JP2023152249A - Ethylene-based polymer obtained from olefin mixture containing biomass-derived olefin and fossil-fuel-derived olefin, and production method of the ethylene-based polymer - Google Patents

Abstract

To provide an ethylene-based polymer having equivalent performance for a desired concentration of biomass-derived carbon without necessity for adding facilities and steps for mixing a biomass-derived ethylene-based polymer and a fossil-fuel-derived ethylene-based polymer, and to provide a low-cost ethylene-based polymer having a desired concentration of biomass-derived carbon and equivalent performance in consideration of market need or the like.SOLUTION: An ethylene-based polymer, which is an ethylene homopolymer or a copolymer of ethylene and a specific olefin, satisfies (I) the condition that at least one olefin contained in the raw material of the ethylene-based polymer is an olefin mixture of a biomass-derived olefin of a specific wt.% and a fossil-fuel-derived olefin of a specific wt.%, and (II) the condition that the ethylene-based polymer has a specific concentration of biomass-derived carbon.SELECTED DRAWING: None

Description

The present invention relates to an ethylene polymer and a method for producing the polymer. More specifically, the present invention relates to an ethylene polymer obtained by polymerizing ethylene consisting of biomass-derived ethylene and fossil fuel-derived ethylene, and a method for producing the polymer.

From the perspective of reducing the environmental burden (greenhouse gas generation) in the life cycle of plastic products, from manufacture to use and disposal, we are developing biomass-derived ethylene production, and ethylene-based polymers that are polymerized from biomass-derived ethylene as raw materials. Polymer (biomass-derived ethylene polymer) has been produced (Non-Patent Document 1, Non-Patent Document 2).
Ethylene/1-butene copolymers consisting of ethylene sourced from renewable natural raw materials and 1-butylene as a comonomer have been produced (US Pat. No. 5,001,302). When examining the equivalence of polyethylene obtained by polymerizing fossil fuel-derived ethylene and biomass-derived ethylene under the same conditions, it was found that no matter which grade of polyethylene is used, the polymerization of fossil fuel-derived ethylene (petroleum-based ethylene) It has been confirmed that the obtained petroleum-based polyethylene and the biomass-based polyethylene obtained by polymerizing biomass-derived ethylene (biomass-based ethylene) are equivalent in quality (Non-Patent Document 2).
In addition, by having a laminate with a biomass polyolefin resin layer containing carbon-neutral polyolefin using biomass-derived ethylene, it is possible to realize a carbon-neutral biomass resin laminate, which uses less fossil fuel than conventional methods. The amount used can be significantly reduced, and the environmental impact can be reduced. In addition, the laminate according to the present invention is comparable in physical properties such as mechanical properties to conventional resin laminates manufactured from raw materials obtained from fossil fuels, so it can be used as a substitute for conventional resin laminates. It is said that it is possible to do so (Patent Document 2).

On the other hand, for a composition consisting of petroleum-derived LLDPE (linear low-density polyethylene) and LDPE (high-pressure low-density polyethylene), 30 to 80 parts by mass of plant-derived LLDPE (linear low-density polyethylene) to be blended is added. It is said that if the amount is increased to 50%, it will not be able to withstand the impact of dropping, and will be less easy to cut by hand (Patent Document 3).
It is said that a resin film containing a plant-derived resin, for example a sealant film containing a plant-derived polyethylene resin, exhibits different properties from a sealant film containing only a petroleum-derived polyethylene resin (Patent Document 4).
For example, linear low-density polyethylene derived from biomass is produced using sugarcane as a raw material. The degree of dispersion of such sugarcane-derived linear low density polyethylene can be 4 or more and 7 or less. On the other hand, the degree of dispersion of fossil-derived linear low-density polyethylene is generally said to be 1.5 or more and 3.5 or less (Patent Document 5).
From a comparison with a film produced with a composition containing no plant-derived linear low-density polyethylene resin (plant-derived resin), the thermal expansion test performance (thermal stability) of the example is clearly good. Therefore, it has been found that incorporating plant-derived linear low-density polyethylene resin into the composition contributes to improved quality. (Patent Document 6)
For reasons that are not clear, polyethylene synthesized from bioethanol is made by polymerizing other general-purpose polyethylenes, such as ethylene obtained through petroleum refining, and comonomer α-olefin in the presence of a metallocene catalyst. It is said that it has superior suitability for high-frequency welding compared to the obtained linear low-density polyethylene (LLDPE) and the like (Patent Document 7).

However, the difference in structure between biomass-derived olefins (ethylene, propylene, α-olefins with 4 to 8 carbon atoms) and fossil fuel-derived olefins (ethylene, propylene, α-olefins with 4 to 8 carbon atoms) is that the ¹⁴ C isotope (In biomass-derived olefins, ¹⁴ C exists at a concentration of about 1×10 ^-12 relative to the total carbon). (Non-patent document 3).
Furthermore, while the world's fossil fuel production is approximately 7.9 billion tons (oil equivalent)/year (Non-patent Document 4), the world's biomass fuel production is approximately 9.5 billion tons (oil equivalent)/year. (Non-Patent Document 5), and the production cost of biomass-derived ethylene is high. Therefore, in order to widely disseminate materials containing polymers made from biomass-derived ethylene, which has a low environmental impact, there is a need for materials with adjusted biomass content, taking into account product price, market needs, etc.

From the perspective of reducing environmental impact, it is preferable to use only biomass-derived polyethylene; however, in consideration of manufacturing costs, etc., a blend of fossil fuel-derived polyethylene and biomass-derived polyethylene may be used. This is being considered (Patent Document 8).
A film containing plant-derived linear low-density polyethylene (LLDPE) and non-plant-derived linear low-density polyethylene (LLDPE), exhibiting excellent hand tearability and impact resistance, and exhibiting a high degree of biomass. A polyethylene-based resin composition for packaging materials and a sealant film for packaging materials using the same have been studied (Patent Document 9).

Special Publication No. 2011-506628 Japanese Patent Application Publication No. 2014-133338 Japanese Patent Application Publication No. 2013-136689 Japanese Patent Application Publication No. 2014-46674 Japanese Patent Application Publication No. 2018-171785 JP 2017-114037 Publication JP 2016-20044 Publication Japanese Patent Application Publication No. 2018-167860 Japanese Patent Application Publication No. 2013-155343

Possibilities of new biomass plastics - From commercialization of "sugarcane-derived polyethylene" -, Polyfile, Vol. 46, No. 550, pages 28-30 (December 2009) Eco-friendly "sugarcane-derived polyethylene", Convertec, No. 437, pages 63-67 (August 2009) Evaluation of biomass origin of biomass plastics by carbon-14 measurement using AMS, Thermal Measurement, 39(4), pp. 143-150 (2012) Strategic Research Seminar: World long-term energy supply and demand outlook and the role of nuclear power (November 24, 2005), Internet <URL: https://www.jaea.go.JP/03/senryaku/seminar/05-1.pdf> International Institute for Environmental Economics, Current status and future of biofuels (1) (October 27, 2020), Internet <URL: https://ieei.or.JP/2020/10/expl201027/>

However, as in Patent Documents 8 and 9, materials in which the degree of biomass is adjusted by mixing biomass-derived polyolefin and fossil fuel-derived polyolefin are mixed with biomass-derived ethylene polymer and conventional fossil fuel-derived ethylene polymer. It is necessary to mix the polymers, a mixing process is required, equipment for this is required, energy is consumed in the mixing process, and there is also concern that the environmental burden will increase as a result.

In addition, in materials with adjusted biomass content obtained by mixing biomass-derived ethylene polymers with conventional fossil fuel-derived ethylene polymers, the molecular weight, molecular weight distribution, composition, and If the physical properties of the ethylene polymer, such as distribution, are not completely the same as the physical properties of the biomass-derived ethylene polymer, the original physical properties of the biomass-derived ethylene polymer will change, and this is desirable in cases where it is significant. There is a concern that physical properties may be impaired.

The purpose of the present invention is to reduce the environmental load (greenhouse gas generation) in the life cycle of ethylene polymers from production to utilization and disposal, and to adjust the amount of biomass-derived olefins in ethylene polymers. To provide an ethylene polymer that does not require additional equipment or processes for mixing a biomass-derived ethylene polymer and a fossil fuel-derived ethylene polymer, and has equivalent performance at any biomass-derived carbon concentration. , and a method for producing the polymer. Another object of the present invention is to provide an ethylene polymer that takes into consideration market needs, has a desired biomass-derived carbon concentration, and has equivalent performance at reduced costs.

As a result of intensive studies to solve the above problems, the present inventors have found that at least one type of monomer selected from the group consisting of ethylene and α-olefins having 3 to 8 carbon atoms is used as a raw material monomer for the ethylene polymer. By making the olefin an ethylene polymer that has a specific biomass-derived carbon concentration by containing an olefin mixture of a specific weight % of biomass-derived olefin and a specific weight % of fossil fuel-derived olefin, the above-mentioned The inventors have discovered that the problem can be solved and have completed the present invention.

The present invention relates to the following [1] to [32].
[1] An ethylene polymer that is an ethylene homopolymer or a copolymer of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms, and the following (I) to An ethylene polymer that satisfies (II).
(I) At least one olefin (a) selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms contained in the raw material of the ethylene polymer contains 0.2% by weight of the biomass-derived olefin (a1) It is an olefin mixture containing 1% to 99.8% by weight of fossil fuel-derived olefin (a2) and 1% to 99.8% by weight of fossil fuel-derived olefin (a2) (the total of biomass-derived olefin (a1) and fossil fuel-derived olefin (a2) %).
(II) The biomass-derived carbon concentration of the ethylene polymer is 0.2 pMC (%) or more and 99.0 pMC (%) or less.
[2] The ethylene polymer according to [1], which further satisfies (I-1) and (i) to (ii) below.
(I-1) Ethylene contained in the raw material of the ethylene polymer contains 0.2% to 99% by weight of biomass-derived ethylene and 1% to 99.8% by weight of fossil fuel-derived ethylene It is a mixture (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight).
(i) Density of ethylene polymer is 0.890g/cm ³ to 0.970g/cm ³
(ii) Melt flow rate (MFR) of ethylene polymer at 190°C and 2.16 kg load is 0.01 g/10 minutes to 1500 g/10 minutes [3] Biomass content is 1% according to ASTM D 6866 The ethylene polymer according to [2], which has a content of 99% or less.

[4] An ethylene homopolymer that satisfies the following (iii) to (iv), or a copolymer of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms (X1) 20 % by mass or more and 80% by mass or less,
(iii) Density d _x1 is 0.890g/cm ³ ~0.970g/cm ³
(iv) Melt flow rate (MFR) at 190°C and 2.16 kg load is 0.01 g/10 minutes to 1,500 g/10 minutes Ethylene homopolymer or ethylene that satisfies the following (v) to (vi) and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms. and the polymer (Y1) is 100% by weight),
(v) Density d _y1 is 0.890g/cm ³ ~0.960g/cm ³
(vi) MFR at 190°C and 2.16 kg load satisfies the following (vii) to (viii) for 0.01 g/10 minutes to 500 g/10 minutes,
(vii) Density is 0.890g/cm ³ ~0.970g/cm ³
(viii) MFR at 190 ° C. and 2.16 kg load is 0.01 g / 10 minutes to 60.0 g / 10 minutes, and satisfies at least one condition selected from the following (iii') and (iv'),
(iii') The density of the polymer (X1) is greater than the density of the polymer (Y1).
(iv') The MFR of the polymer (X1) is larger than the MFR of the polymer (Y1).
Ethylene contained in the raw materials of the ethylene homopolymer and the ethylene/α-olefin copolymer is (I-1) 0.2% to 99% by weight of biomass-derived ethylene and 1% by weight of fossil fuel-derived ethylene; The ethylene polymer according to [1], which is an ethylene mixture containing 99.8% by weight or less (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight).
[5] The ethylene polymer according to [4], which has a biomass degree of 1% or more and 99% or less according to ASTM D 6866.

[6] The ethylene polymer contains 5% by weight or more and 95% by weight or less of a copolymer (X2) of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms, and ethylene. and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms. A copolymer (A2-2) of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms (the total amount with the polymer (Y2) is 100% by mass) and
_{The ratio (d X2 /d Y2 ) of the} density d
The ratio of the intrinsic viscosity [η _X2 ] of _the copolymer (X2) to the intrinsic viscosity [η _Y2 ] of the copolymer ( _Y2 ) ([η
The above copolymer (X2) satisfies the following (ix) to (xii),
(ix) Density d _X2 is 0.890g/cm ³ ~0.940g/cm ³
(x) Intrinsic viscosity [η _X2 ] measured in decalin at 135°C is 1.0 to 10.0 dl/g
(xi) The temperature (Tm (°C)) and density (d _X2 ) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter satisfy Tm<400×d _X2 -250.
(xii) The decane soluble portion (W (wt%)) and density (d _x2 ) at room temperature are
W<80×exp(−100(d _X2 −0.88))+0.1 is satisfied.
The above copolymer (Y2) satisfies the following (xiii) to (xv),
(xiii) Density d _Y2 is 0.910g/cm ³ ~0.970g/cm ³
(xiv) Intrinsic viscosity [η _Y2 ] measured in decalin at 135°C is 0.5 to 2.0 dl/g
(xv) The temperature (Tm (°C)) and density (d _Y2 ) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter satisfy Tm>138×d _Y2 -6.
The density of the copolymer (A2-2) is in the range of 0.890 to 0.955 g/cm ³ ,
The melt flow rate (MFR) of the copolymer (A2-2) at 190 ° C. and 2.16 kg load satisfies the range of 0.1 to 100 g / 10 minutes,
The ethylene contained in the copolymer (X2) contained in the copolymer (A2-2) and the raw material of the copolymer (Y2) is (I-1) 0.2% by weight or more of biomass-derived ethylene 99 It is an ethylene mixture containing 1% by weight or more and 99.8% by weight or less of fossil fuel-derived ethylene (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight), described in [1] ethylene polymer.
[7] The ethylene polymer according to [6], which has a biomass degree of 1% or more and 99% or less according to ASTM D 6866.
[8] The ethylene polymer according to [6],
Low-density polyethylene (D) produced by a high-pressure radical method that satisfies the following (xvi) to (xvii),
(xvi) Melt flow rate (MFR) at 190°C and 2.16 kg load from 0.1 g/10 minutes to 50 g/10 minutes (xvii) Molecular weight distribution (Mw/Mn) obtained by GPC measurement and the above MFR satisfies the following relationship.
Mw/Mn≧7.5×log(MFR)-1.2
The weight ratio (A2-2):(D) of the ethylene polymer (A2-2) and the high-pressure radical-processed low-density polyethylene (D) is within the range of 99:1 to 60:40.
Ethylene polymer mixture.

[9] The ethylene polymer satisfies the following (xviii) to (xxii),
The ethylene contained in the raw material of the ethylene polymer includes (I-1) 0.2% to 99% by weight of biomass-derived ethylene and 1% to 99.8% by weight of fossil fuel-derived ethylene; The ethylene polymer according to [1], which is an ethylene mixture (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight).
(xviii) The content of methyl branches and ethyl branches measured by ¹³ C-NMR [M _{Me + Et} (mol%)] and the content of all branches measured by ¹³ C-NMR [M _all ( mol%)] [M _Me+Et /M _all ] is in the range of 0.30 to 1.00.
(xix) MFR at 190°C and 2.16 kg load is 0.1 g/10 minutes to 100 g/10 minutes (xx) Density is 0.890 g/cm ³ to 0.970 g/cm ³
(xxi) The ratio [MT/η * (g/P)] of the melt tension at 190° ^C [MT (g)] and the shear viscosity [η ^* (P)] at 200°C and an angular velocity of 1.0 rad/sec is It is in the range of 1.50×10 ⁻⁴ to 9.00×10 ⁻⁴ .
(xxii) The zero shear viscosity [η ₀ (P)] at 200°C and the weight average molecular weight (Mw) measured by the GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-1) .
0.01×10 ^-13 ×Mw ^3.4 ≦η ₀ ≦4.50×10 ^-13 ×Mw ^3.4 (Eq-1)
[10] The ethylene polymer according to [9], which has a biomass degree of 1% or more and 99% or less according to ASTM D 6866.

[11] The ethylene polymer satisfies the following (xxiii) to (xxviii),
The ethylene contained in the raw material of the ethylene polymer contains (I-1) 0.2% to 99% by weight of biomass-derived ethylene and 1% to 99.8% by weight of fossil fuel-derived ethylene; The ethylene polymer according to [1], which is an ethylene mixture (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight).
(xxiii) MFR at 190°C and 2.16 kg load is 0.1 g/10 minutes to 100 g/10 minutes (xxiv) Density is 0.890 g/cm ³ to 0.970 g/cm ³
(xxv) The ratio [MT/η * (g/P)] of the melt tension at 190° ^C [MT (g)] and the shear viscosity [η ^* (P)] at 200°C and an angular velocity of 1.0 rad/sec is It is in the range of 2.50×10 ⁻⁴ to 9.00×10 ⁻⁴ .
(xxvi) Sum of the number of methyl branches per 1000 carbon atoms [A (/1000C)] and the number of ethyl branches [B (/1000C)] measured by ¹³ C-NMR [(A+B) (/1000C)] is 1.8 or less (xxvii) The zero shear viscosity [η ₀ (P)] at 200°C and the weight average molecular weight (Mw) measured by the GPC-viscosity detector method (GPC-VISCO) are expressed by the following relational expression (Eq -2) is satisfied.
0.01×10 ^-13 ×Mw ^3.4 ≦η ₀ ≦4.50×10 ^-13 ×Mw ^3.4 (Eq-2)
(xxviii) The molecular weight at the maximum weight fraction (peak top M) in the molecular weight distribution curve obtained by GPC measurement is 1.0×10 ^4.30 to 1.0×10 ^4.50
[12] The ethylene polymer according to [11], which has a biomass degree of 1% to 99% according to ASTM D 6866.

[13] The ethylene polymer satisfies the following (xxix) to (xxxii), and is a copolymer of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms,
The ethylene contained in the raw material of the copolymer includes (I-1) 0.2% to 99% by weight of biomass-derived ethylene and 1% to 99.8% by weight of fossil fuel-derived ethylene; The ethylene polymer according to [1], which is a mixture (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight).
(xxix) MFR at 190℃ and 2.16 kg load is 0.1 g/10 minutes to 100 g/10 minutes (xxx) Density is 0.890 g/cm ³ to 0.970 g/cm ³
(xxxi) Sum of the number of methyl branches per 1000 carbon atoms [A (/1000C)] and the number of ethyl branches [B (/1000C)] measured by ¹³ C-NMR [(A+B) (/1000C)] is 1.8 or less (xxxii) The intrinsic viscosity [[η] (dl/g)] measured in decalin at 135°C and the weight average molecular weight (Mw) measured by GPC-viscosity detector method (GPC-VISCO) satisfies the following relational expression (Eq-3).
0.80×10 ^-4 ×Mw ^0.776 ≦[η]≦1.65×10 ^-4 ×Mw ^0.776 (Eq-3)
[14] The ethylene polymer according to [13], which has a biomass degree of 1% to 99% according to ASTM D 6866.

[15] The ethylene polymer (X3) satisfies the following (xxxiii) to (xxxv): 30% by mass or more and 85% by mass or less;
(xxxiii) Intrinsic viscosity ([η _X3 ]) measured in decalin at 135°C is 0.50 dl/g to 1.50 dl/g
(xxxiv) The ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) measured by GPC is 4.0 to 8.0.
(xxxv) Density d _X3 is 0.940g/cm ³ ~0.980g/cm ³
A copolymer (Y3) of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms, which satisfies the following (xxxvi) to (xxxviii): 15% by mass or more and 70% by mass or less ( However, the ethylene polymer (A2-3) is a mixture of the polymer (X3) and the polymer (Y3) (the total of which is 100% by mass),
(xxxvi) Intrinsic viscosity ([η _Y3 ]) measured in decalin at 135°C is 2.0 dl/g to 8.0 dl/g
(xxxvii) The ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) measured by GPC is 5.0 to 15.0.
(xxxviii) Density d _Y3 is 0.910g/cm ³ ~0.950g/cm ³ (However, density d _X3 ≧density d _Y3 )
The ethylene polymer (A2-3) satisfies the following (xxxix) to (xxxxi),
(xxxix) MFR at 190℃ and 2.16 kg load is 0.01 g/10 minutes to 20 g/10 minutes (xxxx) Density is 0.930 g/cm ³ to 0.960 g/cm ³
(xxxxi) The amount of components eluted at 85°C or lower by cross-fractionation chromatography (CFC) is 10% by mass or less The ethylene polymer (X3) and copolymer (Y3) contained in the above ethylene polymer (A2-3) The ethylene contained in the raw material of (I-1) is an ethylene mixture containing 0.2% to 99% by weight of biomass-derived ethylene and 1% to 99.8% by weight of fossil fuel-derived ethylene. (The total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight), the ethylene polymer according to [1].
[16] The ethylene polymer according to [15], which has a biomass degree of 1% to 99% according to ASTM D 6866.

[17] The ethylene-based polymer satisfies the following (xxxxxii) to (xxxxiv), and is a copolymer of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms,
The ethylene contained in the raw material of the copolymer includes (I-1) 0.2% to 99% by weight of biomass-derived ethylene and 1% to 99.8% by weight of fossil fuel-derived ethylene; The ethylene polymer according to [1], which is a mixture (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight).
(xxxxxii) MFR at 190°C and 2.16 kg load is 0.1 g/10 minutes to 100 g/10 minutes (xxxxiii) Density is 0.890 g/cm ³ to 0.925 g/cm ³
(xxxxiv) The ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) measured by GPC is 1.50 to 3.00.
[18] The ethylene polymer according to [17], which has a biomass degree of 1% to 99% according to ASTM D 6866.

[19] At least one selected from the group consisting of ethylene homopolymer, or ethylene and α-olefin having 3 to 20 carbon atoms, with a biomass-derived carbon concentration of 0.2 pMC (%) to 99.0 pMC (%) A method for producing an ethylene polymer that is a copolymer with a seed olefin,
Including the step of supplying a raw material containing ethylene to a polymerization vessel and polymerizing it with a polymerization catalyst,
At least one olefin (a) selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms contained in the raw material contains 0.2% by weight or more and 99% by weight or less of biomass-derived olefin (a1) and fossil fuels. An olefin mixture containing 1% to 99.8% by weight of fuel-derived olefin (a2) (the total of biomass-derived olefin (a1) and fossil fuel-derived olefin (a2) is 100% by weight), ethylene-based Method for producing polymers.
[20] The ethylene polymer satisfies the following (i) to (ii),
(i) Density is 0.890g/cm ³ ~0.970g/cm ³
(ii) Melt flow rate (MFR) at 190°C and 2.16 kg load is 0.1 g/10 min to 200 g/10 min. It is an ethylene mixture containing 0.2% to 99% by weight of derived ethylene and 1% to 99.8% by weight of fossil fuel-derived ethylene (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight). ), the method for producing an ethylene polymer according to [19].

[21] A step (x1) of polymerizing 20% by mass or more and 80% by mass or less of an ethylene polymer (X1) that satisfies the following (iii) to (iv),
(iii) Density is 0.890g/cm ³ to 0.970g/cm ³
(iv) Melt flow rate (MFR) at 190°C and 2.16 kg load is 0.01 g/10 minutes to 1,500 g/10 minutes Ethylene polymer (Y1) that satisfies the following (v) to (vi) 80% by mass or less and 20% by mass or more (however, the total of the polymer (X1) and the polymer (Y1) is 100% by weight) (y1),
(v) Density is 0.890g/cm ³ ~0.960g/cm ³
(vi) MFR at 190°C and 2.16 kg load is 0.01 g/10 min to 500 g/10 min. 1) It is an ethylene mixture containing 0.2% to 99% by weight of biomass-derived ethylene and 1% to 99.8% by weight of fossil fuel-derived ethylene (the total of biomass-derived ethylene and fossil fuel-derived ethylene 100% by weight),
The ethylene polymer obtained through the above steps (x1) and (y1) satisfies the following (vii) to (viii),
(vii) Density is 0.890g/cm ³ ~0.970g/cm ³
(viii) The method for producing an ethylene polymer according to [19], which has an MFR of 0.01 g/10 minutes to 60.0 g/10 minutes at 190° C. and a load of 2.16 kg.

