminated Film The following various evaluations were made regarding the processability of the resin composition used in Reference Examples 1 to 4 and Reference Comparative Example 1 and the characteristics of the obtained film: (6) Drawdown, ( 7) neck-in, (8) motor load, (9) resin pressure, and (10) seal start temperature were performed.

(6) Drawdown The resin compositions used in Reference Examples 1 to 4 and Reference Comparative Example 1 above 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-mentioned extrusion membrane-forming machine. Under the conditions, the maximum take-up speed (m / min) at which the extruded coating film was cut or surging was measured.
The measurement results are as shown in Table 2 below.

(7) Neck-in The resin compositions used in Reference Examples 1 to 4 and Reference Comparative Example 1 are picked up using the extrusion film-forming machine under the conditions of a T-die width of 560 mm and a screw rotation speed of 105 rpm. Binaural neck-in (mm) was measured at a speed of 140 m / min and an air gap of 120 mm. The measurement results are as shown in Table 2 below.

(8) Motor load In Reference Examples 1 to 4 and Reference Comparative Example 1 above, the motor load (A) when a laminated film was produced using the extrusion film-forming machine was measured. The measurement results are as shown in Table 2 below.

(9) Resin Pressure In Reference Examples 1 to 4 and Reference Comparative Example 1 above, the resin pressure (MPa) when a laminated film was produced using the above extrusion film forming machine was measured. The measurement results are as shown in Table 2 below.

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

Claims (5)

It is composed of two types of resins: high-density polyethylene derived from biomass obtained by polymerizing a monomer containing ethylene derived from biomass, and low-density polyethylene derived from fossil fuel obtained by polymerizing a monomer containing ethylene derived from fossil fuel. A bag made of a single-layer polyolefin resin film for packaging materials made of a resin composition.
The resin composition contains 5% by mass or more of the high-density polyethylene derived from the biomass with respect to the entire resin composition, the biomass degree of the resin composition is 48% or less, and the resin composition is: A bag having a density of 0.91 to 0.96 g / cm ³ . The resin composition has a melt flow rate of 1 to 30 g / 10 minutes when measured by the method A under the conditions of a temperature of 190 ° C. and a load of 21.18 N in the method specified in JIS K7210-1995. The bag according to claim 1. The bag according to claim 1 or 2, wherein the resin composition contains 5 to 95% by mass of the high-density polyethylene derived from the biomass with respect to the entire resin composition. The method for manufacturing a bag according to any one of claims 1 to 3.
A production method comprising extrusion molding the resin composition. The manufacturing method according to claim 4, wherein the extrusion molding is performed by a T-die method or an inflation method.