[22] The ethylene polymer is a copolymer (A2-2) of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms,
The method for producing the copolymer (A2-2) includes:
A copolymer (X2) of 5% by weight or more, which satisfies the following (ix) to (xii) by polymerizing ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms.95 A step (x2) of producing % by weight or less;
(ix) Density d _X2 is 0.890g/cm ³ ~0.940g/cm ³
(x) Intrinsic viscosity [η _X2 ] measured in decalin at 135°C is 1.0 to 10.0 dl/g
(xi) The temperature (Tm (°C)) and density (d _X2 ) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter satisfy Tm<400×d _X2 -250.
(xii) The decane soluble portion (W (wt%)) and density (d _x2 ) at room temperature are
W<80×exp(−100(d _X2 −0.88))+0.1 is satisfied.
A copolymer (Y2) of 5% by weight or more 95 that satisfies the following (xiii) to (xv) by polymerizing ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms. a step (y2) of producing % by weight or less;
(xiii) Density d _Y2 is 0.910g/cm ³ ~0.970g/cm ³
(xiv) Intrinsic viscosity [η _Y2 ] measured in decalin at 135°C is 0.5 to 2.0 dl/g
(xv) The temperature (Tm (°C)) and density (d _Y2 ) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter satisfy Tm>138×d _Y2 -6.
_{The ratio (d X2 /d Y2 ) of the} density d
The ratio of the intrinsic viscosity [η _X2 ] of _the copolymer (X2) to the intrinsic viscosity [η _Y2 ] of the copolymer ( _Y2 ) ([η
Ethylene contained in the raw materials supplied to the polymerization vessel in each step (x2) and (y2) above is (I-1) 0.2% to 99% by weight of biomass-derived ethylene and 1% by weight of fossil fuel-derived ethylene % or more and 99.8% by weight or less (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight),
The density of the obtained copolymer (A2-2) is in the range of 0.890 to 0.955 g/cm ³ ,
The method for producing an ethylene polymer according to [19], wherein the copolymer (A2-2) has an MFR of 0.1 to 100 g/10 minutes at 190° C. and a load of 2.16 kg.
[23] A copolymer (A2-2) of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms, obtained by the production method described in [22],
Low-density polyethylene (D) produced by a high-pressure radical method that satisfies the following (xvi) to (xvii),
(xvi) MFR is 0.1 g/10 min to 50 g/10 min (xvii) If the molecular weight distribution (Mw/Mn) measured by GPC and MFR are Mw/Mn≧7.5×log(MFR)-1. 2
Melt and knead the ethylene polymer (A2-2) and high pressure radical low density polyethylene (D) so that the weight ratio is in the range of 99:1 to 60:40,
A method for producing an ethylene polymer mixture containing an ethylene polymer (A2-2) and a high-pressure radical process low density polyethylene (D).

[24] The ethylene polymer satisfies the following (xviii) to (xxii),
(xviii) The content of methyl branches and ethyl branches measured by ¹³ C-NMR [M _{Me + Et} (mol%)] and the content of all branches measured by ¹³ C-NMR [M _all ( mol%)] [M _Me+Et /M _all ] is in the range of 0.30 to 1.00.
(xix) MFR at 190°C and 2.16 kg load is 0.1 g/10 minutes to 100 g/10 minutes (xx) Density is 0.890 g/cm ³ to 0.970 g/cm ³
(xxi) The ratio [ ^MT /η * (g/P)] of the melt tension at 190 °C [MT (g)] and the shear viscosity [η ^* (P)] at 200 °C and an angular velocity of 1.0 rad/sec is It is in the range of 1.50×10 ⁻⁴ to 9.00×10 ⁻⁴ .
(xxii) Zero shear viscosity [η ₀ (P)] at 200°C and weight average molecular weight (Mw) measured by GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-1) .
0.01×10 ^-13 ×Mw ^3.4 ≦η ₀ ≦4.50×10 ^-13 ×Mw ^3.4 (Eq-1)
The ethylene contained in the raw material supplied to the polymerization vessel contains (I-1) 0.2% to 99% by weight of biomass-derived ethylene and 1% to 99.8% by weight of fossil fuel-derived ethylene; The method for producing an ethylene polymer according to [19], which is an ethylene mixture (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight).
[25] The ethylene polymer satisfies the following (xxiii) to (xxviii),
(xxiii) MFR at 190°C and 2.16 kg load is 0.1 g/10 minutes to 100 g/10 minutes (xxiv) Density is 0.890 g/cm ³ to 0.970 g/cm ³
(xxv) The ratio [MT/η * (g/P)] of the melt tension at 190° ^C [MT (g)] and the shear viscosity [η ^* (P)] at 200°C and an angular velocity of 1.0 rad/sec is It is in the range of 2.50×10 ⁻⁴ to 9.00×10 ⁻⁴ .
(xxvi) Sum of the number of methyl branches per 1000 carbon atoms [A (/1000C)] and the number of ethyl branches [B (/1000C)] measured by ¹³ C-NMR [(A+B) (/1000C)] is 1.8 or less (xxvii) The zero shear viscosity [η ₀ (P)] at 200°C and the weight average molecular weight (Mw) measured by the GPC-viscosity detector method (GPC-VISCO) are expressed by the following relational expression (Eq -2) is satisfied.
0.01×10 ^-13 ×Mw ^3.4 ≦η ₀ ≦4.50×10 ^-13 ×Mw ^3.4 (Eq-2)
(xxviii) The molecular weight at the maximum weight fraction (peak top M) in the molecular weight distribution curve obtained by GPC measurement is 1.0×10 ^4.30 to 1.0×10 ^4.50
The ethylene contained in the raw material supplied to the polymerization vessel contains (I-1) 0.2% to 99% by weight of biomass-derived ethylene and 1% to 99.8% by weight of fossil fuel-derived ethylene; The method for producing an ethylene polymer according to [19], which is an ethylene mixture (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight).

[26] The ethylene polymer satisfies the following (xxix) to (xxxii),
(xxix) MFR at 190°C and 2.16 kg load is 0.1 g/10 minutes to 100 g/10 minutes (xxx) Density is 0.890 g/cm ³ to 0.970 g/cm ³
(xxxi) Sum of the number of methyl branches per 1000 carbon atoms [A (/1000C)] and the number of ethyl branches [B (/1000C)] measured by ¹³ C-NMR [(A + B) (/1000C)] is 1.8 or less (xxxii) The intrinsic viscosity [[η] (dl/g)] measured in decalin at 135°C and the weight average molecular weight (Mw) measured by the GPC-viscosity detector method (GPC-VISCO) satisfies the following relational expression (Eq-3).
0.80×10 ^-4 ×Mw ^0.776 ≦[η]≦1.65×10 ^-4 ×Mw ^0.776 (Eq-3)
The ethylene contained in the raw material supplied to the polymerization vessel contains (I-1) 0.2% to 99% by weight of biomass-derived ethylene and 1% to 99.8% by weight of fossil fuel-derived ethylene; The method for producing an ethylene polymer according to [19], which is an ethylene mixture (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight).

[27] A step (x3) of polymerizing 30% by mass or more and 85% by mass or less of an ethylene polymer (X3) that satisfies the following (xxxiii) to (xxxv),
(xxxiii) Intrinsic viscosity ([η _X3 ]) measured in decalin at 135°C is 0.50 dl/g to 1.50 dl/g
(xxxiv) The ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) measured by GPC is 4.0 to 8.0.
(xxxv) Density d _X3 is 0.940g/cm ³ ~0.980g/cm ³
Contains 15% by mass or more and 70% by mass or less of an ethylene polymer (Y3) that satisfies the following (xxxvi) to (xxxviii) (however, the total of the polymer (X3) and the polymer (Y3) is 100% by mass or more % by mass),
(xxxvi) Intrinsic viscosity ([η _Y3 ]) measured in decalin at 135°C is 2.0 dl/g to 8.0 dl/g
(xxxvii) The ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) measured by GPC is 5.0 to 15.0.
(xxxviii) Density d _Y3 is 0.910g/cm ³ ~0.950g/cm ³ (However, density d _X3 ≧density d _Y3 )
Ethylene contained in the raw materials supplied to the polymerization vessel in steps (x3) and (y3) above is (I-1) 0.2% to 99% by weight of biomass-derived ethylene and 1% by weight of fossil fuel-derived ethylene. It is an ethylene mixture containing 99.8% by weight or less (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight),
The ethylene polymer (A2-3) obtained through the above steps (x3) and (y3) satisfies the following (xxxix) to (xxxxi),
(xxxix) MFR at 190℃ and 2.16 kg load is 0.01 g/10 minutes to 20 g/10 minutes (xxxx) Density is 0.930 g/cm ³ to 0.960 g/cm ³
(xxxxi) The method for producing an ethylene polymer according to [19], wherein the amount of components eluted at 85° C. or lower by cross fractionation chromatography (CFC) is 10% by mass or less.
[28] The ethylene polymer satisfies the following (xxxxxii) to (xxxxiv),
(xxxxxii) MFR at 190°C and 2.16 kg load is 0.1 g/10 minutes to 100 g/10 minutes (xxxxiii) Density is 0.860 g/cm ³ to 0.925 g/cm ³
(xxxxiv) The ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) measured by GPC is 1.50 to 3.00.
The ethylene contained in the raw material supplied to the polymerization vessel contains (I-1) 0.2% to 99% by weight of biomass-derived ethylene and 1% to 99.8% by weight of fossil fuel-derived ethylene; The method for producing an ethylene polymer according to [19], which is an ethylene mixture (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight).

[29] A resin composition comprising the ethylene polymer according to any one of [1] to [7] and [9] to [18].
[30] A resin composition comprising the ethylene polymer mixture according to [8].
[31] A molded article comprising the ethylene polymer according to any one of [1] to [7] and [9] to [18].
[32] A molded article made of the ethylene polymer mixture according to [8].

According to the ethylene polymer and the method for producing the polymer of the present invention, it is possible to reduce the environmental load (greenhouse gas generation) during the life cycle, and to adjust the amount of biomass-derived olefin in the ethylene polymer. No additional equipment or process is required to mix the biomass-derived ethylene polymer and the fossil fuel-derived ethylene polymer. Furthermore, according to the ethylene polymer and the method for producing the polymer of the present invention, it is possible to produce an ethylene polymer that has a desired biomass-derived carbon concentration and has equivalent performance. , it is possible to promote the spread of such ethylene-based polymers at reduced costs.

The present invention will be explained in more detail below.
[Biomass-derived olefin, biomass-derived carbon]
Biomass refers to all renewable natural raw materials and their residues of plant or animal origin, including fungi, yeast, algae, and bacteria, and biomass-derived olefins (ethylene, α-olefins, etc.) This refers to the olefin obtained from this biomass. Biomass-derived carbon contains a certain amount of ¹⁴ C isotope as carbon (at a ratio of about 10 ^-12 ).

[Olefins derived from fossil fuels]
Fossil fuels are fossilized fossilized remains of animals and plants, such as oil, coal, natural gas, and shale gas, which have been increased in volume and pressure over hundreds of millions of years.Olefins derived from fossil fuels ( Ethylene, α-olefin, etc.) are olefins obtained from this fossil fuel. ¹⁴ C is not detected in fossil-derived carbon because it has been sufficiently longer than the half-life of ¹⁴ C isotope, which is 5,730 years.

[Ethylene polymer (A)]
The ethylene polymer (A) of the present invention mainly contains structural units derived from ethylene (typically contains more than 50% by weight, preferably 60% by weight of structural units derived from ethylene). (exceeding and including) polymers. Such an ethylene polymer (A) is typically an ethylene homopolymer (Aα) or at least one olefin (b) selected from the group consisting of ethylene and an α-olefin having 3 to 20 carbon atoms ( Hereinafter, at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms is also simply referred to as olefin (b). ), etc.

As the ethylene copolymer (Aβ), a random copolymer (Aβ-1) of ethylene and olefin (b) (for example, ethylene/propylene random copolymer, ethylene/1-butene random copolymer, etc.) is used. )) (Hereinafter, the random copolymer (Aβ-1) of ethylene and olefin (b) is also simply referred to as the ethylene-based random copolymer (Aβ-1).).

Examples of α-olefins having 3 to 20 carbon atoms that can be the constituent units of the ethylene copolymer (Aβ) include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 4-methyl-1. -pentene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. Among these α-olefins, 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene are preferred from the viewpoint of ease of polymerization and mechanical strength of the resulting copolymer.

(Requirement (I))
The ethylene copolymer (A) of the present invention satisfies the following requirement (I).
Requirement (I): At least one olefin (a) selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms (hereinafter referred to as ethylene and carbon At least one olefin selected from the group consisting of α-olefins of 3 to 20 is also simply referred to as olefin (a). It is an olefin mixture containing 1% to 99.8% by weight of a fuel-derived olefin (a2), preferably 1% to 95% by weight of a biomass-derived olefin (a1) and 5% by weight of a fossil fuel-derived olefin (a2). % or more and 99% by weight or less, more preferably a biomass-derived olefin (a1) of 5% or more and 90% by weight or less, and a fossil fuel-derived olefin (a2) of 10% or more and 95% by weight or less. It is an olefin mixture, more preferably an olefin mixture containing 10% by weight or more and 69% by weight or less of biomass-derived olefin (a1) and 31% by weight or more and 90% by weight or less of fossil fuel-derived olefin (a2). Here, the total of the biomass-derived olefin (a1) and the fossil fuel-derived olefin (a2) is 100% by weight. Moreover, the biomass-derived olefin (a1) means the biomass-derived olefin contained in the olefin (a), and the fossil fuel-derived olefin (a2) means the fossil fuel-derived olefin contained in the olefin (a).
In order to set the ratio (wt%) of the biomass-derived olefin (a1) and the fossil fuel-derived olefin (a2) contained in the above olefin (a) to a desired ratio, for example, separately obtained biomass-derived olefin (a1) and the fossil fuel-derived olefin (a2) may be mixed in a desired ratio (wt%).

In addition, at least one type of olefin (a) contained in the raw material means, for example, when the ethylene copolymer (A) is an ethylene homopolymer (A1), the ethylene that is the raw material meets the above requirements (I). ), and when the ethylene copolymer (A) is an ethylene copolymer (A2), the ethylene and olefins ( b) In the case of a random copolymer of one or more of This means that one or more olefins selected from the group consisting of 20) (ethylene only, propylene only, both ethylene and propylene, etc.) satisfy the above requirement (I).

Since the production cost of biomass-derived olefins is higher than that of fossil fuel-derived olefins, it is necessary to use raw materials in which the ratio of biomass-derived olefins (a1) and fossil fuel-derived olefins (a2) in the olefin mixture satisfies the above range. Ethylene-based polymers manufactured using this technology can promote the spread of ethylene-based polymers that reduce costs while contributing to reducing the environmental impact during their life cycles.
Requirement (I-1): Ethylene must be included as the olefin (a) contained in the raw material of the ethylene polymer (A) (Requirement (I) ), it is preferable that the mixture be an ethylene mixture of biomass-derived ethylene and fossil fuel-derived ethylene in a specified quantitative ratio. When the ethylene polymer (A) is an ethylene copolymer (A2), the olefin species contained in the raw material other than the types applicable to olefin (a) are fossil fuels, even if they are only biomass-derived olefins. Only the derived olefin may be used. For example, when it is desired to emphasize the improvement of the biomass degree of the ethylene polymer (A), it is desirable that the olefin species other than the type corresponding to the olefin (a) are only biomass-derived olefins. For example, if cost control is important, it is desirable that the olefin species other than the olefin (a) be only fossil fuel-derived olefins. Further, an olefin corresponding to olefin (a) can also be selected in consideration of ease of production of the olefin used as a raw material for the ethylene polymer (A).
In addition, biomass-derived olefins and fossil fuel-derived olefins of the same olefin species have different polymerization performance (activity, copolymerizability, stereoregularity, stereoregularity distribution, molecular weight, It is said that there is no significant difference in the distribution (distribution, etc.).

(Requirement (II))
The ethylene polymer (A) of the present invention further satisfies the following requirement (II).
The biomass-derived carbon concentration of the ethylene polymer (A) is 0.2 pMC (%) or more and 99.0 pMC (%) or less, preferably 1.0 pMC (%) or more and 95.0 pMC (%), more preferably It is 5.0 pMC (%) or more and 90.0 pMC (%) or less, more preferably 10.0 pMC (%) or more and 69.0 pMC (%) or less. The ethylene polymer (A) whose biomass-derived carbon concentration satisfies this range can promote the spread of cost-reduced ethylene polymers while contributing to a reduction in environmental load during the life cycle. In addition, from the viewpoint of placing more emphasis on cost control while contributing to a certain reduction of environmental impact, the biomass-derived carbon concentration of the ethylene polymer (A) is preferably 0.2 pMC (%) or more and 10.0 pMC ( %) or less. Note that this requirement (II) must be satisfied in any of the ethylene homopolymer (A1), ethylene copolymer (A2), and ethylene random copolymer (A2-1) described below.

[Method for measuring biomass-derived carbon concentration]
The biomass-derived carbon concentration was the pMC (percent modern carbon) value measured in accordance with ASTM D 6866-21.
pMC refers to the ratio of the ¹⁴ C concentration of sample carbon to standard modern carbon, and is usually a value rounded to two decimal places.

The principle of determining the biomass-derived carbon concentration from the ^14C abundance ratio in carbon is described in, for example, "Evaluation of the degree of biomass-derived carbon in biomass plastics by carbon-14 measurement using AMS," Keiken, 39 (4), 2012. , is described as follows.
Carbon dioxide in the atmosphere contains a certain proportion of carbon-14, and this proportion is maintained even when plants fix carbon dioxide. Carbon-14 is a radioactive isotope element with a half-life of 5,730 years, and decays and decreases at a constant rate. Taking advantage of this fact, this method estimates the number of years that have passed since plants fixed carbon dioxide by measuring the concentration (ratio) of carbon-14. It is believed that oil has been stored underground for over a million years. For this reason, even if petroleum is derived from living organisms, all carbon-14 has decayed and is not contained. On the other hand, plants contain a certain proportion of carbon-14. Whether it is derived from fossil fuels or biomass can be distinguished by whether it contains carbon-14. Furthermore, even if biomass raw materials and petroleum raw materials are mixed, it is possible to identify the ratio by measuring the carbon-14 concentration using a dating method and comparing it with the current ratio of carbon-14 in plants. Become. This is the principle of the method for measuring biomass origin by measuring carbon-14 concentration.

The ethylene polymer (A) of the present invention preferably satisfies any of the following (i) to (ii), more preferably both of the following (i) to (ii).
(i) The density of the ethylene polymer is 0.890 g/cm ³ to 0.970 g/cm ³ , preferably 0.900 g/cm ³ to 0.950 g/cm ³ . When the density is within this range, the properties of the ethylene polymer (A) can be fully exhibited.
(ii) The melt flow rate (MFR) of the ethylene polymer (A) at 190°C and a load of 2.16 kg is 0.01 g/10 minutes to 1500 g/10 minutes, preferably 0.03 g/10 minutes. ~200g/10 minutes. When the melt flow rate (MFR) is within this range, the ethylene polymer (A) has excellent moldability.

The ethylene polymer (A) of the present invention has a biomass degree according to ASTM D6866, preferably 1% or more and 99% or less, more preferably 1 or more and 95% or less, still more preferably 5% or more and 90% or less, and most preferably is 10% or more and 69% or less. In addition, ethylene polymers (A1-1) to (A1-4) and (A2-1) to (A2-3), which are preferred forms of the ethylene polymer (A) described later, are also compliant with ASTM D6866. It is desirable that the biomass level obtained satisfies the above range.

[Method for measuring biomass content (biobased carbon content)]
Based on ASTM D 6866-21, corrected by δ ¹³ C (measurement of ¹³ C concentration ( ¹³ C/ ¹² C) of sample carbon, deviation from reference sample expressed in thousandth deviation (‰)) Calculated using pMC. For the atmospheric correction coefficient, the value for 2019-2021 described in ASTM D6866-21 (latest edition) was used (100.0 pMC).

The ethylene polymer (A) of the present invention is not particularly limited in its production method as long as its biomass-derived carbon concentration is within the above-mentioned range and the raw material contains the above-mentioned olefin mixture. The ethylene polymer (A) of the present invention can be produced, for example, by the method for producing an ethylene polymer (A) described below.

As the ethylene polymer (A) of the present invention, the following ethylene polymers that can be produced by single-stage polymerization under constant reaction conditions are mentioned as preferred forms.

The ethylene polymer (A) of the present invention is an ethylene polymer (A1-1) that satisfies any of the following (xviii) to (xxii), preferably satisfies all of the following (xviii) to (xxii). ) is a preferred form.
(xviii) The content of methyl branches and ethyl branches measured by ¹³ C-NMR [M _{Me + Et} (mol%)] and the content of all branches measured by ¹³ C-NMR [M _all ( mol%)] is in the range of 0.30 _to 1.00, preferably in the range of 0.50 to 1.00, more preferably _in the range of 0.70 to 1. The range is .00.
(xix) MFR at 190°C and 2.16 kg load is 0.1 g/10 minutes to 100 g/10 minutes, preferably 1.0 g/10 minutes to 50 g/10 minutes, more preferably 4.0 g/10 minutes. minutes to 30g/10 minutes.
(xx) Density is 0.890g/cm ³ to 0.970g/cm ³ , preferably 0.890g/cm ³ to 0.945g/cm ³ , more preferably 0.900g/cm ³ to It is 0.936g/cm ³ .
(xxi) The ratio [ ^MT /η * (g/P)] of the melt tension at 190 °C [MT (g)] and the shear viscosity [η ^* (P)] at 200 °C and an angular velocity of 1.0 rad/sec is , in the range of 1.50×10 ⁻⁴ to 9.00×10 ⁻⁴ , preferably in the range of 2.00×10 ⁻⁴ to 7.00×10 ⁻⁴ , more preferably 2.60× It is in the range of 10 ^-4 to 5.00×10 ^-4 .
(xxii) The zero shear viscosity [η ₀ (P)] at 200°C and the weight average molecular weight (Mw) measured by the GPC-viscosity detector method (GPC-VISCO) are expressed by the following relational expression (Eq-1). meet,
0.01×10 ^-13 ×Mw ^3.4 ≦η ₀ ≦4.50×10 ^-13 ×Mw ^3.4 (Eq-1)
Preferably, the following relational expression (Eq-1-1) is satisfied,
0.05×10 ^-13 ×Mw ^3.4 ≦η ₀ ≦4.50×10 ^-13 ×Mw ^3.4 (Eq-1-1)
More preferably, the following relational expression (Eq-1-2) is satisfied,
0.10×10 ^-13 ×Mw ^3.4 ≦η ₀ ≦3.50×10 ^-13 ×Mw ^3.4 (Eq-1-2)
Particularly preferably, the following relational expression (Eq-1-3) is satisfied.
0.15×10 ^-13 ×Mw ^3.4 ≦η ₀ ≦1.80×10 ^-13 ×Mw ^3.4 (Eq-1-3)

The above ethylene polymer (A1-1) also satisfies the above requirements (II), that is, the raw material ethylene is contained in the olefin (a), and the ethylene satisfies the requirements (I). This is a preferable form.
The method for producing the ethylene polymer (A1-1) is not particularly limited as long as a polymer satisfying the above characteristics is obtained, but the polymerization is usually carried out in a single stage. Ethylene polymer (A1-1) can be produced by the production method of -1).

The ethylene polymer (A) of the present invention is an ethylene polymer (A1-2) that satisfies any of the following (xxiii) to (xxviii), preferably satisfies all of the following (xxiii) to (xxviii). ) is a preferred form.
(xxiii) MFR at 190°C and 2.16 kg load is 0.1 g/10 minutes to 100 g/10 minutes, preferably 1.0 g/10 minutes to 50 g/10 minutes, more preferably 1.0 g/10 minutes to 30 g/10 minutes, particularly preferably 4.0 g/10 minutes to 30 g/10 minutes.
(xxiv) Density is 0.890g/cm ³ to 0.970g/cm ³ , preferably 0.890g/cm ³ to 0.964g/cm ³ , more preferably 0.903g/cm ³ to 0.940 g/cm ³ , particularly preferably 0.903 g/cm ³ to 0.935 g/cm ³ .
(xxv) The ratio [MT/η * (g/P)] of the melt tension at 190° ^C [MT (g)] and the shear viscosity [η ^* (P)] at 200°C and an angular velocity of 1.0 rad/sec is , in the range of 2.50×10 ⁻⁴ to 9.00×10 ⁻⁴ , preferably in the range of 2.50×10 ⁻⁴ to 7.00×10 ⁻⁴ , more preferably 3.00× It is in the range of 10 ^-4 to 5.00×10 ^-4 .
(xxvi) Sum of the number of methyl branches per 1000 carbon atoms [A (/1000C)] and the number of ethyl branches [B (/1000C)] measured by ¹³ C-NMR [(A+B) (/1000C)] is 1.8 or less, preferably 1.3 or less, more preferably 0.8 or less, particularly preferably 0.5 or less. Note that the value of [(A+B)(/1000C)] is usually 0.1 or more.
(xxvii) The zero shear viscosity [η ₀ (P)] at 200°C and the weight average molecular weight (Mw) measured by the GPC-viscosity detector method (GPC-VISCO) are expressed by the following relational expression (Eq-2). meet,
0.01×10 ^-13 ×Mw ^3.4 ≦η ₀ ≦4.50×10 ^-13 ×Mw ^3.4 (Eq-2)
Preferably, the following relational expression (Eq-2-1) is satisfied,
0.05×10 ^-13 ×Mw ^3.4 ≦η ₀ ≦4.50×10 ^-13 ×Mw ^3.4 (Eq-2-1)
More preferably, the following relational expression (Eq-2-2) is satisfied,
0.10×10 ^-13 ×Mw ^3.4 ≦η ₀ ≦3.50×10 ^-13 ×Mw ^3.4 (Eq-2-2)
Particularly preferably, the following relational expression (Eq-2-3) is satisfied.
0.15×10 ^-13 ×Mw ^3.4 ≦η ₀ ≦1.80×10 ^-13 ×Mw ^3.4 (Eq-2-3)
(xxviii) The molecular weight at the maximum weight fraction (peak top M) in the molecular weight distribution curve obtained by GPC measurement is 1.0×10 ^4.30 to 1.0×10 ^4.50 , preferably 1.00×10 ^4.30 ~ 1.0×10 ^4.40 .

The above ethylene polymer (A1-2) also satisfies the above requirements (II), that is, the raw material ethylene is contained in the olefin (a), and the ethylene satisfies the requirements (I). This is a preferable form.
The method for producing the ethylene polymer (A1-2) is not particularly limited as long as a polymer satisfying the above characteristics is obtained, but polymerization is usually carried out in a single stage. Ethylene polymer (A1-2) can be produced by the production method of -2).

The ethylene polymer (A) of the present invention is a copolymer of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms, and is a copolymer of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms. A preferred embodiment is an ethylene polymer (A1-3) that satisfies any one of the following (xxix) to (xxxii) below.
(xxix) MFR at 190°C and 2.16 kg load is 0.1 g/10 minutes to 100 g/10 minutes, preferably 1.0 g/10 minutes to 50 g/10 minutes, more preferably 4.0 g/10 minutes. minutes to 30g/10 minutes.
(xxx) Density is 0.890g/cm ³ to 0.970g/cm ³ , preferably 0.890g/cm ³ to 0.964g/cm ³ , more preferably 0.905g/cm ³ to It is 0.960g/cm ³ .
(xxxi) Sum of the number of methyl branches per 1000 carbon atoms [A (/1000C)] and the number of ethyl branches [B (/1000C)] measured by ¹³ C-NMR [(A + B) (/1000C)] is 1.8 or less, preferably 1.3 or less, more preferably 0.8 or less, particularly preferably 0.5 or less. Note that the value of [(A+B)(/1000C)] is usually 0.1 or more.
(xxxii) The following relational expression ( Eq-3) is satisfied,
0.80×10 ^-4 ×Mw ^0.776 ≦[η]≦1.65×10 ^-4 ×Mw ^0.776 (Eq-3)
Preferably, the following relational expression (Eq-3-1) is satisfied,
0.90×10 ^-4 ×Mw ^0.776 ≦[η]≦1.55×10 ^-4 ×Mw ^0.776 (Eq-3-1)
More preferably, the following relational expression (Eq-3-2) is satisfied.
0.90×10 ^-4 ×Mw ^0.776 ≦[η]≦1.40×10 ^-4 ×Mw ^0.776 (Eq-3-2)

The above ethylene polymer (A1-3) also satisfies the above requirements (II), that is, the raw material ethylene is contained in the olefin (a), and the ethylene satisfies the requirements (I). This is a preferable form.
The method for producing the ethylene polymer (A1-3) is not particularly limited as long as a polymer satisfying the above characteristics is obtained, but polymerization is usually carried out in a single stage. The ethylene polymer (A1-3) can be produced by the production method of -3).

The ethylene polymer (A) of the present invention is a copolymer of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms, and is a copolymer of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms. ), preferably all of the following (xxxxxii) to (xxxxiv), is a preferred form of the ethylene polymer (A1-4).
(xxxxxii) MFR at 190°C and 2.16 kg load is 0.1 g/10 minutes to 100 g/10 minutes, preferably 1.0 g/10 minutes to 30.0 g/10 minutes, more preferably 1.0 g /10 minutes to 20.0 g/10 minutes, particularly preferably 5.0 g/10 minutes to 20.0 g/10 minutes.
(xxxxiii) The density is 0.890 g/cm ³ to 0.925 g/cm ³ , preferably 0.890 g/cm ³ to 0.920 g/cm ³ , more preferably 0.890 g/cm ³ to 0.915 g/cm ³ , particularly preferably 0.890 g/cm ³ to 0.910 g/cm ³ .
(xxxxiv) The ratio (Mw/Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) measured by GPC is 1.50 to 3.00, preferably 1.50 to 2.50, More preferably 1.50 to 2.20, particularly preferably 1.60 to 2.10.

The above ethylene polymer (A1-4) also satisfies the above requirements (II), that is, the raw material ethylene is contained in the olefin (a), and the ethylene satisfies the requirements (I). This is a preferable form.
The method for producing the ethylene polymer (A1-4) is not particularly limited as long as a polymer satisfying the above characteristics is obtained, but the polymerization is usually carried out in a single stage. Ethylene polymer (A1-4) can be produced by the production method of -4).

In addition, as the ethylene polymer (A) of the present invention, the following ethylene polymers that can be produced by multistage polymerization in which polymerization is performed in two or more stages with different reaction conditions are preferably used. Can be mentioned.

The ethylene polymer (A) of the present invention may be an ethylene homopolymer or a copolymer of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms, which satisfies specific conditions. selected from the group consisting of a polymer (X1) (hereinafter also referred to as an ethylene polymer (X1)), an ethylene homopolymer that satisfies specific conditions, or ethylene and an α-olefin having 3 to 20 carbon atoms. One preferred form is an ethylene polymer (A2-1), which is a mixture containing a copolymer (Y1) (hereinafter also referred to as an ethylene polymer (Y1)) with at least one type of olefin.

The ethylene polymer (A2-1) is usually a mixture containing 20% by mass to 80% by mass of the ethylene polymer (X1) and 80% by mass to 20% by mass of the ethylene polymer (Y1), Preferably, it is a mixture containing 25% by mass or more and 75% by mass or less of ethylene polymer (X1) and 25% by mass or more of 75% by mass or less of ethylene polymer (Y1), and more preferably ethylene polymer (X1). It is a mixture containing 30% by mass or more and 70% by mass or less and ethylene polymer (Y1) 70% by mass or less and 30% by mass or more. However, the total of the ethylene polymer (X1) and the ethylene polymer (Y1) is 100% by weight.

The ethylene polymer (X1) satisfies any of the following (iii) to (iv), preferably all of the following (iii) to (iv).
(iii) Density d _x1 is 0.890 g/cm ³ to 0.970 g/cm ³ , preferably 0.890 g/cm ³ to 0.960 g/cm ³ , more preferably 0.895 g/cm ³ to It is 0.950g/cm ³ .
(iv) Melt flow rate (MFR) at 190°C and 2.16 kg load is 0.01 g/10 minutes to 1,500 g/10 minutes, preferably 0.01 g/10 minutes to 1400 g/10 minutes. , more preferably 0.01 g/10 minutes to 1300 g/10 minutes.

The ethylene polymer (Y1) satisfies any of the following (v) to (vi), preferably all of the following (v) to (vi).
(v) Density d _y1 is 0.890 g/cm ³ to 0.960 g/cm ³ , preferably 0.890 g/cm ³ to 0.960 g/cm ³ , more preferably 0.890 g/cm ³ to It is 0.950g/cm ³ .
(vi) MFR at 190°C and 2.16 kg load is 0.01 g/10 minutes to 500 g/10 minutes, preferably 0.01 g/10 minutes to 250 g/10 minutes, more preferably 0.05 g/10 minutes. minutes to 200g/10 minutes.

Further, the ethylene polymer (X1) and the ethylene polymer (Y1) satisfy at least one condition selected from the following (iii') and (iv').
(iii') The density of the ethylene/α-olefin copolymer (X1) is greater than the density of the ethylene/α-olefin copolymer (Y1).
(iv') The above MFR of the ethylene/α-olefin copolymer (X1) is larger than the above MFR of the ethylene/α-olefin copolymer (Y1).

The ethylene polymer (A2-1), which is a mixture of the ethylene polymer (X1) and the ethylene polymer (Y1), satisfies any of the following (vii) to (viii), preferably the following ( All of vii) to (viii) are satisfied.
(vii) Density is 0.890 g/cm ³ to 0.970 g/cm ³ , preferably 0.890 g/cm ³ to 0.960 g/cm ³ , more preferably 0.890 g/cm ³ to It is 0.950g/cm ³ .
(viii) MFR at 190°C and 2.16 kg load is 0.01 g/10 minutes to 60.0 g/10 minutes, preferably 0.01 g/10 minutes to 30 g/10 minutes, more preferably 0.01 g /10 minutes to 20g/10 minutes.

The above ethylene polymer (A2-1) also satisfies the above requirements (II), that is, the raw material ethylene is contained in the olefin (a), and the ethylene satisfies the requirements (I). This is a preferable form.
The method for producing the ethylene polymer (A2-1) is not particularly limited as long as a polymer satisfying the above characteristics can be obtained, but usually multi-stage polymerization is typically used to produce the ethylene polymer (X1). The polymerization is carried out in a multi-stage polymerization having two or more stages including a step and a step of producing the ethylene polymer (Y1), for example, ethylene polymerization by the method for producing the ethylene polymer (A2-1) described below. The system polymer (A2-1) can be produced.

The ethylene polymer (A) of the present invention is a copolymer (X2) of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms, which satisfies specific conditions. (hereinafter also referred to as ethylene/α-olefin copolymer (X2)) and at least one olefin selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms that satisfy specific conditions. At least one type selected from the group consisting of ethylene and α-olefin having 3 to 20 carbon atoms, which is a mixture containing polymer (Y2) (hereinafter also referred to as ethylene/α-olefin copolymer (Y2)). A copolymer (A2-2) with an olefin (hereinafter also referred to as an ethylene/α-olefin copolymer (A2-2) or an ethylene polymer (A2-2)) is a preferred form.

Ethylene/α-olefin copolymer (A2-2) is usually 5% to 95% by mass of ethylene/α-olefin copolymer (X2) and 95% by mass of ethylene/α-olefin copolymer (Y2). It is a mixture containing 5% by mass or more of ethylene/α-olefin copolymer (X2) and 80% by mass or less of ethylene/α-olefin copolymer (Y2) and 80% by mass or less of ethylene/α-olefin copolymer (Y2). It is a mixture containing 30% by mass or more and 70% by mass or less of ethylene/α-olefin copolymer (X2) and 70% by mass or less of ethylene/α-olefin copolymer (Y2) 30% by mass or more. % or more. However, the total of the ethylene/α-olefin copolymer (X2) and the ethylene/α-olefin copolymer (Y2) is 100% by weight.

_First , the ratio ( _{d X2 /} d _Y2 ) of the density d be. The density ratio (d _X2 /d _Y2 ) is preferably 0.930 to 0.999.

Further _{, the} ratio of the intrinsic viscosity [ _η [η _Y2 ]) is 1 or more. The limiting viscosity ratio ([η _X2 ]/[η _Y2 ]) is preferably 1.05 to 10, more preferably 1.1 to 5.

The ethylene/α-olefin copolymer (X2) satisfies any of the following (ix) to (xii), preferably all of the following (ix) to (xii).
⁽ _ix ^{) Density d _} .930g/cm ³ .
( _x ) Intrinsic viscosity [η .0dl/g.
(xi) The temperature (Tm (°C)) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter and _the density ( _d d _X2 -297, more preferably Tm<500×d _X2 -344, particularly preferably Tm<550×d _X2 -391.
(xii) The decane soluble portion (W (wt%)) and density (d _x2 ) at room temperature are
W<80×exp(-100(d _- 0.88))+0.1, preferably W<60×exp(-100(d-0.88)+0.1), more preferably W<40×exp(-100(d-0.88)+0.1) is satisfied.

The ethylene/α-olefin copolymer (Y2) satisfies any of the following (xiii) to (xv), preferably all of the following (xiii) to (xv).
(xiii) Density d _Y2 is 0.910g/cm ³ to 0.970g/cm ³ , preferably 0.915g/cm ³ to 0.960g/cm ³ , more preferably 0.925g/cm ³ to 0 .960g/cm ³ .
(xiv) The intrinsic viscosity [η _Y2 ] measured in decalin at 135°C is 0.5 to 2.0 dl/g, preferably 0.55 to 1.9 dl/g, more preferably 0.6 to 1 .8 dl/g.
(xv) The temperature (Tm (°C)) and density (d _Y2 ) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter satisfy Tm>138×d _Y2 -6, preferably Tm>128× It satisfies d _Y2 +4, and more preferably satisfies Tm>110×d+21.

The density of the ethylene/α-olefin copolymer (A2-2), which is a mixture of the ethylene/α-olefin copolymer (X2) and the ethylene/α-olefin copolymer (Y2), is usually 0.890. ~0.955g/cm ³ , preferably 0.900g/cm ³ ~0.950g/cm ³ .
The melt flow rate (MFR) of the ethylene/α-olefin copolymer (A2-2) at 190°C and a load of 2.16 kg is usually 0.1 to 100 g/10 minutes, preferably 0.2 g/10 min. 10 minutes to 50g/10 minutes.

The above ethylene/α-olefin copolymer (A2-2) also satisfies the above requirements (II), that is, the raw material ethylene is contained in the olefin (a), and the ethylene is ) is a preferable form.
The method for producing the ethylene/α-olefin copolymer (A2-2) is not particularly limited as long as a polymer satisfying the above characteristics can be obtained, but it is usually multi-stage polymerization, typically the above ethylene/α-olefin copolymer. Polymerization is carried out in a multi-stage polymerization having two or more stages, including a step of producing the polymer (X2) and a step of producing the ethylene/α-olefin copolymer (Y2). Ethylene/α-olefin copolymer (A2-2) can be produced by the method for producing α-olefin copolymer (A2-2).

The ethylene polymer (A) of the present invention may be an ethylene homopolymer or a copolymer of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms, which satisfies specific conditions. A polymer (X3) (hereinafter also referred to as an ethylene polymer (X3)), and at least one olefin selected from the group consisting of ethylene and an α-olefin having 3 to 20 carbon atoms, which satisfies specific conditions. One preferred form is the ethylene polymer (A2-3), which is a mixture containing the copolymer (Y3) (hereinafter also referred to as ethylene/α-olefin copolymer (Y3)).

The ethylene polymer (A2-3) usually contains an ethylene polymer (X3) of 30% by mass or more and 85% by mass or less and an ethylene/α-olefin copolymer (Y3) of 15% by mass or more and 70% by mass or less. It is a mixture, preferably a mixture containing 30% by mass or more and 70% by mass or less of ethylene polymer (X3) and 70% by mass or more and 30% by mass or less of ethylene/α-olefin copolymer (Y3), and more preferably is a mixture containing 30% by mass or more and 60% by mass or less of an ethylene polymer (X3) and 40% by mass or more and 70% by mass or less of an ethylene/α-olefin copolymer (Y3). However, the total amount of the ethylene polymer (X3) and the ethylene/α-olefin copolymer (Y3) is 100% by weight.

The ethylene polymer (X3) satisfies any of the following (xxxiii) to (xxxv), preferably all of the following (xxxiii) to (xxxv).
(xxxiii) The intrinsic viscosity ([ _η 0.70 to 1.30 dl/g, particularly preferably 0.80 dl/g to 1.20 dl/g.
(xxxiv) The ratio (Mw/Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) measured by GPC is 4.0 to 8.0, preferably 4.2 to 7.5, or more. It is preferably 4.5 to 7.0, particularly preferably 5.0 to 6.5.
⁽ _xxxv ^{) Density d _} .980 g/cm ³ , particularly preferably 0.965 g/cm ³ to 0.975 g/cm ³ .

The ethylene/α-olefin copolymer (Y3) satisfies any of the following (xxxvi) to (xxxviii), preferably all of the following (xxxvi) to (xxxviii).
(xxxvi) The intrinsic viscosity ([η _Y3 ]) measured in decalin at 135°C is 2.0 dl/g to 8.0 dl/g, preferably 2.0 to 6.0 dl/g, more preferably It is 2.0 to 5.0 dl/g, particularly preferably 2.5 dl/g to 4.0 dl/g.
(xxxvii) The ratio (Mw/Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) measured by GPC is 5.0 to 15.0, preferably 6.0 to 13.0, and more. It is preferably 7.0 to 11.0, particularly preferably 8.0 to 10.0.
(xxxviii) Density d _Y3 is 0.910g/cm ³ to 0.950g/cm ³ , preferably 0.915g/cm ³ to 0.945g/cm ³ , more preferably 0.920g/cm ³ to 0 .940 g/cm ³ , particularly preferably 0.925 g/cm ³ to 0.935 g/cm ³ . However, the density d _X3 of the ethylene polymer (X3) ≧ the density d _Y3 of the ethylene/α-olefin copolymer (Y3).

The ethylene polymer (A2-3), which is a mixture of the ethylene polymer (X3) and the ethylene/α-olefin copolymer (Y3), satisfies any of the following (xxxix) to (xxxxi): Preferably, all of the following (xxxix) to (xxxxi) are satisfied.
(xxxix) MFR at 190°C and 2.16 kg load is 0.01 g/10 minutes to 20 g/10 minutes, preferably 0.05 g/10 minutes to 10 g/10 minutes, more preferably 0.1 g/10 minutes. ~2.0 g/10 min, particularly preferably 0.2 g/10 min ~ 1.0 g/10 min.
(xxxx) Density is 0.930g/cm ³ to 0.960g/cm ³ , preferably 0.935g/cm ³ to 0.960g/cm ³ , more preferably 0.940g/cm ³ to 0 .960 g/cm ³ , particularly preferably 0.945 g/cm ³ to 0.955 g/cm ³ .
(xxxxi) The amount of components eluted at 85° C. or lower by cross fractionation chromatography (CFC) is 10% by mass or less, preferably 9.5% by mass or less, more preferably 9.0% by mass or less. Note that the amount of components eluted at 85° C. or lower by cross-fractionation chromatography (CFC) is usually 0.1% by mass or more.

The above ethylene polymer (A2-3) also satisfies the above requirements (II), that is, the raw material ethylene is contained in the olefin (a), and the ethylene satisfies the requirements (I). This is a preferable form.
The method for producing the ethylene polymer (A2-3) is not particularly limited as long as a polymer satisfying the above characteristics is obtained, but usually involves multi-stage polymerization, typically producing the ethylene polymer (X3) above. Polymerization is carried out in a multi-stage polymerization process having two or more stages, including a step and a step of producing the ethylene/α-olefin copolymer (Y3). For example, the ethylene polymer (A2-3) described below is The ethylene polymer (A2-3) can be produced by the production method.

The ethylene polymer (A) may be mixed with an ethylene polymer other than the ethylene polymer (A) and used as an ethylene polymer mixture.
For example, an ethylene polymer containing an ethylene polymer (A2-2) (ethylene/α-olefin copolymer (A2-2)) and a low density polyethylene (D) produced by a high-pressure radical method that meets specific requirements. It can be used as a combined mixture (A3).

The weight ratio (A2-2):(D) between the ethylene polymer (A2-2) and the high-pressure radical-processed low-density polyethylene (D) is usually in the range of 99:1 to 60:40, preferably The range is from 98:2 to 70:30, more preferably from 98:2 to 80:20.

The low density polyethylene (D) satisfies any of the following (xvi) to (xvii), preferably all of the following (xvi) to (xvii).
(xvi) Melt flow rate (MFR) at 190°C and 2.16 kg load is 0.1 g/10 minutes to 50 g/10 minutes, preferably 0.2 g/10 minutes to 10 g/10 minutes, more preferably is 0.2 g/10 minutes to 8.0 g/10 minutes.
(xvii) The molecular weight distribution (Mw/Mn) obtained by GPC measurement and the above MFR satisfy the following relationship,
Mw/Mn≧7.5×log(MFR)-1.2
Preferably, the following relational expression is satisfied,
Mw/Mn≧7.5×log(MFR)-0.5
More preferably, the following relational expression is satisfied.
Mw/Mn≧7.5×log(MFR)

The ethylene-containing olefin (monomer) that is the raw material for low-density polyethylene (D) may consist only of fossil fuel-derived olefins, or may consist only of biomass-derived olefins, It may be a mixture of biomass-derived olefins and fossil fuel-derived olefins. For example, when it is desired to place importance on improving the biomass degree of the ethylene polymer mixture (A3), it is desirable that the olefin used as a raw material for the low density polyethylene (D) is only a biomass-derived olefin. Furthermore, for example, if the emphasis is on reducing the cost of the ethylene polymer mixture (A3), it is desirable that the olefins used as raw materials for the low-density polyethylene (D) be only fossil fuel-derived olefins. Alternatively, a mixture of a biomass-derived olefin and a fossil fuel-derived olefin that satisfies the requirements (I) in the same way as the raw material for the ethylene polymer (A) can be selected as the raw material for the low-density polyethylene (D). .

The low-density polyethylene (D) is not particularly limited as long as it satisfies the above conditions, and for example, it may be a high-pressure radical low-density polyethylene produced by radical polymerization under high pressure, or it may be low-density polyethylene produced by high-pressure radical polymerization under medium or low pressure of several tens of atmospheres or less. Although linear low-density polyethylene produced by coordination anionic polymerization using a transition metal catalyst may be used, high-pressure radical low-density polyethylene is preferred.

The above-mentioned ethylene polymer mixture (A3) is, for example, an ethylene polymer (A2-2) (ethylene/α-olefin copolymer (A2-2)) and a high-pressure radical process low-density polyethylene (D). It can be manufactured by melt-kneading so that the weight ratio of the two becomes a desired value. Examples of devices used for melt-kneading include an extruder and a kneader.

[Method for producing ethylene polymer (A)]
The ethylene polymer (A) of the present invention is produced by polymerizing a raw material containing ethylene and an olefin (b) contained as necessary that satisfies the above-mentioned condition (I) using a polymerization catalyst. can.

The ethylene polymer (A) of the present invention is preferably produced by supplying a raw material containing ethylene (the raw material contains an olefin (a) satisfying the above requirement (I)) to a polymerization vessel, and treating the raw material with a polymerization catalyst. It can be manufactured by a manufacturing method including a step of polymerization.

The olefin (ethylene, α-olefin having 3 to 8 carbon atoms), which is a raw material used in the production of the ethylene polymer (A), can be produced, for example, by the following method.

Biomass-derived olefins (biomass-derived ethylene, biomass-derived α-olefins having 3 to 8 carbon atoms) can be produced by known methods.

Examples of methods for producing biomass-derived ethylene include the method described in International Publication No. 2007/055361 or International Publication No. 2008/062709, in which ethylene is produced using biomass-derived ethanol as a raw material, and the method described in International Publication No. 2008/062709, in which ethylene is produced using biomass-derived ethanol as a raw material; The method described in International Publication No. 2008/67627 for producing ethanol, the method described in International Publication No. 2009/070858 for producing ethanol from ethanol produced by fermentation of sugars obtained by extraction and processing of plant-derived raw materials, biorenewable Examples include the method described in International Publication No. 2016/184893 or International Publication No. 2016/184894, which is produced by thermally cracking a feedstock.

Examples of methods for producing biomass-derived propylene include the method described in International Publication No. 2007/055361 in which ethanol obtained from biomass is used as a raw material, and the method described in International Publication No. 2008/067627 in which it is produced using residues of agricultural natural raw materials as a raw material. The method described in WO 2016/184893, wherein the method described in WO 2016/184893 is produced from any biorenewable source, e.g. plant or animal, including fungi, yeasts, algae and bacteria. Examples include the method described in International Publication No. 2016/184894, which is produced by thermally cracking feedstock.

Examples of methods for producing biomass-derived 1-butene include the method described in International Publication No. 2008/067627, which uses residues of agricultural natural raw materials as raw materials, and the method produced by fermentation of saccharides obtained by extraction and processing of plant-derived raw materials. Examples include the method described in International Publication No. 2009/070858 in which the ethanol is produced from ethanol. Furthermore, as a method for producing biomass-derived 1-butene, for example, in the method described in JP-A-58-146518 and International Publication No. 1989/000553, 1-butene is produced using biomass-derived ethylene as the raw material ethylene. Examples include methods of manufacturing.

As a method for producing biomass-derived 1-pentene, for example, in the method described in JP-A-3-041036, JP-A-8-109144, and JP-A-8-133992, biomass-derived ethylene or biomass-derived ethylene or biomass-derived ethylene or propylene is used as the raw material ethylene or propylene. Examples include a method for producing 1-pentene using propylene.

Examples of methods for producing biomass-derived 1-hexene include methods described in JP-A-7-149672 and JP-A-8-183747, in which 1-hexene is produced using biomass-derived ethylene as the raw material ethylene. As a method for producing biomass-derived 1-octene, for example, in the method described in JP 2009-072666A and WO 2008/088178, 1-octene is produced using biomass-derived ethylene as the raw material ethylene. Examples include methods of manufacturing.

As a method for producing biomass-derived 4-methyl-1-pentene, for example, in the method described in JP-A-60-132924 and JP-A-61-083135, 4-methyl-1-pentene is produced using biomass-derived propylene as the raw material propylene. -1 A method for producing pentene can be mentioned.

The above-mentioned biomass-derived olefin may be produced by a known or similar method other than the above. In addition, when producing ethylene or propylene as a raw material, biomass-derived ethylene is used as the ethylene, and biomass-derived propylene is used as the propylene.

Fossil fuel-derived olefins (fossil fuel-derived ethylene, fossil fuel-derived propylene, fossil fuel-derived α-olefins having 4 to 8 carbon atoms) can be produced by known methods practiced in the petrochemical industry. Fossil fuel-derived ethylene and fossil fuel-derived propylene can be produced, for example, by thermal decomposition and fractional distillation of naphtha obtained in the process of petroleum refining, as posted on the website of the Japan Petrochemical Industry Association. Explore (2) Naphtha cracking plant [searched on September 1, 2021], Internet <URL: https://www.jpca.or.JP/studies/junior/tour02.html>).

Fossil fuel-derived α-olefins having 4 to 8 carbon atoms can be produced by known synthesis methods using, for example, fossil fuel-derived propylene or fossil fuel-derived ethylene as raw materials. Examples of methods for producing 1-butene derived from fossil fuels include the methods described in JP-A-58-146518 and International Publication No. 1989/000553, and methods for producing 1-pentene derived from fossil fuels include: For example, methods described in JP-A-3-041036, JP-A-8-109144, and JP-A-8-133992 are mentioned, and methods for producing fossil fuel-derived 1-hexene include, for example, JP-A-7-149672. Examples of the method for producing fossil fuel-derived 1-octene include the method described in JP-A No. 2009-072666 and International Publication No. 2008/088178. Can be mentioned.

As a method for producing fossil fuel-derived 4-methyl-1-pentene, for example, the method described in JP-A-60-132924 and JP-A-61-083135 uses fossil fuel-derived ethylene and fossil fuel-derived propylene as raw materials. Examples include a method for producing 4-methyl-1pentene.

Olefin (a) is an olefin mixture containing the above-mentioned biomass-derived olefin (a1) and fossil fuel-derived olefin (a2) in a desired ratio (for example, biomass-derived olefin (a1) 0.2% by weight or more and 99% by weight or less) and a fossil fuel-derived olefin (a2) from 1% to 99.8% by weight), the biomass-derived olefin (a1) and the fossil fuel-derived olefin (a2) are mixed in a desired specific ratio. It can be prepared by

In addition, when the olefin (a) is ethylene (ethylene mixture of biomass-derived ethylene and fossil fuel-derived ethylene) or propylene (propylene mixture of biomass-derived propylene and fossil fuel-derived propylene), fossil fuel-derived light naphtha and, for example, Naphtha obtained from any biorenewable source, e.g. plant or animal, including fungi, yeasts, algae and bacteria as described in WO 2016/184893, mixed in the desired specific proportions. It can be prepared by charging this mixture into a pyrolysis furnace and taking it out as ethylene and propylene from the cracked gas fractionator. Note that a naphtha cracker that includes a pyrolysis furnace and a cracked gas fractionator in series is a device called an "ethylene cracker" in the petrochemical industry.

In addition, when olefin (a) is an α-olefin having 4 to 8 carbon atoms (an α-olefin mixture of a biomass-derived α-olefin having 4 to 8 carbon atoms and a fossil fuel-derived α-olefin having 4 to 8 carbon atoms) can be produced by a known method or a method similar to a known method using the ethylene mixture of biomass-derived ethylene and fossil fuel-derived ethylene or the propylene mixture of biomass-derived propylene and fossil fuel-derived propylene obtained as described above as a raw material.

In the method for producing an ethylene polymer (A) of the present invention, a raw material containing ethylene introduced into a polymerization vessel is polymerized, and the polymerization can be carried out by bulk polymerization, solution polymerization, suspension (slurry) polymerization, etc. It may be carried out by a liquid phase polymerization method or a gas phase polymerization method. Moreover, such polymerization may be carried out by combining two or more of these polymerization methods.

As the polymerization solvent used in the liquid phase polymerization method, an inert organic solvent is usually used. Examples of inert organic solvents include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons; aromatic hydrocarbons; halogenated hydrocarbons; Examples include mixtures thereof. Among these, aliphatic hydrocarbons are preferred. Further, when a slurry polymerization method is used as the polymerization method, an olefin that becomes liquid at the polymerization temperature can also be used as at least a part of the polymerization solvent.

In the method for producing an ethylene polymer (A) of the present invention, a raw material containing ethylene introduced into a polymerization vessel is polymerized using a polymerization catalyst. As the polymerization catalyst, a polymerization catalyst that is normally used for polymerizing olefins containing ethylene can be used. Examples of such polymerization catalysts include Ziegler-Natta catalysts and metallocene catalysts comprising a titanium catalyst component and an organic aluminum compound.

The ethylene polymer (A) of the present invention can be produced, for example, by polymerizing an ethylene-containing olefin under the conditions described above. The physical property values of the ethylene polymer (A) can be set to desired values by appropriately selecting these conditions. For example, the density of the ethylene polymer (A) can be determined by appropriately selecting the catalyst used, polymerization conditions such as polymerization pressure, or by selecting at least one member selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms. In the case of a copolymer with an olefin, the desired value can be obtained by adjusting the ratio of the raw materials, ethylene and α-olefin having 3 to 20 carbon atoms, to an appropriate ratio. In addition, the melt flow rate (MFR) of the ethylene polymer (A) at 190°C and a load of 2.16 kg can be adjusted to a desired value by adjusting the ratio of the ethylene-containing olefin to the polymerization catalyst appropriately. It can be done.

In addition, when producing the ethylene polymer (A) of the present invention, it may be produced by single-stage polymerization under constant reaction conditions, or it may be produced by multi-stage polymerization conducted in two or more stages with different reaction conditions. You may.
Among these, ethylene polymers (A1-1) to (A1-4) are preferably produced by single-stage polymerization, and ethylene polymers (A2-1) to (A2-3) are produced by multi-stage polymerization. Preferably, it is manufactured by.

[Production method of ethylene polymer (A1-1)]
The ethylene polymer (A1-1) can be produced, for example, by single-stage polymerization of the ethylene polymer (A1-1) that satisfies (xviii) to (xxii) described above under constant reaction conditions.

Physical property values of the ethylene polymer (A1-1), for example, the amount of methyl branches and ethyl branches measured by ¹³ C-NMR, MFR, density, melt tension, shear viscosity under specific conditions, weight average molecular weight etc. can be set to desired values by adjusting the polymerization conditions.

Detailed production conditions (polymerization catalyst, polymerization temperature, polymerization pressure, etc.) for the ethylene polymer (A1-1) can be determined with reference to, for example, the polymerization conditions described in JP-A-2009-173798.

[Production method of ethylene polymer (A1-2)]
The ethylene polymer (A1-2) can be produced, for example, by single-stage polymerization under constant reaction conditions.

Physical property values of the ethylene polymer (A1-2), such as MFR, density, melt tension, shear viscosity under specific conditions, amount of methyl branch and ethyl branch measured by ¹³ C-NMR, weight average molecular weight etc. can be set to desired values by adjusting the polymerization conditions.

Detailed production conditions (polymerization catalyst, polymerization temperature, polymerization pressure, etc.) for the ethylene polymer (A1-2) can be determined with reference to, for example, the polymerization conditions described in JP-A-2009-197225.

[Production method of ethylene polymer (A1-3)]
The ethylene polymer (A1-3) can be produced, for example, by single-stage polymerization under constant reaction conditions.

Physical properties of the ethylene polymer (A1-3), such as MFR, density, amount of methyl and ethyl branches measured by ¹³ C-NMR, intrinsic viscosity, weight average molecular weight, etc., can be determined by adjusting the polymerization conditions. Accordingly, a desired value can be obtained.

Detailed production conditions (polymerization catalyst, polymerization temperature, polymerization pressure, etc.) for the ethylene polymer (A1-3) can be determined with reference to, for example, the polymerization conditions described in JP-A-2006-233207.

[Production method of ethylene polymer (A1-4)]
The ethylene polymer (A1-4) can be produced, for example, by single-stage polymerization under constant reaction conditions.

The physical properties of the ethylene polymer (A1-4), such as MFR, density, weight average molecular weight, number average molecular weight, etc., can be adjusted to desired values by adjusting the polymerization conditions.

For detailed production conditions (polymerization catalyst, polymerization temperature, polymerization pressure, etc.) of the ethylene polymer (A1-4), for example, refer to the polymerization conditions described in JP-A Nos. 2008-2312657 and 2008-230068. can be determined.

[Method for producing ethylene polymer (A2-1)]
The ethylene polymer (A2-1) can be produced by, for example, the step (x1) of polymerizing the ethylene polymer (X1) that satisfies the above-mentioned (iii) to (iv), and the above-mentioned (v) to (vi). It can be produced by multistage polymerization including a step (y1) of polymerizing an ethylene polymer (Y1) that satisfies the requirements.

In the steps (x1) and (y1), the steps are carried out so that the ethylene polymer (X1) and the ethylene polymer (Y1) in the ethylene polymer (A2-1) have a desired content ratio. (x1) and step (y1).
In addition, the physical properties of the ethylene polymers (X1), (Y1), and (A2-1), such as density and MFR, are based on the polymerization conditions of each step described above, and the ethylene polymers (X1) and ethylene polymers. By adjusting the ratio of coalescence (Y1), etc., a desired value can be obtained.

Detailed production conditions (polymerization catalyst, polymerization temperature, polymerization pressure, etc.) of the ethylene polymer (A2-1) are determined with reference to the polymerization conditions described in, for example, JP-A-10-182854 and JP-A-10-195263. can do.

[Method for producing ethylene polymer (A2-2)]
The ethylene polymer (A2-2) (ethylene/α-olefin copolymer (A2-2)) is, for example, at least one olefin selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms. (x2) of producing an ethylene/α-olefin copolymer (X2) that satisfies (ix) to (xii) above by polymerizing ethylene and an α-olefin having 3 to 20 carbon atoms; By multistage polymerization, including the step (y1) of polymerizing at least one olefin selected from the group to produce an ethylene/α-olefin copolymer (Y2) satisfying the above (xiii) to (xv). Can be manufactured.

In the steps (x2) and (y2), the ethylene/α-olefin copolymer (X2) and the ethylene/α-olefin copolymer (Y2) in the ethylene/α-olefin copolymer (A2-2) are What is necessary is just to manufacture by process (x2) and process (y2) so that it may become a desired content ratio.
In addition, the physical properties of the ethylene polymers (X2), (Y2), and (A2-2), such as density, intrinsic viscosity, decane soluble portion at room temperature, and temperature at the maximum peak position of the endothermic curve, are as described above. A desired value can be obtained by adjusting the polymerization conditions of each step, the ratio of the ethylene polymer (X2) and the ethylene polymer (Y2), etc.

The detailed production conditions (polymerization catalyst, polymerization temperature, polymerization pressure, etc.) of the ethylene-α-olefin copolymer (A2-2), which is the ethylene polymer (A2-2), are described in, for example, JP-A-8-283477. , and can be determined with reference to the polymerization conditions described in JP-A-9-169359.

[Production method of ethylene polymer (A2-3)]
The ethylene polymer (A2-3) can be produced by, for example, the step (x3) of polymerizing the ethylene polymer (X3) that satisfies the above (xxxiii) to (xxxv), and the above (xxxvi) to (xxxviii). It can be produced by multi-stage polymerization including a step (y3) of polymerizing an ethylene polymer (Y3) that satisfies the requirements.

In the steps (x3) and (y3), the steps are carried out so that the ethylene polymer (X3) and the ethylene polymer (Y3) in the ethylene polymer (A2-3) have a desired content ratio. (x3) and step (y3).
In addition, the physical properties of the ethylene polymers (X3), (Y3), and (A2-3), such as intrinsic viscosity, weight average molecular weight, number average molecular weight, density, MFR, and cross fractionation chromatography (CFC) at 85°C The amount of components eluted below can be set to a desired value by adjusting the polymerization conditions of each step described above, the ratio of the ethylene polymer (X3) and the ethylene polymer (Y3), etc.

Detailed production conditions for the ethylene polymer (A2-3) (polymerization catalyst, polymerization temperature, polymerization pressure, etc.) can be determined, for example, with reference to the polymerization conditions described in JP-A-2018-141099.

[Resin composition]
According to the present invention, the ethylene polymer (A) or ethylene polymer mixture (A3) obtained as described above is one of the fossil fuel-derived ethylene polymers obtained using only fossil fuel-derived olefins as raw materials. It can be used as a resin composition containing an ethylene polymer by replacing part or all of it. Note that, depending on the purpose, such a resin composition may further contain, as an ethylene polymer, a biomass-derived ethylene polymer obtained using only a biomass-derived olefin as a raw material. Further, the resin composition may contain only the ethylene polymer (A) as the ethylene polymer, or may contain the ethylene polymer (A) and the fossil fuel as the ethylene polymer. A mixture with a derived ethylene polymer may also be included.

[Other ingredients]
The ethylene polymer (A), the ethylene polymer mixture (A3), the resin composition containing the ethylene polymer (A), or the resin composition containing the ethylene polymer mixture (A3) of the present invention are as follows. It may also contain other components such as additives.

<Additives>
The ethylene polymer (A), the ethylene polymer mixture (A3), the resin composition containing the ethylene polymer (A), or the resin composition containing the ethylene polymer mixture (A3) of the present invention includes: Additives may also be included. Examples of such additives include stabilizers such as heat-resistant stabilizers, weather-resistant stabilizers, and light-resistant stabilizers, chloride absorbers, fillers such as inorganic fillers, α-crystal nucleating agents, β-crystal nucleating agents, softeners, Examples include antistatic agents, slip agents, antiblocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, surface modifiers, aluminum flakes, and other known additives.

<Inorganic filler>
Examples of the inorganic filler include talc, magnesium sulfate fiber, glass fiber (short fiber), carbon fiber (short fiber), mica, calcium carbonate, magnesium hydroxide, ammonium phosphate, silicates, carbonates, and carbon. Examples of organic fillers such as black include wood flour, cellulose, polyester fiber, nylon fiber, kenaf fiber, bamboo fiber, jude fiber, rice flour, starch, and cornstarch. Among these inorganic fillers, talc, magnesium sulfate fibers, glass fibers, and carbon fibers are preferred. When these inorganic fillers are used as components of a resin composition containing the propylene polymer (A), the content of the inorganic fillers is usually 1% by weight or more and 75% by weight or less.

<Stabilizer>
Examples of the stabilizer include known phenol stabilizers, organic phosphite stabilizers, thioether stabilizers, hindered amine stabilizers, higher fatty acid metal salts such as calcium stearate, and inorganic oxides.

<Surface modifier>
As the surface modifier, those known as antistatic agents are suitably used, typical examples of which include fatty acid amides, monoglycerides, etc., with fatty acid amides being preferred. Specific examples of the fatty acid amide include oleic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, palmitic acid amide, myristic acid amide, lauric acid amide, caprylic acid amide, caproic acid amide, n-oleyl palmitate. toamide, n-oleyl erucamide, and dimers thereof, among which oleic acid amide, stearic acid amide, erucic acid amide, and erucic acid amide dimer are preferred, and erucic acid amide is more preferred. . These can be used alone or in combination of two or more.

<Pigment>
Examples of the pigment include chromatic inorganic pigments and/or organic pigments. Specific examples of inorganic pigments include metal oxides, sulfides, and sulfates. Specific examples of organic pigments include phthalocyanine compounds, quinacridone compounds, and benzidine compounds.

<Carbon black>
As the carbon black, any known carbon black can be used without particular limitation. There is no limit to the average particle size of carbon black, but its primary particles are preferably 10 to 40 nm.

<Aluminum flakes>
The aluminum flakes can be manufactured by a known method. Specifically, it can be manufactured by, for example, pulverizing or grinding a material such as atomized powder, aluminum foil, or vapor-deposited aluminum foil using a device such as a ball mill, an attritor, or a stamp mill. In particular, aluminum flakes obtained by grinding aluminum powder obtained by an atomization method using a ball mill are preferable. The purity of aluminum is not particularly limited, and it may be alloyed with other metals as long as it has malleability. Specific examples of other metals include Si, Fe, Cu, Mn, Mg, and Zn.
The average particle size of the aluminum flakes is preferably 5 to 90 μm, more preferably 10 to 70 μm. One type of aluminum flakes may be used alone, or two or more types may be used in combination.

[Denaturation]
The ethylene polymer (A), the ethylene polymer mixture (A3), the resin composition containing the ethylene polymer (A), and the resin composition containing the ethylene polymer mixture (A3) of the present invention are α , β-unsaturated carboxylic acid, or its acid anhydride by a known method. Such modification is carried out, for example, by dissolving the ethylene polymer (A) or the ethylene polymer (A) and the α,β-unsaturated carboxylic acid and/or its acid anhydride in a solvent, or by dissolving the ethylene polymer (A) or the ethylene polymer (A) in a solvent. This can be carried out by reacting the resin composition in the presence of a radical generator in a melt-kneaded state.

As α,β-unsaturated carboxylic acids and their acid anhydrides, those having 20 or less carbon atoms, particularly those having 4 to 16 carbon atoms, are preferable, and specifically, acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, etc. The acids include fumaric acid, itaconic acid, citraconic acid, 3,6-endomethylene-2,3,4,6-tetrahydrosis-phthalic acid and acid anhydrides thereof.

[Propylene polymer modification]
The ethylene polymer (A), the ethylene polymer mixture (A3), the resin composition containing the ethylene polymer (A), and the resin composition containing the ethylene polymer mixture (A3) of the present invention include propylene It can be used to modify polymers. Note that the propylene polymer mainly contains structural units derived from propylene (typically contains more than 50% by weight, preferably more than 60% by weight). It is a polymer. Propylene-based polymers typically include propylene homopolymers, copolymers of propylene with at least one olefin selected from the group consisting of ethylene and α-olefins having 4 to 20 carbon atoms; Examples of the copolymer include propylene/ethylene random copolymer, propylene/α-olefin (carbon number 4 to 20) random copolymer, propylene/ethylene/α-olefin (carbon number 4 to 20) random copolymer. and propylene/ethylene block copolymers.
Propylene polymer modification can be carried out, for example, by replacing part or all of the ethylene polymer described in International Publication No. 2016/114393 with an ethylene polymer (A) or an ethylene polymer mixture (A3). It can be carried out.

[Molded object]
A part or all of the conventionally known ethylene polymers (ethylene homopolymers, copolymers of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms) are converted into ethylene polymers. Replaced with a combination (A) (for example, ethylene polymers (A1-1) to (A1-4), (A2-1) to (A2-3)) or an ethylene polymer mixture (A3), and this replaced By molding the obtained polymer, the molded article of the present invention can be obtained. In addition, by molding a resin composition containing an ethylene polymer in which part or all of the conventionally known ethylene polymer is replaced with an ethylene polymer (A) or an ethylene polymer mixture (A3), the present invention can be applied. A molded article of the invention is obtained.

When replacing conventionally known ethylene polymers with ethylene polymers (A), the molecular structure of these polymers other than the presence or absence of ^14C isotopes, such as average molecular weight, molecular weight distribution, type of comonomer, amount of comonomer, etc. If the characteristics are the same, the performance of the molded product can be made the same even after replacement. This replacement makes it possible to reduce the environmental burden (reduce greenhouse gas emissions) in the life cycle of polymers, from production, processing, use, and disposal.

The ethylene polymer (A) is an ethylene polymer whose biomass-derived carbon concentration, biomass degree, etc. are adjusted to desired ranges from the viewpoint of cost reduction, popularization, etc. Therefore, for the purpose of setting the biomass-derived carbon concentration, biomass degree, etc. of the material used as a molded object to desired values, the above-mentioned biomass-derived ethylene polymer (or a resin composition containing a biomass-derived ethylene polymer) is used. As such, additional dilution with fossil fuel-derived propylene-based polymers is not required. Therefore, in the molded article of the present invention, the equipment and process for its production can be simplified, and the environmental load can be reduced.

Ethylene polymer (A) of the present invention (for example, ethylene polymers (A1-1) to (A1-4), (A2-1) to (A2-3)), ethylene polymer mixture (A3) , the resin composition containing the ethylene polymer (A), and the resin composition containing the ethylene polymer mixture (A3) can be processed by injection molding, extrusion molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, Injection stretch blow molding, press molding (compression molding), vacuum forming, calendar molding, foam molding, injection foam molding, foam blow molding, blow molding, stretch molding (uniaxial stretch molding, biaxial stretch molding), extrusion lamination molding, casting It can be molded into various molded bodies by known molding methods such as molding and rotational molding.

<Injection molding>
The ethylene polymer (A) of the present invention, the ethylene polymer mixture (A3), the resin composition containing the ethylene polymer (A), and the resin composition containing the ethylene polymer mixture (A3) can be By molding, it can be made into molded bodies for various uses.
Injection molding methods include, for example, ethylene polymers or resins containing ethylene polymers described in JP 2001-064331, JP 2017-128692, JP 2018-172489, and International Publication 2019/139125. Examples include methods of injection molding the composition.

<Hollow molding>
The ethylene polymer (A) of the present invention, the ethylene polymer mixture (A3), the resin composition containing the ethylene polymer (A), and the resin composition containing the ethylene polymer mixture (A3) have hollow By molding, it can be made into molded bodies for various uses.
Examples of the blow molding method include JP-A-09-194534, JP-A 2003-292534, WO 2004/083265, JP-A 2006-083370, WO 2006/019147, and JP-A 2018-197120. Examples include a method for blow molding an ethylene polymer or a resin composition containing an ethylene polymer as described in .

<Injection stretch blow molding>
The ethylene polymer (A) of the present invention, the ethylene polymer mixture (A3), the resin composition containing the ethylene polymer (A), and the resin composition containing the ethylene polymer mixture (A3) can be By stretch blow molding, molded products for various uses can be obtained.
Examples of the method of injection stretch blow molding include the method of injection stretch blow molding of an ethylene polymer or a resin composition containing an ethylene polymer described in JP 2021-138870A.

<Rotational molding>
The ethylene polymer (A) of the present invention, the ethylene polymer mixture (A3), the resin composition containing the ethylene polymer (A), and the resin composition containing the ethylene polymer mixture (A3) are By molding, it can be made into molded bodies for various uses.
Examples of the rotational molding method include the method of rotational molding of an ethylene polymer or a resin composition containing an ethylene polymer described in JP-A No. 2001-089615.

<Inflation molding>
The ethylene polymer (A) of the present invention, the ethylene polymer mixture (A3), the resin composition containing the ethylene polymer (A), and the resin composition containing the ethylene polymer mixture (A3) are By molding, it can be made into molded bodies used for various purposes.
Inflation molding methods include, for example, ethylene polymers or ethylene polymers described in JP-A-11-012558, International Publication No. 2004/089626, JP-A No. 2008-31380, and JP-A No. 2016-074900. Examples include a method of inflation molding a resin composition.

<Stretch molding>
The ethylene polymer (A) of the present invention, the ethylene polymer mixture (A3), the resin composition containing the ethylene polymer (A), and the resin composition containing the ethylene polymer mixture (A3) are By molding, it can be made into molded bodies (for example, stretched films such as biaxially stretched films) used for various purposes.
Examples of the stretching method include, for example, JP 2006-007529, JP 2006-239877, JP 2008-031381, JP 2009-007589, WO 2005/028553, and JP 2016-187933. Examples include a method for stretch-molding an ethylene polymer or a resin composition containing an ethylene polymer as described in .
Stretching may be uniaxially stretching or biaxially stretching depending on the application. Moreover, when the molded object is a stretched film, the stretched film obtained may be a single layer film or a laminated film.

<Cast molding>
The ethylene polymer (A) of the present invention, the ethylene polymer mixture (A3), the resin composition containing the ethylene polymer (A), and the resin composition containing the ethylene polymer mixture (A3) are cast By molding, it can be made into molded bodies for various uses.
Examples of the cast molding method include the method of cast molding an ethylene polymer or a resin composition containing an ethylene polymer described in International Publication No. 2016/056524.

Examples of molded products produced by the above molding method include the following.
<Tube, tube>
Extrusion from the ethylene polymer (A) of the present invention, the ethylene polymer mixture (A3), the resin composition containing the ethylene polymer (A), and the resin composition containing the ethylene polymer mixture (A3) By forming methods such as molding, tubes and pipes used for various purposes can be formed. For example, tubes and pipes are formed from ethylene polymers or resin compositions containing ethylene polymers described in International Publication No. 2017/093008, JP 2018-168228, and JP 2018-168229. It can be produced by the method described below.

<Extrusion laminated products>
Extrusion from the ethylene polymer (A) of the present invention, the ethylene polymer mixture (A3), the resin composition containing the ethylene polymer (A), and the resin composition containing the ethylene polymer mixture (A3) By laminating, extruded laminate products for various uses can be produced. Extrusion laminate products are, for example, ethylene-based polymers or resin compositions containing ethylene-based polymers described in JP-A-2008-031374, JP-A-2008-031377, JP-A-2008-031383, and JP-A-2014-074103. It can be produced by a method of producing extrusion laminate products from objects. Note that the laminate layer of such an extrusion laminate product may be a single layer or a laminate.

<Wire covering material>
The ethylene polymer (A), the ethylene polymer mixture (A3), the resin composition containing the ethylene polymer (A), and the resin composition containing the ethylene polymer mixture (A3) of the present invention can be used for electric wires. It can be used as an insulating layer for electric wires. The ethylene polymer (A), the ethylene polymer mixture (A3), the resin composition containing the ethylene polymer (A), or the resin composition containing the ethylene polymer mixture (A3) of the present invention can be used as a conductor. An electric wire having an insulating layer can be obtained by extrusion coating directly on the conductor or on a semiconductive layer, shielding layer, etc. coated on the conductor. An electric wire having an electric wire coating material as an insulating layer can be coated by extrusion coating from an ethylene polymer or a resin composition containing an ethylene polymer described in JP-A-11-029616 and JP-A-2000-256422, for example. It can be produced by a method of producing an electric wire having the material as an insulating layer.

<Application>
By the method described above, the ethylene polymer (A) of the present invention, the ethylene polymer mixture (A3), the resin composition containing the ethylene polymer (A), and the resin containing the ethylene polymer mixture (A3) The molded product obtained from the composition can be applied to a variety of known uses, such as automobile parts, containers for food and medical uses, and packaging materials for food and electronic materials.

Examples of containers for food and medical use include tableware, retort containers, frozen storage containers, retort pouches, microwave heat-resistant containers, frozen food containers, frozen dessert cups, cups, beverage bottles, and other food containers, retort containers, and bottles. Containers, tear-off caps, liquid paper containers, etc., blood transfusion sets, medical bottles, medical containers, medical hollow bottles, medical bags, infusion bags, blood storage bags, infusion bottles, drug containers, detergent containers, cosmetic containers, perfume containers. , toner containers, etc.
Examples of packaging materials include food packaging, meat packaging, processed fish packaging, vegetable packaging, fruit packaging, fermented food packaging, sugar bags, oil packaging, water packaging, and liquid soup packaging. , special shaped liquid packaging materials (standing pouches, etc.), confectionery packaging materials, oxygen absorber packaging materials, retort food packaging materials, freshness preservation films, pharmaceutical packaging materials, cell culture bags, cell inspection films, bulb packaging materials, seed packaging materials These include materials for growing vegetables and mushrooms, heat-resistant vacuum-formed containers, prepared food containers, lids for prepared foods, commercial wrap films, household wrap films, baking cartons, standard bags, heavy bags, and agricultural materials.

When the molded article of the present invention is a film, sheet, tape, etc., its uses include, for example, a protective film for polarizing plates, a protective film for liquid crystal panels, a protective film for optical components, a protective film for lenses, and electrical components.・Protective films such as protective films for electrical appliances, protective films for mobile phones, protective films for computers, masking films, capacitor films, reflective films, laminates (including glass), radiation-resistant films, gamma-ray-resistant films, porous films, etc. Examples include. It can also be used as a multilayer film by laminating it with a base material such as nylon or polyester.

Other uses of the molded product of the present invention include, for example, housings for home appliances, hoses, tubes, wire covering materials, insulators for high-voltage wires, tubes for cosmetics and perfume sprays, medical tubes, infusion tubes, pipes, and kerosene. Cans, drums, gasoline tanks, wire harnesses, interior materials for motorcycles, railway vehicles, aircraft, ships, etc., instrument panel skins, door trim skins, rear package trim skins, ceiling skins, rear pillar skins, seat back garnishes, console boxes, For automobiles such as armrests, airbag case lids, shift knobs, assist grips, side step mats, reclining covers, trunk seats, seat belt buckles, inner/outer moldings, roof moldings, belt moldings, door seals, body seals, etc. Sealing materials, glass run channels, mudguards, kicking plates, step mats, license plate housings, automotive hose parts, air duct hoses, air duct covers, air intake pipes, air dam skirts, timing belt cover seals, bonnet cushions, door cushions, etc. Automotive interior and exterior materials, vibration damping tires, static tires, car racing tires, special tires such as radio-controlled tires, packing, automobile dust covers, lamp seals, automobile boot materials, rack and pinion boots, timing belts, wire harnesses, grommets. , emblems, air filter packings, skin materials for furniture, footwear, clothing, bags, building materials, etc., sealing materials for construction, waterproof sheets, construction material sheets, construction material gaskets, window films for construction materials, iron core protection members, gaskets, doors, doors. Frames, window frames, edges, baseboards, opening frames, etc., flooring materials, ceiling materials, wallpaper, health products (e.g. non-slip mats/sheets, fall prevention films/mats/sheets, etc.), health equipment components, shock absorption Pads, protectors/protective equipment (e.g. helmets, guards), sporting goods (e.g. sports grips, protectors), sports armor, rackets, mouthguards, balls, golf balls, transportation equipment (e.g. shock absorbing grips for transportation) shock absorbing materials such as shock absorbing sheets), vibration damping pallets, shock absorbing dampers, insulators, shock absorbing materials for footwear, shock absorbing foams, shock absorbing films, grip materials, miscellaneous goods, toys, shoe soles, shoe soles, Shoe midsoles/inner soles, soles, sandals, suction cups, toothbrushes, flooring materials, gymnastics mats, power tool parts, agricultural equipment parts, heat dissipation materials, transparent substrates, soundproofing materials, cushioning materials, electric wire cables, shape memory materials, medical care gaskets, medical caps, drug stoppers, gaskets, packing materials for applications that require high-temperature processing such as boiling or high-pressure steam sterilization after filling bottles with baby food, dairy products, pharmaceuticals, sterilized water, etc., industrial sealing materials, Industrial sewing machine tables, license plate housings, cap liners such as PET bottle cap liners, stationery, office supplies, precision equipment and OA equipment support members such as OA printer legs, FAX legs, sewing machine legs, motor support mats, audio vibration isolation materials, etc. , heat-resistant packing for office automation, physical and chemical laboratory equipment such as animal cages, beakers, graduated cylinders, cells for optical measurement, clothing cases, clear cases, clear files, clear sheets, desk mats, fibers, etc., such as non-woven fabrics, elastic Non-woven fabrics, fibers, waterproof fabrics, breathable fabrics and fabrics, disposable diapers, sanitary products, sanitary products, filters, bag filters, dust collection filters, air cleaners, hollow fiber filters, water filters, gas separation membranes, etc. It will be done.

In a conventional molded article made of an ethylene polymer, a composition containing an ethylene polymer, and a molded article made of the composition, part or all of the ethylene polymer is replaced with the ethylene polymer (A) of the present invention. Alternatively, it can be replaced with an ethylene polymer mixture (A3). Such replacement makes it possible to reduce the environmental burden (greenhouse gas generation) during the life cycle of the ethylene polymer, from production to utilization and disposal.

The ethylene polymer (A) of the present invention is an ethylene polymer whose biomass-derived carbon concentration, biomass degree, etc. are adjusted to desired ranges from the viewpoint of cost reduction, popularization, etc. Therefore, for the purpose of setting the biomass-derived carbon concentration, biomass degree, etc. of the molded body to desired values, like the above-mentioned biomass-derived ethylene polymer (or resin composition containing a biomass-derived ethylene polymer), An additional step of mixing a fossil fuel-derived propylene copolymer is not required. For this reason, in order to obtain materials for producing molded bodies, equipment and processes for blending in-line and equipment and processes for melt-kneading are not required. In other words, the equipment for obtaining the molding material for producing the molded body can be simplified, and post-processes for producing the molding material after producing the biomass-derived ethylene polymer are not necessary. For these reasons, it is thought that reducing power consumption will contribute to reducing environmental impact.

The ethylene polymer (A) of the present invention includes an ethylene polymer manufactured using a mass balance method certified by ISCC PLUS certification or the like. The propylene polymer products assigned as biomass products by the mass balance method may not be the ethylene polymer (A) of the present invention, but the product covers the entire production, use, and disposal of various products in the petrochemical industry. It contributes to reducing environmental load, and can be used in accordance with the ethylene polymer (A), resin composition, and molded article of the present invention. Even ethylene polymer products that are not assigned as biomass products according to the mass balance method may become the ethylene polymer (A) of the present invention depending on the manufacturing method.

The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these Examples unless the gist thereof is exceeded.

<Various physical property measurement conditions>
The physical properties of the polymer and the physical properties of the molded article (film) described in Reference Examples, Examples, etc. were measured according to the following conditions.
(1) Measurement of ¹⁴ C concentration (pMC (percent Modern Carbon)) It was measured as follows in accordance with ASTM D 6866-21.
The sample was combusted to generate carbon dioxide (CO ₂ ), and the carbon dioxide was purified in a vacuum line. Graphite was produced by reducing purified carbon dioxide with hydrogen using iron as a catalyst.
Graphite was packed into a cathode with an inner diameter of 1 mm using a hand press machine, and it was fitted into a wheel and attached to a measuring device ( ^{a 14} C-AMS dedicated device based on a tandem accelerator (manufactured by NEC Corporation)). Using this measuring device, ¹⁴ C counts, ¹³ C concentrations ( ¹³ C/ ¹² C), and ¹⁴ C concentrations ( ¹⁴ C/ ¹² C) were measured. In the measurement, oxalic acid (HOxII) provided by the US National Institute of Standards (NIST) was used as a standard sample. Measurements of this standard sample and background sample were also performed at the same time.
¹⁴ C concentration (pMC) refers to the ratio of the ¹⁴ C concentration of sample carbon to standard modern carbon.

(2) Biomass-derived carbon concentration (pMC (%))
In accordance with ASTM D 6866-21, the value obtained by rounding off ^{the 14} C concentration (pMC) measured as described above to two decimal places was taken as the biomass-derived carbon concentration.

(3) Biomass content (%) (biobased carbon content (%))
Based on ASTM D 6866-21, corrected by δ ¹³ C (measurement of ¹³ C concentration ( ¹³ C/ ¹² C) of sample carbon, deviation from reference sample expressed in thousandth deviation (‰)) Calculated using pMC. The value of biomass degree (%) is an integer value rounded to one decimal place. For the atmospheric correction coefficient, the value for 2019-2021 described in ASTM D6866-21 (latest edition) was used (100.0 pMC). It is possible that the ^14C concentration in the atmosphere will continue to decrease (change) year after year. In the future, if the value of the atmospheric correction coefficient described in ASTM D6866 (latest edition) is changed from 100.0 pMC, the value described in ASTM D6866 of the year in which the ethylene polymer related to the present invention was manufactured will be changed to the atmospheric correction coefficient. shall be. When the year of production of the material that is the raw material for producing biomass-derived olefin is unknown, the atmospheric correction coefficient was set to 100.0 pMC.

(4) Biomass-derived olefin in raw material monomer (wt%)
A raw material source (1) containing only a biomass-derived olefin of one type of olefin (for example, ethylene) and a raw material source (2) containing only a fossil fuel-derived olefin of the same olefin as the one type of olefin are prepared. By adjusting the mixing ratio of the raw material source (1) and the raw material source (2), the weight percent of biomass-derived olefin and the weight percent of fossil fuel-derived olefin in the raw material monomer were set to desired values. In addition, when two or more types of olefins become olefin (a) (a mixture of biomass-derived olefins and fossil fuel-derived olefins), a raw material source (1') containing only two or more types of biomass-derived olefins and a raw material source (1') containing only two or more types of biomass-derived olefins are used. A raw material source (2') containing only fossil fuel-derived olefins is mixed, and if necessary (for example, when it is desired to change the weight percent of biomass-derived olefins for each olefin type), one or more types of biomass-derived olefins are separately added. A raw material source (1'a) consisting only of olefins or a raw material source (2'a) consisting only of one or more fossil fuel-derived olefins is mixed to determine the weight percent of biomass-derived olefins and the amount of fossil fuel-derived olefins in the raw material monomers. The weight percentage may be adjusted to the desired value.

(5) Melt flow rate (MFR: [g/10 minutes])
Measurement was performed with a load of 2.16 kg in accordance with ASTM D1238E. The measurement temperature was 190°C.

(6) α-olefin content (content of structural units derived from α-olefin)
The assignment of nuclear magnetic resonance spectra ( ^13C -NMR) and the method for quantifying α-olefin content are described in J. Appl. Polym. Sci. It was determined according to the method described in Vol. 42, p. 399 (1991).
Put 220 mg of the sample into an NMR sample tube with a diameter of 10 mm, add 3 ml of 1,2,4-trichlorobenzene/deuterobenzene (90/10 volume %) mixed solvent, and then homogenize at 140°C using an aluminum block heater. Dissolved.
A sample tube was loaded into an EX-400 manufactured by JEOL Ltd., and a nuclear magnetic resonance spectrum ( ¹³ C-NMR) was measured under the following conditions using the proton complete decoupling method.
(Measurement condition)
Pulse width: 9.2μs (45° pulse)
Spectral width: 25000Hz
Measurement temperature: 130℃
Pulse repetition time: 4 seconds Total number of times: 1000 to 10000 times

(7) The content of methyl branches and ethyl branches measured by ¹³ C-NMR [M _{Me + Et} (mol%)] and the content of all branches measured by ¹³ C-NMR [M _all ( mol%)] [M _Me+Et /M _all ]
M _Me+Et /M _all is determined using ¹³ C-NMR as follows. The measurement is performed using an ECP500 nuclear magnetic resonance apparatus ( ^1H : 500MHz) manufactured by JEOL Ltd., and the measurement is performed at a cumulative number of 10,000 to 30,000 times. Note that the main chain methylene peak (29.97 ppm) was used as a chemical shift reference. In a commercially available NMR measurement quartz glass tube with a diameter of 10 mm, a mixture of 250 to 400 mg of PE sample and special grade o-dichlorobenzene manufactured by Wako Pure Chemical Industries, Ltd.: benzene-d6 manufactured by ISOTEC Co., Ltd. = 5:1 (volume ratio) This is done by adding 3 ml of the solution and heating it at 120°C to uniformly disperse it. The attribution of each absorption in the NMR spectrum is given in Chemistry Area Special Edition No. 141, NMR - Review and Experiment Guide [I], p. Perform according to 132-133.
The content of each branch can be calculated from the integrated intensity ratio of absorption appearing in the following regions. Methyl branch: 19.9ppm, ethyl branch: 10.8ppm, propyl branch: 14.4ppm, butyl branch: 23.1ppm, isobutyl group: 25.7ppm, hexyl branch: 31.9ppm

(8) Sum of the number of methyl branches [A(/1000C)] and the number of ethyl branches [B(/1000C)] measured by ^13C -NMR [(A+B)(/1000C)]
The number of methyl branches and the number of ethyl branches are defined as the number per 1000 carbons, as described below.
The number of methyl branches and the number of ethyl branches measured by ¹³ C-NMR are determined as follows. The measurement is performed using an ECP500 type nuclear magnetic resonance apparatus ( ^1H : 500MHz) manufactured by JEOL Ltd., and the measurement is performed at a cumulative number of 10,000 to 30,000 times. Note that the main chain methylene peak (29.97 ppm) was used as a chemical shift reference. In a commercially available NMR measurement quartz glass tube with a diameter of 10 mm, a mixture of 250 to 400 mg of PE sample and special grade o-dichlorobenzene manufactured by Wako Pure Chemical Industries, Ltd.: benzene-d6 manufactured by ISOTEC Co., Ltd. = 5:1 (volume ratio) This is done by adding 3 ml of the solution and heating it at 120°C to uniformly disperse it. The attribution of each absorption in the NMR spectrum is given in Chemistry Area Special Issue No. 141, NMR - Review and Experiment Guide [I], p. Perform according to 132-133. The number of methyl branches per 1,000 carbons is calculated from the integrated intensity ratio of the absorption of methyl groups derived from methyl branches (19.9 ppm) to the integral sum of absorption appearing in the range of 5 to 45 ppm. The number of ethyl branches is calculated from the integrated intensity ratio of the absorption of ethyl groups derived from ethyl branches (10.8 ppm) to the integral sum of absorptions appearing in the range of 5 to 45 ppm.

(9) Density The measurement sample was heat-treated at 120° C. for 1 hour, slowly cooled to room temperature over 1 hour, and then the density was measured using a density gradient tube.

(10) Melting point Measured using a differential scanning calorimeter (DSC, manufactured by PerkinElmer (Diamond DSC)) in accordance with JIS-K7121. The apex of the endothermic peak in the third step measured under the following conditions was defined as the melting point (Tm (° C.)). When there were multiple endothermic peaks, the peak of the maximum endothermic peak was defined as the melting point (Tm (°C)).

<Measurement conditions>
・Measurement environment: Nitrogen gas atmosphere ・Sample amount: 5mg
・Sample shape: Press film (molded at 230℃, thickness 200-400μm)
- Sample set: sealed in an aluminum pan - 1st step: Raise the temperature from 30°C to 200°C at a rate of 10°C/min and hold for 10 minutes.
・Second step: Lower the temperature to 30°C at a rate of 10°C/min.
・Third step: Raise the temperature to 200°C at 10°C/min.

(11) Intrinsic viscosity ([η] (dl/g))
Approximately 20 mg of the sample was dissolved in 15 ml of decalin, and the specific viscosity η _sp was measured in an oil bath at 135°C. After diluting the decalin solution by adding 5 ml of decalin solvent, the specific viscosity η _sp was measured in the same manner. This dilution operation was repeated two more times, and the value of η _sp /C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity [η].
[η]=lim(η _sp /C) (C→0)

(12) N-decane soluble content (23°C)
The amount of n-decane soluble (at 23°C) is as follows: 10 g of ethylene polymer is added to 1 L of n-decane at 130°C, and the heat stabilizer 2,5-tert. After dissolving in the coexistence of butyl-4-methyl-phenol and keeping at 130°C for 1 hour, 1°C/min. The weight of the ethylene polymer precipitated when the sample was cooled to 23° C. at a cooling rate of 10 g was determined, and this value was subtracted from 10 g of the sample, and the value was expressed as a percentage (% by weight) of the weight of the sample.

(13) Hexane soluble fraction (boiling hexane soluble fraction)
The ethylene polymer pellets were pulverized using a pulverizer with a rotary cutter (manufactured by Kasuga Co., Ltd.) until the maximum length was 2 mm. Using about 3 g of the obtained pulverized material, Soxhlet extraction was performed with boiling hexane for 6 hours while adjusting the reflux time so that a siphon phenomenon occurred at a rate of about 1 time/1 minute.
After the extraction, the remaining ethylene polymer is dried at 70° C. for 3 hours, cooled to room temperature, and its weight is measured.
The weights of the ethylene polymer before and after extraction were taken as W1 and W2, and the value of (W1-W2)/W1×100 was determined as the hexane soluble fraction (%).

(14) Melt tension (MT (g))
Melt tension (MT(g)) is determined by measuring the stress when a molten polymer is stretched at a constant speed. That is, the obtained ethylene polymer powder was melted and pelletized using a conventional method to obtain a measurement sample, and the sample was rolled up using a MT measuring device manufactured by Toyo Seiki Seisakusho at a resin temperature of 190°C and an extrusion speed of 15 mm/min. The test was carried out at a speed of 10 to 20 m/min, a nozzle diameter of 2.09 mmφ, and a nozzle length of 8 mm. During pelletization, 0.05% by weight of tri(2,4-di-t-butylphenyl) phosphate as a secondary antioxidant was added to the ethylene polymer in advance, and n-octadecyl- 0.1% by weight of 3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate and 0.05% by weight of calcium stearate as a hydrochloric acid absorbent were blended.

(15) Weight average molecular weight (Mw), number average molecular weight (Mn), ratio of weight average molecular weight to number average molecular weight (Mw/Mn) (Tables 3-1, 3-2, 7-1, 7-2, 8 , 9-1, 9-2, 10-1, 10-2, 11-1, 11-2, 12, 13)
The weight average molecular weight (Mw), number average molecular weight (Mn), and ratio of weight average molecular weight to number average molecular weight (Mw/Mn) of the polymer were measured using a gel permeation chromatograph alliance GPC2000 model (high temperature size exclusion chromatograph) manufactured by Waters. It was calculated as follows.
<Equipment used and conditions>
Analysis software: Chromatography data system Empower2 (Waters, registered trademark)
Column; TSKgel GMH6-HT x 2 + TSKgel GMH6-HTL x 2 (inner diameter 7.5 mm x length 30 cm, Tosoh Corporation)
Mobile phase: o-dichlorobenzene (Wako Pure Chemical Industries, Ltd. special grade reagent)
Detector: Differential refractometer (built-in device)
Column temperature: 140℃
Flow rate: 1.0 mL/min Injection volume: 500 μL
Sampling time interval: 1 second Sample concentration: 0.15% (w/v)
Molecular weight calibration: Monodisperse polystyrene (Tosoh Corporation)/molecular weight 495 to 20.6 million Z. Crubisic, P. Rempp, H. Benoit, J. Polym. Sci. , B5, 753 (1967), and weight average molecular weight (Mw) and number average molecular weight (Mn) calculated as polyethylene molecular weight equivalents. ) ratio (Mw/Mn) is calculated.

(16) Amount of cross-fractionation chromatograph (CFC) eluted components For ethylene polymers, the amount of components eluted at 85°C or lower by cross-fractionation chromatograph (CFC) (CFC eluted component amount) is measured using CFC2 type cross-fractionation manufactured by PolymerChar. It was measured as follows using a chromatograph. Three Shodex HT-806M were used as separation columns. O-dichlorobenzene was used as the eluent. Sample concentration was 0.1-0.3% w/v. The injection volume was 0.5ml. The flow rate was 1.0 ml/min.
After heating the sample at 145°C for 2 hours, the temperature was lowered to 0°C at a rate of 0.17°C/min, and the temperature was further maintained at 0°C for 60 minutes to coat the sample. An IR4 type infrared spectrophotometer manufactured by PolymerChar was used as a detector. The elution temperature was divided into 35 to 55 fractions ranging from 0°C to 145°C, and especially in the vicinity of the elution peak, fractions were divided into 1°C increments. All temperature indications are integers; for example, the eluted fraction at 90°C indicates a component eluted at 89°C to 90°C. The molecular weights of the components that were not coated even at 0° C. and the fractions eluted at each temperature were measured, and the molecular weights in terms of polyethylene were determined using a general-purpose calibration curve.
SEC temperature was 145°C. Data sampling time was 0.10 min. Note that if too many components elute in a narrow temperature range and pressure abnormalities occur, the sample concentration may be set to less than 0.1% by mass/volume. Data processing was performed using the analysis program "CFC Calc" attached to the device.

(17) Number average molecular weight (Mn), weight average molecular weight (Mw), Z average molecular weight (Mz), molecular weight at maximum weight fraction (peak top) measured by GPC-viscosity detector method (GPC-VISCO) M), ratio of weight average molecular weight to number average molecular weight (Mw/Mn), ratio of Z average molecular weight to weight average molecular weight (Mz/Mw) (Table 8, 9-1, 9-2, 10-1, 10-2)
Number average molecular weight (Mn), weight average molecular weight (Mw), Z average molecular weight (Mz), molecular weight at the maximum weight fraction (peak top M), ratio of weight average molecular weight to number average molecular weight (Mw/Mn), The ratio of Z-average molecular weight to weight-average molecular weight (Mz/Mw) was measured using GPC/V2000 manufactured by Waters Corporation as follows. A Shodex AT-G guard column and two AT-806 analytical columns were used, the column temperature was 145°C, o-dichlorobenzene was used as a mobile phase, and 0.3% by weight of BHT was used as an antioxidant.1. It was moved at a rate of 0 ml/min, the sample concentration was 0.1% by weight, and a differential refractometer and a 3-capillary viscometer were used as detectors. Standard polystyrene manufactured by Tosoh Corporation was used. Molecular weight calculation is performed by calculating the actually measured viscosity using a viscometer and refractometer, and then using the actually measured universal calibration.

(18) Shear viscosity (η ^* ) at 200°C and angular velocity of 1.0 rad/sec
The shear viscosity (η ^* ) at 200°C and angular velocity of 1.0 rad/sec is the dispersion of the angular velocity [ω (rad/sec)] of the shear viscosity (η ^* ) at the measurement temperature of 200°C in the range of 0.02512≦ω≦100. Determined by measuring at . For the measurement, a dynamic stress rheometer SR-5000 manufactured by Rheometrics is used, a 25 mmφ parallel plate is used as the sample holder, and the sample thickness is about 2.0 mm. Furthermore, the number of measurement points is 5 for each digit of ω. The amount of distortion is appropriately selected in the range of 3 to 10% so that torque can be detected within the measurement range and torque is not exceeded. The sample used for the shear viscosity measurement was made using a press molding machine manufactured by Shinto Metal Industry Co., Ltd., and was preheated at a temperature of 190°C, a preheating time of 5 minutes, a heating temperature of 190°C, a heating time of 2 minutes, a heating pressure of 100 kg/cm ² , and a cooling temperature of 20°C. ℃, a cooling time of 5 minutes, and a cooling pressure of 100 kg/cm ² , the measurement sample is prepared by press molding to a thickness of 2 mm.

(19) Zero shear viscosity at 200°C (η ⁰ )
The zero shear viscosity [η ⁰ (P)] at 200°C is determined as follows. The angular velocity [ω (rad/sec)] dispersion of shear viscosity (η ^* ) at a measurement temperature of 200° C. is measured in the range of 0.02512≦ω≦100. A dynamic stress rheometer SR-5000 manufactured by Rheometrics was used for the measurement. A parallel plate with a diameter of 25 mm is used as the sample holder, and the sample thickness is about 2.0 mm. There are 5 measurement points per digit of ω. The amount of distortion is appropriately selected in the range of 3 to 10% so that torque can be detected within the measurement range and torque is not exceeded. The sample used for the shear viscosity measurement was made using a press molding machine manufactured by Shinto Metal Industry Co., Ltd., and was preheated at a temperature of 190°C, a preheating time of 5 minutes, a heating temperature of 190°C, a heating time of 2 minutes, a heating pressure of 100 kg/cm ² , and a cooling temperature of 20°C. ℃, cooling time for 5 minutes, and cooling pressure of 100 kg/cm ² , the measurement sample is prepared by press molding to a thickness of 2 mm.
Zero shear viscosity η ⁰ is calculated by fitting the Carreau model of the following formula (Eq-A) to the actually measured rheology curve [angular velocity (ω) dispersion of shear viscosity (η ^* )] using the nonlinear least squares method.
Η ^* =η ⁰ [1+(λω) ^a ] ^(n-1)/a …(Eq-A)
Here, λ is a parameter having a time dimension, and n is a power law index of the material. Note that the fitting by the nonlinear least squares method is performed so that d in the following equation (Eq-B) is minimized.

Here, η _exp (ω) represents the actually measured shear viscosity, and η _calc (ω) represents the shear viscosity calculated using the Carreau model.

(20) Young's modulus (film tensile modulus) (Tables 1 to 3-2, 11-1, 11-2)
Young's modulus (film tensile modulus) (MPa) was measured under the following conditions in accordance with JIS K7127.
<Measurement conditions>
- The evaluation film was cut into strips with a width of 10 mm and a length of 150 mm. A tensile test was carried out by pulling at a crosshead speed of 500 mm/min. The machine direction (film take-up direction) was defined as MD, and the direction perpendicular to MD was defined as TD.

(21) Yield point stress (Tables 5-1, 5-2)
The yield point stress was determined by conducting a tensile test in accordance with the method of ASTM-D-882. Note that the point where strain increases even though stress does not increase is defined as the yield point, and the stress at the yield point is defined as the yield point stress. The machine direction (film take-off direction) was defined as MD, and the direction perpendicular to MD was defined as TD.

(22) Dirt impact strength (Table 1, 2-1, 2-2, 3-1, 3-2, 11-1, 11-2, 12)
Dirt impact strength was measured according to ASTM D1709 under the following conditions.
<Measurement conditions>
The test piece was tightened using an air clamp method, a dart with a hemispherical diameter was dropped from a certain height, and the load at which the test piece would break by 50% was read from the graph. The number of drops per level was 10, and method A was used.

(23) Film impact strength (Tables 4-1, 4-2, 5-1, 5-2, 6-1, 6-2, 7-1, 7-2)
Film impact strength was evaluated by impact breaking strength using a 1/2 inch impact head in a film impact tester manufactured by Toyo Seiki Seisakusho.

(24) Low temperature drop bag strength test (Table 1)
The low-temperature properties of the film were evaluated by the following low-temperature drop bag strength tests (a) and (b). The numbers in the table are the total number of bags torn at each height in the tests (a) and (b) below.
(a) Low-temperature vertical drop bag strength test The content weight was 25 kg, and New Long HS-33D Top Sealer [trade name, manufactured by Tester Sangyo Co., Ltd.] was used under the conditions of a heater gap of 150% and a cooler gap of 200%. Ten bags with sealed bottoms were prepared, and the bags were dropped from the bottom of the bag from a height of 2 m in an atmosphere of -10°C, and the number of bags torn was counted. Similarly, 10 bags were tested at different drop heights of 1.75 m, 1.5 m, and 1 m.
(b) Low-temperature horizontal drop bag strength test The top and bottom were tested using New Long HS-33D Top Sealer [trade name, manufactured by Tester Sangyo Co., Ltd.] with a content weight of 25 kg and a heater gap of 150% and a cooler gap of 200%. Ten sealed bags were prepared and dropped from the side of the bag from a height of 2 m in an atmosphere of -20°C to count the number of bags that were torn. In addition, the same test was conducted with 10 bags each at drop heights of 1.75 m, 1.5 m, and 1 m.

(25) Tear strength (1) (Tables 2-1, 2-2, 3-1, 3-2)
Using an Elmendorf tensile tester (manufactured by Toyo Seiki Seisakusho), the film was measured in the drawing direction (MD) and the direction perpendicular to the MD (TD) in accordance with JIS Z1702.
(26) Tear strength (2) (Tables 5-1, 5-2)
In accordance with ASTM-D-1004, measurements were made in the direction of film take-up (MD) and in the direction perpendicular to MD (TD).
(27) Tear strength (3) (Tables 6-1, 6-2, 7-1, 7-2, 12)
Tear strength (3) (Elmendorf tear strength) was measured according to ASTM D1922 as described below.
<Measurement conditions>
Using a light load tear tester (manufactured by Toyo Seiki Seisakusho; capacity weight B: 79 g attached to the left end of the pendulum), the length from the film in the tear direction is 63.5 mm (long side) and the width in the direction perpendicular to the tear direction is 50 mm. A rectangular test piece (short side) was cut out, and a cut of 12.7 mm from the end was made in the center of the short side to prepare a plurality of test pieces. After that, a preliminary test was performed by stacking multiple test pieces so that the pointer (placement needle) of the testing machine was within the range of 20 to 80. After adjusting the number of test pieces used for measurement, a tear test was performed. The tear strength (N/cm) was determined using the following formula. Note that the measurement range (R) of the tester was set to 200.
(28) Tear strength (4) (Table 11)
From the obtained film, a rectangular test piece was cut out with a length of 63.5 mm in the tear direction (for each of the MD and TD directions) and 75.0 mm in the direction perpendicular to the tear direction. A plurality of test pieces were prepared by making a slit in the center 20 mm from the edge. Tear strength (4) (Elmendorf tear strength) was measured using 4N and SA-W (32N) manufactured by Toyo Seiki Seisakusho in accordance with JIS 7128-2.

(29) Haze (total haze), internal haze (Tables 3-1, 3-2, 5-1, 5-2, 6-1, 6-2, 7-1, 7-2)
Haze (total haze) was measured using a Nippon Denshoku haze meter according to ASTM D1003. The internal haze was measured by placing an ethylene polymer film in a cell filled with cyclohexanol, and using a Nippon Denshoku haze meter in the same manner as the total haze.
(30) Gross (Tables 5-1, 5-2)
Measured according to ASTM-D-2457.

(31) Complete heat sealing temperature (Tables 2-1, 2-2, 3-1, 3-2)
It was measured by the following method. That is, with two sheets of film cut out to a size of 120 x 120 mm stacked one on top of the other, a seal bar with a width of 5 mm kept at a temperature of 90°C is pressed against one side of the stacked films for 1 second at a pressure of 2 kg/cm ² . The two films were heat-sealed to form a test piece. The heat sealer manufactured by Intesco was used. Next, cut out the two films to a size of 15 x 15 mm including the heat-sealed parts, peel off the parts other than the two heat-sealed parts, and place the other side of the heat-sealed film into the chuck of a tensile tester, keeping the distance between the chucks. I set it to 15mm. The film was stretched at a stretching speed of 300 mm/min until it broke. When the seal portion peeled off, the temperature of the seal bar was increased in 5°C increments and the above operation was repeated. The lowest temperature of the seal bar when the seal part broke without peeling was defined as the complete heat sealing temperature.

(32) Heat sealing start temperature (Tables 6-1, 6-2, 7-1, 7-2)
Heat sealing was performed using a heat sealer manufactured by Toyo Tester at a specified temperature, a pressure of 2 kg/cm ² , and a sealing time of 1 second. The test piece width was 15 mm, and the peel test speed was 300 mm/min. The heat sealing start temperature was set as the temperature (° C.) at which the test piece began to break not due to peeling of the sealing surface but to the thick portion during the peel test.

(33) Heat seal strength (1) (Tables 5-1, 5-2)
Heat seal strength was measured according to JIS X-1707.
(34) Heat seal strength (2) (Table 8, 9-1, 9-2, 10-1, 10-2, 13)
The obtained ethylene polymer was applied onto a substrate using a Sumitomo Heavy Industries laminator having an extruder with a diameter of 65 mm and a T-die with a die width of 500 mm, with an air gap of 130 mm, a resin temperature under the die of 295°C, and a take-up speed of 80 m/min. Extrusion lamination was carried out under conditions of 10 minutes to obtain a film thickness of 25 μm. For the base material, a urethane-based anchor coating agent was applied to one side of a biaxially stretched nylon film (product name: Emblem ONM, manufactured by Unitika Co., Ltd.) with a thickness of 15 μm, and then a linear film obtained using a Ziegler catalyst was applied. A laminate was used, in which a 25 μm thick ethylene-based mixed resin was extruded and laminated with a blend of 50 parts by weight of low-density polyethylene and high-pressure low-density polyethylene. The ethylene polymer was extruded and laminated on the ethylene mixed resin layer side of the laminate.
The heat seal strength between the ethylene polymer layers of this extruded laminate film was measured and evaluated according to the following method.
Use a single-sided heated bar sealer Heat sealing pressure: 2kg/cm ²
Heat sealing time: 0.5 seconds Seal bar width: 10mm
Test piece width: 15mm
Peeling angle: 180 degrees Peeling speed: 300mm/min

(35) Blocking force (Tables 2-1, 2-2, 3-1, 3-2)
An ethylene polymer film cut out to a size of 7 (width) x 20 cm was sandwiched between type paper, further sandwiched between glass plates, and a 10 kg load was applied for 24 hours in an air bath at 50°C. The film was attached to an opening jig and pulled apart at a rate of 200 mm/min. The load at this time was Ag, and the blocking force F (g/cm) was expressed as F=A/width of the test piece. The smaller the value of F, the harder it is to block, that is, the better the blocking resistance is.

(36) Fisheye (F.E.) (Tables 4-1, 4-2)
Fisheye (F.E.) refers to spherical lumps and streaks that appear on the film surface. The number of FEs in 1000 cm ² of the film was visually counted by shining the ethylene polymer film under a fluorescent lamp.

(37) Neck-in (Table 8, 9-1, 9-2, 10-1, 10-2)
The obtained ethylene polymer was extrusion laminated on a 50 g/m ² kraft paper as a base material under the following conditions using a 65 mmφ extruder and a Sumitomo Heavy Industries laminator having a T-die with a die width of 500 mm. .
・Air gap: 130mm
・Resin temperature under die: 295℃
・Take-up speed: 50 m/min, 80 m/min, 120 m/min, 200 m/min ・Film thickness: 20 μm when take-up speed is 80 m/min, 13 μm when take-up speed is 120 m/min, and when take-up speed is 200 m/min is 8μm
When the width of the T-die is L ₀ and the width of the film laminated on the kraft paper at each take-up speed is L, the neck-in is calculated by L ₀ -L.

(38) Membrane breakage speed, take-up surging occurrence speed (Table 8, 9-1, 9-2, 10-1, 10-2)
The obtained ethylene polymer was applied onto a 50 g/m ² kraft paper as a base material with an air gap of 130 mm under the die using a Sumitomo Heavy Industries laminator having a 65 mmφ extruder and a T-die with a die width of 500 mm. Extrusion lamination was performed at a resin temperature of 295°C. The extrusion rate was set so that the film thickness was 20 μm when the take-up speed was 80 m/min.
The drawing speed was increased, and the drawing speed at which the molten film broke (including when only the end of the molten film was cut) was defined as the film breaking speed. In addition, increase the take-up speed, measure the neck-in five times at each take-up speed, and check the take-up speed when a value that is ±1.5 mm or more from the average value of the neck-in is measured two or more times. was taken as the take-up surging occurrence rate.

(39) Resin pressure (Table 8, 9-1, 9-2, 10-1, 10-2)
Using a Sumitomo Heavy Industries laminator equipped with a 65 mmφ extruder and a T-die with a die width of 500 mm, the obtained ethylene polymer was applied onto a 50 g/m ² kraft paper as a base material with an air gap of 130 mm below the die. Extrusion lamination was carried out at a resin temperature of 295° C. and a take-up speed of 80 m/min to give a film thickness of 20 μm. The resin pressure at the crosshead portion at that time was measured.

(40) Hot tack test (Table 13)
Using a laminate prepared for the measurement of heat seal strength, film pieces of the laminate with a length of 550 mm and a width of 50 mm were overlapped, and a sealing bar with a width of 10 mm and a length of 300 mm was used to seal 2.0 kg/ ^cm2. After sealing for 1 second at a pressure of The distance was determined and used as an index of hot tackability.

[Reference Example 1] (Fossil fuel-derived ethylene/1-hexene copolymer: PE-1-0)
(1-1) Preparation of catalyst 10 kg of silica dried at 250°C for 10 hours was suspended in 154 liters of toluene, and then cooled to 0°C. Thereafter, 57.5 liters of a toluene solution of methylaluminoxane (1.33 mol/l) was added dropwise over 1 hour. At this time, the temperature in the system was maintained at 0°C. Subsequently, the reaction was carried out at 0°C for 30 minutes, then the temperature was raised to 95°C over 1.5 hours, and the reaction was carried out at that temperature for 20 hours. Thereafter, the temperature was lowered to 60°C, and the supernatant liquid was removed by decantation. The solid component thus obtained was washed twice with toluene and then resuspended in 100 liters of toluene. 16.8 liters of a toluene solution of bis(1,3-dimethylcyclopentadienyl)zirconium dichloride (Zr=27.0 mmol/l) was dropped into this system at 80°C over 30 minutes, and then at 80°C for 2 hours. Allowed time to react. Thereafter, the supernatant liquid was removed and the solid catalyst containing 3.5 mg of zirconium per gram was obtained by washing twice with hexane.

(1-2) Preparation of prepolymerized catalyst 870 g of the solid catalyst obtained above and 260 g of 1-hexene were added to 87 liters of hexane containing 2.5 mol of triisobutylaluminum, and ethylene prepolymerization was carried out at 35°C for 5 hours. By performing the polymerization, a prepolymerized catalyst in which 10 g of polyethylene was prepolymerized per 1 g of the solid catalyst was obtained.

(1-3) Polymerization Ethylene and 1-hexene were copolymerized using a continuous fluidized bed gas phase polymerization apparatus at a total pressure of 20 kg/cm ² -G and a polymerization temperature of 80°C. The prepolymerized catalyst prepared above was continuously supplied at a rate of 0.33 mmol/hr in terms of zirconium atoms, and triisobutylaluminum was continuously supplied at a rate of 10 mmol/hr, and in order to maintain a constant gas composition during polymerization, ethylene, 1- Hexene, hydrogen, and nitrogen were continuously supplied (gas composition: 1-hexene/ethylene/=0.02, hydrogen/ethylene=10.5×10 ⁻⁴ , ethylene concentration=70%). Note that fossil fuel-derived ethylene was used as ethylene, and fossil fuel-derived 1-hexene was used as 1-hexene. Table 1 shows the resin physical properties of the ethylene/1-hexene copolymer (PE-1-0) thus obtained.

(1-4) Production of film The ethylene/1-hexene copolymer (PE-1-0) obtained in (1-3) above was pelletized using an extruder, and the air-cooled inflation method was used under the following molding conditions. A film having a thickness of 150 μm and a width of 450 mm was produced.
<Molding conditions>
Molding machine: 90mmφ inflation molding machine manufactured by Modern Machinery Co., Ltd. (uses high-pressure low-density polyethylene resin)
Screw: L/D=28, C/R=2.8, die with intermediate mixing: 200mmφ (diameter), 2.5mm (lip width)
Air ring: 2 gap type Molding temperature: 190℃
Pick-up speed: 20m/min
The Young's modulus, dart impact strength, and low-temperature properties of the bag (low-temperature falling ball strength test) of the film obtained as described above were measured using the measurement methods described above. The results obtained are shown in Table 1.

[Example 1] (Ethylene/1-hexene copolymer: PE-1-1)
In (1-3) polymerization of Reference Example 1, as ethylene, an ethylene mixture containing 10% by weight of biomass-derived ethylene and 90% by weight of fossil fuel-derived ethylene was used instead of fossil fuel-derived ethylene, and as 1-hexene, (1-1) of Reference Example 1 except that instead of fossil fuel-derived 1-hexene, a 1-hexene mixture containing 10% by weight of biomass-derived 1-hexene and 90% by weight of fossil fuel-derived 1-hexene was used. An ethylene/1-hexene copolymer (PE-1-1) was obtained in the same manner as in ~(1-3). Table 1 shows the resin physical properties of the obtained ethylene/1-hexene copolymer (PE-1-1).
Using the obtained ethylene/1-hexene copolymer (PE-1-1) in place of the fossil fuel-derived ethylene/1-hexene copolymer (PE-1-0), (1 -4) A film was produced according to the film manufacturing procedure. Table 1 shows the physical properties of the obtained film.

[Example 2] (Ethylene/1-hexene copolymer: PE-1-2)
In (1-3) polymerization of Reference Example 1, as ethylene, an ethylene mixture containing 30% by weight of biomass-derived ethylene and 70% by weight of fossil fuel-derived ethylene was used instead of fossil fuel-derived ethylene, and as 1-hexene, (1-1) of Reference Example 1 except that instead of fossil fuel-derived 1-hexene, a 1-hexene mixture containing 30% by weight of biomass-derived 1-hexene and 70% by weight of fossil fuel-derived 1-hexene was used. In the same manner as in ~(1-3), an ethylene/1-hexene copolymer (PE-1-2) was obtained. Table 1 shows the resin physical properties of the obtained ethylene/1-hexene copolymer (PE-1-2).
Using the obtained ethylene/1-hexene copolymer (PE-1-2) in place of the fossil fuel-derived ethylene/1-hexene copolymer (PE-1-0), (1 -4) A film was produced according to the procedure for producing a film. Table 1 shows the physical properties of the obtained film.

[Example 3] (Ethylene/1-hexene copolymer: PE-1-3)
In (1-3) polymerization of Reference Example 1, as ethylene, an ethylene mixture containing 35% by weight of biomass-derived ethylene and 65% by weight of fossil fuel-derived ethylene was used instead of fossil fuel-derived ethylene, and as 1-hexene, (1-1) of Reference Example 1 except that instead of fossil fuel-derived 1-hexene, a 1-hexene mixture containing 35% by weight of biomass-derived 1-hexene and 65% by weight of fossil fuel-derived 1-hexene was used. An ethylene/1-hexene copolymer (PE-1-3) was obtained in the same manner as in ~(1-3). Table 1 shows the resin properties of the obtained ethylene/1-hexene copolymer (PE-1-3).
Using the obtained ethylene/1-hexene copolymer (PE-1-3) in place of the fossil fuel-derived ethylene/1-hexene copolymer (PE-1-0), (1 -4) A film was produced according to the procedure for producing a film. Table 1 shows the physical properties of the obtained film.

[Reference Example 2-1] (Fossil fuel-derived ethylene/1-hexene random copolymer: PE-2-0)
(2-1) Preparation of catalyst 7.9 kg of silica dried at 250°C for 10 hours was suspended in 121 liters of toluene, and then cooled to 0°C. Thereafter, 41 liters of a toluene solution of methylaluminoxane (1.47 mol/l) was added dropwise over 1 hour. At this time, the temperature in the system was maintained at 0°C. Subsequently, the mixture was reacted at 0°C for 30 minutes, then the temperature was raised to 95°C over 1.5 hours, and the reaction was continued at that temperature for 4 hours. Thereafter, the temperature was lowered to 60°C, and the supernatant liquid was removed by decantation. The solid component thus obtained was washed twice with toluene and then resuspended in 125 liters of toluene. 20 liters of a toluene solution (Zr=28.4 mmol/l) of bis(1,3-dimethylcyclopentadienyl)zirconium dichloride was added dropwise into this system at 30°C over 30 minutes, and the reaction was further continued at 30°C for 2 hours. I let it happen. Thereafter, the supernatant liquid was removed and washed twice with hexane to obtain a solid catalyst containing 4.6 mg of zirconium per gram.

(2-2) Preparation of prepolymerized catalyst Add 4.3 kg of the solid catalyst obtained above to 160 liters of hexane containing 16 mol of triisobutylaluminum and perform prepolymerization of ethylene at 35°C for 3.5 hours. As a result, a prepolymerized catalyst in which 3 g of ethylene polymer was prepolymerized per 1 g of solid catalyst was obtained. The intrinsic viscosity [η] of this ethylene polymer was 1.27 dl/g.

(2-3) Polymerization Ethylene and 1-hexene were copolymerized using a continuous fluidized bed gas phase polymerization apparatus at a total pressure of 20 kg/cm ² -G and a polymerization temperature of 80°C. The prepolymerization catalyst prepared above was continuously supplied at a rate of 0.05 mmol/hr in terms of zirconium atoms, and triisobutylaluminum was continuously supplied at a rate of 10 mmol/hr to maintain a constant gas composition during polymerization. Hexene, hydrogen, and nitrogen were continuously supplied (gas composition (volume ratio): 1-hexene/ethylene = 0.034, hydrogen/ethylene = 11.8 x 10 ^-4 , ethylene concentration = 70%). Note that fossil fuel-derived ethylene was used as ethylene, and fossil fuel-derived 1-hexene was used as 1-hexene. The resin physical properties of the ethylene/1-hexene copolymer (PE-2-0) thus obtained are shown in Table 2-1.

(2-4) Production of film The ethylene/1-hexene copolymer (PE-2-0) obtained in (2-3) above was pelletized using an extruder, and the air-cooled inflation method was used under the following molding conditions. A film with a thickness of 30 μm and a width of 450 mm was produced.
<Molding conditions>
Molding machine: Plako LM 65mmφ inflation molding machine (manufactured by Plako Co., Ltd., high pressure method low density polyethylene resin specification)
Screw: L/D=28, C/R=2.8, die with intermediate mixing: 200mmφ (diameter), 1.2mm (lip width)
Air ring: 2 gap type Molding temperature: 200℃
Pick-up speed: 18m/min
For the film obtained as described above, moldability, Young's modulus, dart impact strength, tear strength (MD direction (longitudinal direction (sheet taking direction))), complete sealing temperature, and blocking force were measured. The results obtained are shown in Table 2-1. The moldability was determined by observing the stability of bubbles during molding, and was evaluated as ○ if it was good and × if it was bad.

[Example 4] (Ethylene/1-hexene random copolymer: PE-2-1)
In (2-3) polymerization of Reference Example 2-1, an ethylene mixture containing 10% by weight of biomass-derived ethylene and 90% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1-hexene was used. ( of Reference Example 2-1) except that instead of fossil fuel-derived 1-hexene, a 1-hexene mixture containing 10% by weight of biomass-derived 1-hexene and 90% by weight of fossil-fuel-derived 1-hexene was used. Ethylene/1-hexene copolymer (PE-2-1) was obtained in the same manner as in 2-1) to (2-3). The resin physical properties of the obtained ethylene/1-hexene copolymer (PE-2-1) are shown in Table 2-1.
Using the obtained ethylene/1-hexene copolymer (PE-2-1) in place of the fossil fuel-derived ethylene/1-hexene copolymer (PE-2-0), the procedure of Reference Example 2-1 was carried out. (2-4) A film was produced according to the procedure for producing a film. The physical properties of the obtained film are shown in Table 2-1.

[Example 5] (Ethylene/1-hexene random copolymer: PE-2-2)
In (2-3) polymerization of Reference Example 2-1, an ethylene mixture containing 30% by weight of biomass-derived ethylene and 70% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1-hexene was used. ( of Reference Example 2-1) except that a 1-hexene mixture containing 30% by weight of biomass-derived 1-hexene and 70% by weight of fossil fuel-derived 1-hexene was used instead of 1-hexene derived from fossil fuel. An ethylene/1-hexene copolymer (PE-2-2) was obtained in the same manner as in 2-1) to (2-3). The resin physical properties of the obtained ethylene/1-hexene copolymer (PE-2-2) are shown in Table 2-1.
Using the obtained ethylene/1-hexene copolymer (PE-2-2) in place of the fossil fuel-derived ethylene/1-hexene copolymer (PE-2-0), the procedure of Reference Example 2-1 was carried out. (2-4) A film was produced according to the procedure for producing a film. The physical properties of the obtained film are shown in Table 2-1.

[Example 6] (Ethylene/1-hexene copolymer: PE-2-3)
In (2-3) polymerization of Reference Example 2-1, an ethylene mixture containing 35% by weight of biomass-derived ethylene and 65% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1-hexene was used. ( of Reference Example 2-1) except that instead of fossil fuel-derived 1-hexene, a 1-hexene mixture containing 35% by weight of biomass-derived 1-hexene and 65% by weight of fossil fuel-derived 1-hexene was used. An ethylene/1-hexene copolymer (PE-2-3) was obtained in the same manner as in 2-1) to (2-3). The resin physical properties of the obtained ethylene/1-hexene copolymer (PE-2-3) are shown in Table 2-1.
Using the obtained ethylene/1-hexene copolymer (PE-2-3) in place of the fossil fuel-derived ethylene/1-hexene copolymer (PE-2-0), the procedure of Reference Example 2-1 was carried out. (2-4) A film was produced according to the procedure for producing a film. The physical properties of the obtained film are shown in Table 2-1.

[Reference Example 2-2] (Fossil fuel-derived ethylene/1-hexene random copolymer: PE-3-0)
Ethylene/1-hexene copolymer (PE- 3-0). The resin physical properties of the obtained ethylene/1-hexene copolymer (PE-3-0) are shown in Table 2-2. A film was formed and evaluated in the same manner as in Reference Example 2-1 (2-4) except that the obtained ethylene/1-hexene copolymer (PE-3-0) was used. The physical properties of the obtained film are shown in Table 2-2.

[Example 7] (Ethylene/1-hexene random copolymer: PE-3-1)
In the polymerization of Reference Example 2-2, as ethylene, an ethylene mixture containing 10% by weight of biomass-derived ethylene and 90% by weight of fossil fuel-derived ethylene was used instead of fossil fuel-derived ethylene, and as 1-hexene, fossil fuel-derived ethylene was used. Ethylene and A 1-hexene copolymer (PE-3-1) was obtained. The resin physical properties of the obtained ethylene/1-hexene copolymer (PE-3-1) are shown in Table 2-2.
Using the obtained ethylene/1-hexene copolymer (PE-3-1) in place of the fossil fuel-derived ethylene/1-hexene copolymer (PE-3-0), the procedure of Reference Example 2-1 was carried out. (2-4) A film was produced according to the procedure for producing a film. The physical properties of the obtained film are shown in Table 2-2.

[Example 8] (Ethylene/1-hexene random copolymer: PE-3-2)
In the polymerization of Reference Example 2-2, as ethylene, an ethylene mixture containing 30% by weight of biomass-derived ethylene and 70% by weight of fossil fuel-derived ethylene was used instead of fossil fuel-derived ethylene, and as 1-hexene, fossil fuel-derived ethylene was used. Ethylene and A 1-hexene copolymer (PE-3-2) was obtained. The resin physical properties of the obtained ethylene/1-hexene copolymer (PE-3-2) are shown in Table 2-2.
Using the obtained ethylene/1-hexene copolymer (PE-3-2) in place of the fossil fuel-derived ethylene/1-hexene copolymer (PE-3-0), the procedure of Reference Example 2-1 was carried out. (2-4) A film was produced according to the procedure for producing a film. The physical properties of the obtained film are shown in Table 2-2.

[Example 9] (Ethylene/1-hexene random copolymer: PE-3-3)
In the polymerization of Reference Example 2-2 in which the density and MFR were adjusted as shown in Table 2-2, 35% by weight of biomass-derived ethylene and 65% by weight of fossil-fuel-derived ethylene were used instead of fossil fuel-derived ethylene. Except for using a 1-hexene mixture containing 35% by weight of 1-hexene derived from biomass and 65% by weight of 1-hexene derived from fossil fuel instead of 1-hexene derived from fossil fuel. An ethylene/1-hexene copolymer (PE-3-3) was obtained in the same manner as in Reference Example 2-2. The resin physical properties of the obtained ethylene/1-hexene copolymer (PE-3-3) are shown in Table 2-2.
Using the obtained ethylene/1-hexene copolymer (PE-3-3) in place of the fossil fuel-derived ethylene/1-hexene copolymer (PE-3-0), the procedure of Reference Example 2-1 was carried out. (2-4) A film was produced according to the procedure for producing a film. The physical properties of the obtained film are shown in Table 2-2.

[Reference Example 3-1] (Fossil fuel-derived ethylene polymer mixture: PE-4-0)
Production of ethylene/1-hexene copolymer (X2-1-0) (3-1-1) Preparation of catalyst component 10.0 kg of silica dried at 250°C for 10 hours was suspended in 154 liters of toluene. Thereafter, it was cooled to 0°C. Thereafter, 57.5 liters of a toluene solution of methylaluminoxane (Al=1.33 mol/l) was added dropwise over 1 hour. At this time, the temperature in the system was maintained at 0°C. Subsequently, the mixture was reacted at 0°C for 30 minutes, then the temperature was raised to 95°C over 1.5 hours, and the reaction was continued at that temperature for 20 hours. Thereafter, the temperature was lowered to 60°C, and the supernatant liquid was removed by decantation. The solid component thus obtained was washed twice with toluene and then resuspended in 100 liters of toluene. 16.8 liters of a toluene solution (Zr=27.0 mmol/l) of bis(1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride was dropped into this system at 80°C over 30 minutes, and then The reaction was carried out at 80°C for 2 hours. Thereafter, the supernatant liquid was removed and the solid catalyst containing 3.5 mg of zirconium per gram was obtained by washing twice with hexane.

(3-1-2) Preparation of prepolymerized catalyst 870 g of the solid catalyst obtained in (3-1-1) above and 260 g of 1-hexene were added to 87 liters of hexane containing 2.5 mol of triisobutylaluminum. By performing prepolymerization of ethylene at 35° C. for 5 hours, a prepolymerized catalyst in which 10 g of polyethylene was prepolymerized per 1 g of solid catalyst was obtained.

(3-1-3) Polymerization Ethylene and 1-hexene were copolymerized using a continuous fluidized bed gas phase polymerization apparatus at a total pressure of 18 kg/cm ² -G and a polymerization temperature of 75°C. The prepolymerized catalyst prepared above was continuously supplied at a rate of 0.15 mmol/hr in terms of zirconium atoms, and triisobutylaluminum was continuously supplied at a rate of 10 mmol/hr, and in order to maintain a constant gas composition during polymerization, ethylene, 1- Hexene, hydrogen, and nitrogen were continuously supplied (gas composition; 1-hexene/ethylene = 0.022, hydrogen/ethylene = 0.00006, ethylene concentration = 80%). Note that fossil fuel-derived ethylene was used as ethylene, and fossil fuel-derived 1-hexene was used as 1-hexene. The resin physical properties of the obtained ethylene/1-hexene copolymer (X2-1-0) are shown in Table 3-1.

Production of ethylene/4-methyl-1-pentene copolymer (Y2-1-0) (3-1-4) Preparation of catalyst component Hexane obtained by dehydrating and purifying 1 mol of anhydrous magnesium chloride (commercial product) under a nitrogen atmosphere The suspension was suspended in 2 liters, 6 moles of ethanol was added dropwise over 1 hour while stirring, and the mixture was reacted at room temperature for 1 hour. After the reaction, 2.6 mol of diethylaluminum chloride was added dropwise to the mixture at room temperature, and stirring was continued for 2 hours. Next, after further adding 6 moles of titanium tetrachloride, the system was heated to 80° C. and the reaction was carried out with stirring for 3 hours. After the reaction, the resulting solid was separated and washed repeatedly with purified hexane. Next, 500 mmol of ethanol was added at room temperature to the above solid in an amount of 50 mmol in terms of Ti suspended in purified hexane, the temperature was raised to 50° C., and the mixture was reacted for 1.5 hours. After the reaction, the obtained solid portion was repeatedly washed with purified hexane. The produced solid was decomposed and extracted with H ₂ O-acetone, and then quantitatively determined using gas chromatography as ethanol.

(3-1-5) Polymerization Using a continuous reactor with an internal volume of 200 liters, dehydrated and purified hexane was fed at 100 liters/hr, diethylaluminum chloride 7 mmol/hr, ethyl aluminum sesquichloride 14 mmol/hr and the above (3-1-4 ) was continuously supplied at 0.6 mmol/hr in terms of Ti at such a rate, and the raw materials were ethylene 13 kg/hr, 4-methyl-1-pentene 19 kg/hr, and hydrogen 45 l/hr. The copolymer was continuously fed into the polymerization vessel at ^a ratio of A polymerization reaction was performed. The catalyst activity was 22100 g-copolymer/mmol-Ti. Note that fossil fuel-derived ethylene was used as ethylene, and fossil fuel-derived 4-methyl-1-pentene was used as 4-methyl-1-pentene. The resin physical properties of the obtained ethylene/4-methyl-1-pentene copolymer (Y2-1-0) are shown in Table 3-1.

(3-1-6) Preparation of ethylene/α-olefin copolymer mixture (Z-1-0) Ethylene/1-hexene copolymer (X2-1) obtained in (3-1-3) above -0) and the ethylene/4-methyl-1-pentene copolymer (Y2-1-0) obtained in (3-1-5) above were melt-kneaded in a 60/40 ratio to form ethylene/4-methyl-1-pentene copolymer (Y2-1-0). A mixture of α-olefin copolymers (Z-1-0) was obtained. The resin physical properties of the obtained ethylene/α-olefin copolymer mixture (Z-1-0) are shown in Table 3-1.

(3-1-7) Preparation of ethylene polymer mixture (PE-4-0) Ethylene/α-olefin copolymer mixture (Z-1-0) obtained in (3-1-6) above and high-pressure radical low-density polyethylene (D) were dry-blended at a mixing ratio of Z-1-0/D=85/15, and tri(2, 0.05 parts by weight of 4-di-t-butylphenyl) phosphate, and n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl) propionate as a heat stabilizer. 0.1 part by weight and 0.05 part by weight of calcium stearate as a hydrochloric acid absorbent were added. Thereafter, the mixture was kneaded using a conical tapered twin-screw extruder manufactured by Haake Co., Ltd. at a set temperature of 180° C. to obtain an ethylene polymer mixture (PE-4-0). Note that the high-pressure radical process low-density polyethylene may be ethylene derived from fossil fuels, ethylene derived from biomass, or a mixture of ethylene derived from fossil fuels and ethylene derived from biomass. The resin physical properties of the obtained ethylene polymer mixture (PE-4-0) are shown in Table 3-1.

(3-1-8) Production of film Using the ethylene polymer mixture (PE-4-0) obtained in (3-1-7) above, a single screw extruder with a diameter of 50 mm and L/D = 26; Using a 150mmφ die, lip width 2.0mm, and two-stage air ring, adjust the air flow rate so that the frost line is 20cm, extrusion amount 380g/min, blow ratio = 1.8, take-up speed = 18m/min A film with a thickness of 30 μm was inflation-molded under conditions of a processing temperature of 200° C. The resulting film was measured for haze, dart impact, complete heat seal temperature, blocking force, tear strength, and Young's modulus. The measurement results are shown in Table 3-1.

[Example 10] (Ethylene polymer mixture: PE-4-1)
Production of ethylene/1-hexene copolymer (X2-1-1) In the (3-1-3) polymerization of Reference Example 3-1, 10% by weight of biomass-derived ethylene was used instead of fossil fuel-derived ethylene as ethylene. % and 90% by weight of fossil fuel-derived ethylene, and as 1-hexene, 10% by weight of biomass-derived 1-hexene and 90% by weight of fossil fuel-derived 1-hexene were used instead of fossil fuel-derived 1-hexene. An ethylene/1-hexene copolymer (X2- 1-1) was obtained. The resin physical properties of the obtained ethylene/1-hexene copolymer (X2-1-1) are shown in Table 3-1.

Production of ethylene/4-methyl-1-pentene copolymer (Y2-1-1) In the (3-1-5) polymerization of Reference Example 3-1, biomass-derived ethylene was used instead of fossil fuel-derived ethylene as ethylene. Using an ethylene mixture containing 10% by weight of ethylene of (3-1-4) of Reference Example 3-1 except that a 4-methyl-1-pentene mixture containing 10% by weight of 1-pentene and 90% by weight of 4-methyl-1-pentene derived from fossil fuels was used. In the same manner as in ~(3-1-5), an ethylene/4-methyl-1-pentene copolymer (Y2-1-1) was obtained. The resin physical properties of the obtained ethylene/4-methyl-1-pentene copolymer (Y2-1-1) are shown in Table 3-1.

Preparation of ethylene/α-olefin copolymer mixture (Z-1-1) In the same manner as in the preparation of the ethylene/α-olefin copolymer mixture (3-1-6) in Reference Example 3-1, the above ethylene/α-olefin copolymer mixture (Z-1-1)・The 1-hexene copolymer (X2-1-1) and the above ethylene/4-methyl-1-pentene copolymer (Y2-1-1) were melt-kneaded in a ratio of 60/40 to form ethylene/α- An olefin copolymer mixture (Z-1-1) was obtained. The resin physical properties of the obtained ethylene/α-olefin copolymer mixture are shown in Table 3-1.

Preparation of ethylene polymer mixture (PE-4-1) Preparation of ethylene/α-olefin copolymer obtained in place of fossil fuel-derived ethylene/α-olefin copolymer mixture (Z-1-0) Using the mixture (Z-1-1), an ethylene polymer mixture (PE-4-1) was obtained in accordance with the preparation of (3-1-7) ethylene polymer mixture in Reference Example 3-1. The resin physical properties of the obtained ethylene polymer mixture are shown in Table 3-1.

Production of film Using the ethylene polymer mixture (PE-4-1) obtained in place of the fossil fuel-derived ethylene polymer mixture (PE-4-0), (3- 1-8) A film was produced according to the procedure for producing a film. The physical properties of the obtained film are shown in Table 3-1.

[Example 11] (Ethylene polymer mixture: PE-4-2)
Production of ethylene/1-hexene copolymer (X2-1-2) In the (3-1-3) polymerization of Reference Example 3-1, 30% by weight of biomass-derived ethylene was used instead of fossil fuel-derived ethylene as ethylene. % and 70% by weight of fossil fuel-derived ethylene, and as 1-hexene, 30% by weight of biomass-derived 1-hexene and 70% by weight of fossil fuel-derived 1-hexene were used instead of fossil fuel-derived 1-hexene. An ethylene/1-hexene copolymer (X2- 1-2) was obtained. The resin physical properties of the obtained ethylene/1-hexene copolymer (X2-1-2) are shown in Table 3-1.

Production of ethylene/4-methyl-1-pentene copolymer (Y2-1-2) In the (3-1-5) polymerization of Reference Example 3-1, biomass-derived ethylene was used instead of fossil fuel-derived ethylene as ethylene. Using an ethylene mixture containing 30% by weight of ethylene of (3-1-4) of Reference Example 3-1 except that a 4-methyl-1-pentene mixture containing 30% by weight of 1-pentene and 70% by weight of 4-methyl-1-pentene derived from fossil fuels was used. In the same manner as in ~(3-1-5), an ethylene/4-methyl-1-pentene copolymer (Y2-1-2) was obtained. The resin physical properties of the obtained ethylene/4-methyl-1-pentene copolymer (Y2-1-2) are shown in Table 3-1.

Preparation of ethylene/α-olefin copolymer mixture (Z-1-2) In the same manner as in the preparation of the ethylene/α-olefin copolymer mixture (3-1-6) in Reference Example 3-1, the above ethylene/α-olefin copolymer mixture (Z-1-2)・The 1-hexene copolymer (X2-1-2) and the above ethylene/4-methyl-1-pentene copolymer (Y2-1-2) are melt-kneaded in a ratio of 60/40 to form ethylene/α- An olefin copolymer mixture (Z-1-2) was obtained. The resin physical properties of the obtained ethylene/α-olefin copolymer mixture are shown in Table 3-1.

Preparation of ethylene polymer mixture (PE-4-2) Preparation of ethylene/α-olefin copolymer obtained in place of fossil fuel-derived ethylene/α-olefin copolymer mixture (Z-1-0) Using the mixture (Z-1-2), an ethylene polymer mixture (PE-4-2) was obtained in accordance with the preparation of (3-1-7) ethylene polymer mixture in Reference Example 3-1. The resin physical properties of the obtained ethylene polymer mixture are shown in Table 3-1.

Production of film Using the obtained ethylene polymer mixture (PE-4-2) in place of the fossil fuel-derived ethylene polymer mixture (PE-4-0), (3- 1-8) A film was produced according to the procedure for producing a film. The physical properties of the obtained film are shown in Table 3-1.

[Example 12] (Ethylene polymer mixture: PE-4-3)
Production of ethylene/1-hexene copolymer (X2-1-3) In the (3-1-3) polymerization of Reference Example 3-1, 35% by weight of biomass-derived ethylene was used instead of fossil fuel-derived ethylene as ethylene. % and 65% by weight of fossil fuel-derived ethylene, and as 1-hexene, 35% by weight of biomass-derived 1-hexene and 65% by weight of fossil fuel-derived 1-hexene were used instead of fossil fuel-derived 1-hexene. An ethylene/1-hexene copolymer (X2- 1-3) was obtained. The resin physical properties of the obtained ethylene/1-hexene copolymer (X2-1-3) are shown in Table 3-1.

Production of ethylene/4-methyl-1-pentene copolymer (Y2-1-3) In the (3-1-5) polymerization of Reference Example 3-1, biomass-derived ethylene was used instead of fossil fuel-derived ethylene as ethylene. Using an ethylene mixture containing 35% by weight of ethylene of (3-1-4) of Reference Example 3-1 except that a 4-methyl-1-pentene mixture containing 35% by weight of 1-pentene and 65% by weight of 4-methyl-1-pentene derived from fossil fuels was used. In the same manner as in ~(3-1-5), an ethylene/4-methyl-1-pentene copolymer (Y2-1-3) was obtained. The resin physical properties of the obtained ethylene/4-methyl-1-pentene copolymer (Y2-1-3) are shown in Table 3-1.

Preparation of ethylene/α-olefin copolymer mixture (Z-1-3) In the same manner as in the preparation of the ethylene/α-olefin copolymer mixture (3-1-6) in Reference Example 3-1, the above ethylene/α-olefin copolymer mixture (Z-1-3)・The 1-hexene copolymer (X2-1-3) and the above ethylene/4-methyl-1-pentene copolymer (Y2-1-3) are melt-kneaded in a ratio of 60/40 to form ethylene/α- A mixture of olefin copolymers (Z-1-3) was obtained. The resin physical properties of the obtained ethylene/α-olefin copolymer mixture are shown in Table 3-1.

Preparation of ethylene polymer mixture (PE-4-1) Preparation of ethylene/α-olefin copolymer obtained in place of fossil fuel-derived ethylene/α-olefin copolymer mixture (Z-1-0) Using the mixture (Z-1-3), an ethylene polymer mixture (PE-4-3) was obtained in accordance with the preparation of the ethylene polymer mixture (3-1-7) in Reference Example 3-1. The resin physical properties of the obtained ethylene polymer mixture are shown in Table 3-1.

Production of film Using the ethylene polymer mixture (PE-4-3) obtained in place of the fossil fuel-derived ethylene polymer mixture (PE-4-0), (3- 1-8) A film was produced according to the procedure for producing a film. The physical properties of the obtained film are shown in Table 3-1.

[Reference Example 3-2] (Fossil fuel-derived ethylene polymer mixture: PE-5-0)
(3-2-1) Production of ethylene/1-hexene copolymer (A-2-0) Except for adjusting the density and MFR as shown in Table 3-2, (3- Ethylene/1-hexene copolymer (X2-2-0) was obtained in the same manner as in 1-1) to (3-1-3). The resin physical properties of the obtained ethylene/1-hexene copolymer (X2-2-0) are shown in Table 3-2.

(3-2-2) Production of ethylene/4-methyl-1-pentene copolymer (Y2-2-0) Reference Example 3-1 except that the density and MFR were adjusted as shown in Table 3-2. Ethylene/4-methyl-1-pentene copolymer (Y2-2-0) was obtained in the same manner as in (3-1-4) to (3-1-5). The resin physical properties of the obtained ethylene/4-methyl-1-pentene copolymer (Y2-2-0) are shown in Table 3-2.

(3-2-3) Preparation of ethylene/α-olefin copolymer mixture (Z-2-0) In the same manner as in (3-1-6) of Reference Example 3-1, the above ethylene/1-hexene The copolymer (X2-2-0) and the above ethylene/4-methyl-1-pentene copolymer (Y2-2-0) were melt-kneaded in a 60/40 ratio to obtain an ethylene/α-olefin copolymer. A polymer mixture (Z-2-0) was obtained. The resin physical properties of the obtained ethylene/α-olefin copolymer mixture (Z-2-0) are shown in Table 3-2.

(3-2-4) Preparation of ethylene polymer mixture (PE-5-0) The above ethylene/α-olefin copolymer mixture (Z-2-0) and high-pressure radical process low-density polyethylene (D) were dry blended at a mixing ratio of C-2-0/D=85/15, and an ethylene polymer mixture (PE-5-0) was prepared in the same manner as in (3-1-7) of Reference Example 3-1. Obtained. Note that the high-pressure radical process low-density polyethylene may be ethylene derived from fossil fuels, ethylene derived from biomass, or a mixture of ethylene derived from fossil fuels and ethylene derived from biomass. The resin physical properties of the obtained ethylene polymer mixture (PE-5-0) are shown in Table 3-2.

(3-2-5) Production of film Using the ethylene polymer mixture (PE-5-0) obtained in (3-2-4) above, (3-1-8) of Reference Example 3-1 was prepared. A film was made according to the film manufacturing procedure. The physical properties of the obtained film are shown in Table 3-2.

[Example 13] (Ethylene polymer mixture: PE-5-1)
Production of ethylene/1-hexene copolymer (X2-2-1) In the production of ethylene/1-hexene copolymer (3-2-1) in Reference Example 3-2, fossil fuel-derived ethylene was used as ethylene. An ethylene mixture containing 10% by weight of ethylene derived from biomass and 90% by weight of ethylene derived from fossil fuel was used instead of 1-hexene, and 10% by weight of 1-hexene derived from biomass was used instead of 1-hexene derived from fossil fuel. Ethylene/1-hexene copolymer (X2 -2-1) was obtained. The resin physical properties of the obtained ethylene/1-hexene copolymer (X2-2-1) are shown in Table 3-2.

Production of ethylene/4-methyl-1-pentene copolymer (Y2-2-1) In the production of ethylene/4-methyl-1-pentene copolymer (3-2-2) of Reference Example 3-2, As ethylene, an ethylene mixture containing 10% by weight of ethylene derived from biomass and 90% by weight of ethylene derived from fossil fuel was used instead of ethylene derived from fossil fuel, and as 4-methyl-1-pentene, 4-methyl derived from fossil fuel was used. -1-Pentene was replaced with a 4-methyl-1-pentene mixture containing 10% by weight of 4-methyl-1-pentene derived from biomass and 90% by weight of 4-methyl-1-pentene derived from fossil fuels. Ethylene/4-methyl-1-pentene copolymer (Y2-2-1) was obtained in the same manner as in Reference Example 3-2 (3-2-2). The resin physical properties of the obtained ethylene/4-methyl-1-pentene copolymer (Y2-2-1) are shown in Table 3-2.

Preparation of ethylene/α-olefin copolymer mixture (Z-2-1) In the same manner as in the preparation of the ethylene/α-olefin copolymer mixture (3-2-3) in Reference Example 3-2, the above ethylene/α-olefin copolymer mixture (Z-2-1)・The 1-hexene copolymer (X2-2-1) and the above ethylene/4-methyl-1-pentene copolymer (Y2-2-1) are melt-kneaded in a ratio of 60/40 to form ethylene/α- An olefin copolymer mixture (Z-2-1) was obtained. The resin physical properties of the obtained ethylene/α-olefin copolymer mixture (Z-2-1) are shown in Table 3-2.

Preparation of ethylene polymer mixture (PE-5-1) Preparation of ethylene/α-olefin copolymer obtained in place of fossil fuel-derived ethylene/α-olefin copolymer mixture (Z-2-0) Using the mixture (Z-2-1), an ethylene polymer mixture (PE-5-1) was obtained according to the preparation of (3-2-4) ethylene polymer mixture in Reference Example 3-2. The resin physical properties of the obtained ethylene polymer mixture (PE-5-1) are shown in Table 3-2.

Production of film Using the ethylene polymer mixture (PE-5-1) obtained in place of the fossil fuel-derived ethylene polymer mixture (PE-5-0), (3- 2-5) A film was produced according to the procedure for producing a film. The physical properties of the obtained film are shown in Table 3-2.

[Example 14] (Ethylene polymer mixture: PE-5-2)
Production of ethylene/1-hexene copolymer (X2-2-2) In the production of ethylene/1-hexene copolymer (3-2-1) in Reference Example 3-2, fossil fuel-derived ethylene was used as ethylene. An ethylene mixture containing 30% by weight of ethylene derived from biomass and 70% by weight of ethylene derived from fossil fuel was used instead of 1-hexene, and 30% by weight of 1-hexene derived from biomass was used instead of 1-hexene derived from fossil fuel. Ethylene/1-hexene copolymer (X2 -2-2) was obtained. The resin physical properties of the obtained ethylene/1-hexene copolymer (X2-2-2) are shown in Table 3-2.

Production of ethylene/4-methyl-1-pentene copolymer (Y2-2-2) In the production of ethylene/4-methyl-1-pentene copolymer (3-2-2) of Reference Example 3-2, As ethylene, an ethylene mixture containing 30% by weight of ethylene derived from biomass and 70% by weight of ethylene derived from fossil fuel was used instead of ethylene derived from fossil fuel, and as 4-methyl-1-pentene, 4-methyl derived from fossil fuel was used. -1-Pentene was replaced with a 4-methyl-1-pentene mixture containing 30% by weight of biomass-derived 4-methyl-1-pentene and 70% by weight of fossil fuel-derived 4-methyl-1-pentene. Ethylene/4-methyl-1-pentene copolymer (Y2-2-2) was obtained in the same manner as (3-2-2) in Reference Example 3-2. The resin physical properties of the obtained ethylene/4-methyl-1-pentene copolymer (Y2-2-2) are shown in Table 3-2.

Preparation of ethylene/α-olefin copolymer mixture (Z-2-2) In the same manner as in the preparation of the ethylene/α-olefin copolymer mixture (3-2-3) in Reference Example 3-2, the above ethylene/α-olefin copolymer mixture (Z-2-2)・The 1-hexene copolymer (X2-2-2) and the above ethylene/4-methyl-1-pentene copolymer (Y2-2-2) are melt-kneaded in a 60/40 ratio to form ethylene/α- An olefin copolymer mixture (Z-2-2) was obtained. The resin physical properties of the obtained ethylene/α-olefin copolymer mixture (Z-2-2) are shown in Table 3-2.

Preparation of ethylene polymer mixture (PE-5-2) Preparation of ethylene/α-olefin copolymer obtained in place of fossil fuel-derived ethylene/α-olefin copolymer mixture (Z-2-0) Using the mixture (Z-2-2), an ethylene polymer mixture (PE-5-2) was obtained in accordance with the preparation of (3-2-4) ethylene polymer mixture in Reference Example 3-2. The resin physical properties of the obtained ethylene polymer mixture (PE-5-2) are shown in Table 3-2.

Production of film Using the ethylene polymer mixture (PE-5-2) obtained in place of the fossil fuel-derived ethylene polymer mixture (PE-5-0), (3- 2-5) A film was produced according to the procedure for producing a film. The physical properties of the obtained film are shown in Table 3-2.

[Example 15] (Ethylene polymer mixture: PE-5-3)
Production of ethylene/1-hexene copolymer (X2-2-3) In the production of ethylene/1-hexene copolymer (3-2-1) in Reference Example 3-2, fossil fuel-derived ethylene was used as ethylene. An ethylene mixture containing 35% by weight of ethylene derived from biomass and 65% by weight of ethylene derived from fossil fuel was used instead of 1-hexene, and 35% by weight of 1-hexene derived from biomass was used instead of 1-hexene derived from fossil fuel. Ethylene/1-hexene copolymer (X2 -2-3) was obtained. The resin physical properties of the obtained ethylene/1-hexene copolymer (X2-2-3) are shown in Table 3-2.

Production of ethylene/4-methyl-1-pentene copolymer (Y2-2-3) In the production of ethylene/4-methyl-1-pentene copolymer (3-2-2) of Reference Example 3-2, As ethylene, an ethylene mixture containing 35% by weight of ethylene derived from biomass and 65% by weight of ethylene derived from fossil fuel was used instead of ethylene derived from fossil fuel, and as 4-methyl-1-pentene, 4-methyl derived from fossil fuel was used. -1-Pentene was replaced with a 4-methyl-1-pentene mixture containing 35% by weight of 4-methyl-1-pentene derived from biomass and 65% by weight of 4-methyl-1-pentene derived from fossil fuels. Ethylene/4-methyl-1-pentene copolymer (Y2-2-3) was obtained in the same manner as (3-2-2) of Reference Example 3-2. The resin physical properties of the obtained ethylene/4-methyl-1-pentene copolymer (Y2-2-3) are shown in Table 3-2.

Preparation of ethylene/α-olefin copolymer mixture (Z-2-3) In the same manner as in the preparation of the ethylene/α-olefin copolymer mixture (3-2-3) in Reference Example 3-2, the above ethylene/α-olefin copolymer mixture (Z-2-3)・The 1-hexene copolymer (X2-2-3) and the above ethylene/4-methyl-1-pentene copolymer (Y2-2-3) are melt-kneaded in a 60/40 ratio to form ethylene/α- A mixture of olefin copolymers (Z-2-3) was obtained. The resin physical properties of the obtained ethylene/α-olefin copolymer mixture (Z-2-3) are shown in Table 3-2.

Preparation of ethylene polymer mixture (PE-5-3) Preparation of ethylene/α-olefin copolymer obtained in place of fossil fuel-derived ethylene/α-olefin copolymer mixture (Z-2-0) Using the mixture (Z-2-3), an ethylene polymer mixture (PE-5-3) was obtained according to the preparation of (3-2-4) ethylene polymer mixture in Reference Example 3-2. The resin physical properties of the obtained ethylene polymer mixture (PE-5-3) are shown in Table 3-2.

Production of film Using the ethylene polymer mixture (PE-5-3) obtained in place of the fossil fuel-derived ethylene polymer mixture (PE-5-0), (3- 2-5) A film was produced according to the procedure for producing a film. The physical properties of the obtained film are shown in Table 3-2.

[Reference Example 4-1] (Fossil fuel-derived ethylene/1-butene copolymer: PE-6-0)
(4-1) Production of catalyst component (4-1-1) Preparation of solid substance After sufficiently purging a glass reactor (inner volume 0.5 liters) with a stirrer with nitrogen gas, 8 g of metallic magnesium, 121 g of ethanol and 0.1 g of iodine were added, and the reaction was carried out under reflux conditions with stirring until no hydrogen gas was generated from the system, to obtain a solid product. 25 g of the solid obtained by drying the reaction solution containing this solid product under reduced pressure and 200 ml of hexane were placed in a stainless steel ball mill (400 ml internal volume, 100 stainless steel balls with a diameter of 1.2 cm) for 10 hours. Shredded. After distilling off the hexane under reduced pressure, the particle size of the solid material obtained was 4.4 μm on average and 11.0 μm at maximum (as measured by particle size distribution analyzer CIS-1 manufactured by GALAI using laser scanning analysis method). , particle shape was measured).

(4-1-2) Preparation of solid catalyst component Add 15 g of the solid substance obtained above and 350 ml of dehydrated hexane to a glass three-necked flask (inner volume: 0.5 liters) that has been sufficiently purged with nitrogen gas, and stir. Below, 3.8 ml of silicon tetrachloride and 3.8 ml of ethanol were added, and the reaction was carried out at 70°C for 2 hours.
Next, 20 ml of titanium tetrachloride was added and reacted at 70°C for 6 hours, followed by washing with hexane to obtain a solid catalyst component. The titanium content per gram of this solid catalyst component was measured by a colorimetric method and was found to be 44 mg.

(4-2) Polymerization The first stage polymerization was performed as follows. That is, to a polymerization apparatus with an internal volume of 200 liters equipped with a stirrer, ethylene was continuously supplied at a rate of 6.0 kg/hr, hexane 17 l/hr, and hydrogen 70 l/hr, and the solid catalyst component was fed in terms of titanium atoms. 1 mmol/hr, triethylaluminum at a rate of 2.8 mmol/hr, and diethylaluminum chloride at a rate of 30.2 mmol/hr, and polymerization was carried out continuously under the conditions of a polymerization temperature of 80° C. and a residence time of 3.5 hours. Ta. Note that fossil fuel-derived ethylene was used as the ethylene, and fossil fuel-derived 1-butene was used as the 1-butene.
The hexane suspension solution containing the obtained polyethylene was introduced into a hydrogen degassing layer at the same temperature (80°C) to separate hydrogen, and then the entire amount was transferred to the next second stage polymerization reactor (inner volume: 200 liters). ).
The second stage polymerization vessel was further supplied with ethylene at a rate of 5.3 kg/hr, hexane 15.1 l/hr, butene-1 at 280 g/hr, and hydrogen at a rate of 0.1 l/hr, and the polymerization temperature was maintained at 80 g/hr. C. and a residence time of 2.6 hours to obtain an ethylene/1-butene copolymer (PE-6-0). Note that fossil fuel-derived ethylene was used as the ethylene, and fossil fuel-derived 1-butene was used as the 1-butene.
The obtained suspension of the ethylene polymer in hexane is subjected to solid-liquid separation using a centrifuge in an atmosphere of 60° C. to separate a wet powder cake.
This powder cake was continuously dried in a powder dryer adjusted to 100°C with a residence time of 1 hour.

(4-3) Pelletization The ethylene/1-butene copolymer (PE-6-0) obtained in (4-2) above was made to never come into contact with air, and Irgafos 168 (Ciba) was used as an antioxidant. Specialty Chemicals) 1000ppm, Irganox 1010 (Ciba Specialty Chemicals) 500ppm as an antioxidant, and calcium stearate 3000ppm as a neutralizing agent were blended and continuously introduced into the supply hopper of a tandem twin-screw extruder. The mixture was melt-kneaded and the strands were cut to obtain pellet-shaped ethylene/1-butene copolymer (PE-6-0). The resin physical properties of the obtained ethylene/1-butene copolymer (PE-6-0) are shown in Table 4-1.

(4-4) Production of film The pellet-shaped ethylene/1-butene copolymer (PE-6-0) obtained in (4-3) above was molded by the inflation method under the following molding conditions. A film with a thickness of 20 μm and a width of 500 mm was produced.
<Molding conditions>
Extruder: Placo NLM (50mmφ)
Die model: Placo SG-11-100F6 special Lip part outer diameter: 100mmφ, gap: 1.2mm, land length: 20mm
Spiral part outer diameter: 110mmφ, number of threads: 6
Discharge amount: 56kg/hr
Pick-up speed: 42m/min
Set temperature: 200℃
Blow up ratio: 3.4
Film impact strength and fish eye (FE) were measured for the film obtained as described above. The results obtained are shown in Table 4-1.

[Example 16] (Ethylene/1-butene copolymer: PE-6-1)
In (4-2) polymerization of Reference Example 4-1, an ethylene mixture containing 10% by weight of biomass-derived ethylene and 90% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1-butene was used. ( of Reference Example 4-1) except that a 1-butene mixture containing 10% by weight of biomass-derived 1-butene and 90% by weight of fossil fuel-derived 1-butene was used instead of 1-butene derived from fossil fuel. An ethylene/1-butene copolymer (PE-6-1) was obtained in the same manner as in 4-1) to (4-3). The resin physical properties of the obtained ethylene/1-butene copolymer (PE-6-1) are shown in Table 4-1.
Using the obtained ethylene/1-butene copolymer (PE-6-1) in place of the fossil fuel-derived ethylene/1-butene copolymer (PE-6-0), the procedure of Reference Example 4-1 was carried out. (4-4) A film was produced according to the procedure for producing a film. The physical properties of the obtained film are shown in Table 4-1.

[Example 17] (Ethylene/1-butene copolymer: PE-6-2)
In (4-2) polymerization of Reference Example 4-1, an ethylene mixture containing 30% by weight of biomass-derived ethylene and 70% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1-butene was used. ( of Reference Example 4-1) except that instead of fossil fuel-derived 1-butene, a 1-butene mixture containing 30% by weight of biomass-derived 1-butene and 70% by weight of fossil fuel-derived 1-butene was used. Ethylene/1-butene copolymer (PE-6-2) was obtained in the same manner as in 4-1) to (4-3). The resin physical properties of the obtained ethylene/1-butene copolymer (PE-6-2) are shown in Table 4-1.
Using the obtained ethylene/1-butene copolymer (PE-6-2) in place of the fossil fuel-derived ethylene/1-butene copolymer (PE-6-0), the procedure of Reference Example 4-1 was carried out. (4-4) A film was produced according to the procedure for producing a film. The physical properties of the obtained film are shown in Table 4-1.

[Example 18] (Ethylene/1-butene copolymer: PE-6-3)
In (4-2) polymerization of Reference Example 4-1, an ethylene mixture containing 35% by weight of biomass-derived ethylene and 65% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1-butene was used. ( of Reference Example 4-1) except that a 1-butene mixture containing 35% by weight of biomass-derived 1-butene and 65% by weight of fossil fuel-derived 1-butene was used instead of 1-butene derived from fossil fuel. An ethylene/1-butene copolymer (PE-6-3) was obtained in the same manner as in 4-1) to (4-3). The resin physical properties of the obtained ethylene/1-butene copolymer (PE-6-3) are shown in Table 4-1.
Using the obtained ethylene/1-butene copolymer (PE-6-3) in place of the fossil fuel-derived ethylene/1-butene copolymer (PE-6-0), the procedure of Reference Example 4-1 was carried out. (4-4) A film was produced according to the procedure for producing a film. The physical properties of the obtained film are shown in Table 4-1.

[Reference Example 4-2] (Fossil fuel-derived ethylene/1-butene copolymer: PE-7-0)
Ethylene/1-butene copolymer (PE- 7-0). The resin physical properties of the obtained ethylene/1-butene copolymer (PE-7-0) are shown in Table 4-2. A film was formed and evaluated in the same manner as in (4-4) of Reference Example 4-1, except that the obtained ethylene/1-butene copolymer (PE-7-0) was used. The physical properties of the obtained film are shown in Table 4-2.

[Example 19] (Ethylene/1-butene copolymer: PE-7-1)
In the polymerization of Reference Example 4-2, as ethylene, an ethylene mixture containing 10% by weight of biomass-derived ethylene and 90% by weight of fossil fuel-derived ethylene was used instead of fossil fuel-derived ethylene, and as 1-butene, fossil fuel-derived ethylene was used. Ethylene and A 1-butene copolymer (PE-7-1) was obtained. The resin physical properties of the obtained ethylene/1-butene copolymer (PE-7-1) are shown in Table 4-2.
Using the obtained ethylene/1-butene copolymer (PE-7-1) in place of the fossil fuel-derived ethylene/1-butene copolymer (PE-7-0), the procedure of Reference Example 4-1 was carried out. (4-4) A film was produced according to the procedure for producing a film. The physical properties of the obtained film are shown in Table 4-2.

[Example 20] (ethylene/1-butene copolymer: PE-7-2)
In the polymerization of Reference Example 4-2, as ethylene, an ethylene mixture containing 30% by weight of biomass-derived ethylene and 70% by weight of fossil fuel-derived ethylene was used instead of fossil fuel-derived ethylene, and as 1-butene, fossil fuel-derived ethylene was used. Ethylene and A 1-butene copolymer (PE-7-2) was obtained. The resin physical properties of the obtained ethylene/1-butene copolymer (PE-7-2) are shown in Table 4-2.
Using the obtained ethylene/1-butene copolymer (PE-7-2) in place of the fossil fuel-derived ethylene/1-butene copolymer (PE-7-0), the procedure of Reference Example 4-1 was carried out. (4-4) A film was produced according to the procedure for producing a film. The physical properties of the obtained film are shown in Table 4-2.

[Example 21] (ethylene/1-butene copolymer: PE-7-3)
In the polymerization of Reference Example 4-2, as ethylene, an ethylene mixture containing 35% by weight of biomass-derived ethylene and 65% by weight of fossil fuel-derived ethylene was used instead of fossil fuel-derived ethylene, and as 1-butene, fossil fuel-derived ethylene was used. Ethylene and A 1-butene copolymer (PE-7-3) was obtained. The resin physical properties of the obtained ethylene/1-butene copolymer (PE-7-3) are shown in Table 4-2.
Using the obtained ethylene/1-butene copolymer (PE-7-3) in place of the fossil fuel-derived ethylene/1-butene copolymer (PE-7-0), the procedure of Reference Example 4-1 was carried out. (4-4) A film was produced according to the procedure for producing a film. The physical properties of the obtained film are shown in Table 4-2.

[Reference Example 5-1] (Fossil fuel-derived ethylene/1-pentene copolymer: PE-8-0)
(5-1) Preparation of titanium catalyst component 476 g of commercially available anhydrous magnesium chloride was suspended in 10 liters of n-decane under a nitrogen atmosphere, 4.0 kg of oleyl alcohol was added, and the mixture was reacted at 135°C for 5 hours with stirring. Ta. As a result, a colorless and transparent liquid was obtained.
After the temperature of this solution was lowered to 110°C, 0.45 mol of Ti(OC ₂ H ₅ ) ₄ was added, and the reaction was continued at 110°C for 5 hours. The resulting solution was stored at room temperature.

(5-2) Polymerization Using a continuous polymerization reactor with an internal volume of 200 liters, dehydrated and purified hexane at 100 liters/hr, ethylaluminum sesquichloride at 19.9 mmol/hr, and the titanium catalyst component obtained above converted into Ti atoms. It was continuously supplied at a rate of 0.50 mmol/hr. At the same time, ethylene was continuously supplied at a rate of 13 kg/hr, 1-pentene at 2.2 kg/hr, and hydrogen at 9.0 l/hr, at a polymerization temperature of 170°C, total pressure of 31 kg/cm ² -G, and retention. Copolymerization was carried out for 1 hour under conditions such that the copolymer concentration with respect to the solvent hexane was 105 g/l. Note that fossil fuel-derived ethylene was used as ethylene, and fossil fuel-derived 1-pentene was used as 1-pentene. The resin physical properties of the ethylene/1-pentene copolymer (PE-8-0) thus obtained are shown in Table 5-1.

(5-3) Production of film After blending a heat-resistant stabilizer with the ethylene/1-pentene copolymer (PE-8-0) obtained in (5-2) above, it is melt-extruded to pelletize it, and a commercially available polyolefin A film with a width of 180 mm and a thickness of 30 μm was molded using a tubular film molding machine. The resin temperature during molding was 180°C, and the extruder screw rotation speed was 60r. p. m. The test was carried out using a die diameter of 100 mmφ, a die slit width of 0.5 mm, and a single cooling air ring. The film thus obtained was measured for haze, gloss, film impact strength, tear strength, heat seal strength, and stress at yield point. The results obtained are shown in Table 5-1.

[Example 22] (ethylene/1-pentene copolymer: PE-8-1)
In (5-2) polymerization of Reference Example 5-1, an ethylene mixture containing 10% by weight of biomass-derived ethylene and 90% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1-pentene was used. ( of Reference Example 5-1) except that a 1-pentene mixture containing 10% by weight of biomass-derived 1-pentene and 90% by weight of fossil fuel-derived 1-pentene was used instead of fossil fuel-derived 1-pentene. Ethylene/1-pentene copolymer (PE-8-1) was obtained in the same manner as in 5-1) and (5-2). The resin physical properties of the obtained ethylene/1-pentene copolymer (PE-8-1) are shown in Table 5-1.
Using the obtained ethylene/1-pentene copolymer (PE-8-1) in place of the fossil fuel-derived ethylene/1-pentene copolymer (PE-8-0), the procedure of Reference Example 5-1 was carried out. (5-3) A film was produced according to film production. The physical properties of the obtained film are shown in Table 5-1.

[Example 23] (Ethylene/1-pentene copolymer: PE-8-2)
In (4-2) polymerization of Reference Example 4-1, an ethylene mixture containing 30% by weight of biomass-derived ethylene and 70% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1-pentene was added. ( of Reference Example 5-1) except that a 1-pentene mixture containing 30% by weight of biomass-derived 1-pentene and 70% by weight of fossil fuel-derived 1-pentene was used instead of 1-pentene derived from fossil fuel. An ethylene/1-pentene copolymer (PE-8-2) was obtained in the same manner as in 5-1) and (5-2). The resin physical properties of the obtained ethylene/1-pentene copolymer (PE-8-2) are shown in Table 5-1.
Using the obtained ethylene/1-pentene copolymer (PE-8-2) in place of the fossil fuel-derived ethylene/1-pentene copolymer (PE-8-0), the procedure of Reference Example 5-1 was carried out. (5-3) A film was produced according to the procedure for producing a film. The physical properties of the obtained film are shown in Table 5-1.

[Example 24] (Ethylene/1-pentene copolymer: PE-8-3)
In (4-2) polymerization of Reference Example 4-1, an ethylene mixture containing 35% by weight of biomass-derived ethylene and 65% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1-pentene was used. ( of Reference Example 5-1) except that a 1-pentene mixture containing 35% by weight of biomass-derived 1-pentene and 65% by weight of fossil fuel-derived 1-pentene was used instead of fossil fuel-derived 1-pentene. Ethylene/1-pentene copolymer (PE-8-3) was obtained in the same manner as in 5-1) and (5-2). The resin physical properties of the obtained ethylene/1-pentene copolymer (PE-8-3) are shown in Table 5-1.
Using the obtained ethylene/1-pentene copolymer (PE-8-3) in place of the fossil fuel-derived ethylene/1-pentene copolymer (PE-8-0), the procedure of Reference Example 5-1 was carried out. (5-3) A film was produced according to film production. The physical properties of the obtained film are shown in Table 5-1.

[Reference Example 5-2] (Fossil fuel-derived ethylene/1-pentene copolymer: PE-9-0)
Ethylene/1-pentene copolymer (PE- 9-0). The resin physical properties of the obtained ethylene/1-pentene copolymer (PE-9-0) are shown in Table 5-2. A film was formed and evaluated in the same manner as in Reference Example 5-1 (5-3) except that the obtained ethylene/1-pentene copolymer (PE-9-0) was used. The physical properties of the obtained film are shown in Table 5-2.

[Example 25] (Ethylene/1-pentene copolymer: PE-9-1)
In the polymerization of Reference Example 5-2, as ethylene, an ethylene mixture containing 10% by weight of biomass-derived ethylene and 90% by weight of fossil fuel-derived ethylene was used instead of fossil fuel-derived ethylene, and as 1-pentene, fossil fuel-derived ethylene was used. Ethylene and A 1-pentene copolymer (PE-9-1) was obtained. The resin physical properties of the obtained ethylene/1-pentene copolymer (PE-9-1) are shown in Table 5-2.
Using the obtained ethylene/1-pentene copolymer (PE-9-1) in place of the fossil fuel-derived ethylene/1-pentene copolymer (PE-9-0), the procedure of Reference Example 5-1 was carried out. (5-3) A film was produced according to film production. The physical properties of the obtained film are shown in Table 5-2.

[Example 26] (Ethylene/1-pentene copolymer: PE-9-2)
In the polymerization of Reference Example 5-2, as ethylene, an ethylene mixture containing 30% by weight of biomass-derived ethylene and 70% by weight of fossil fuel-derived ethylene was used instead of fossil fuel-derived ethylene, and as 1-pentene, fossil fuel-derived ethylene was used. Ethylene and A 1-pentene copolymer (PE-9-2) was obtained. The resin physical properties of the obtained ethylene/1-pentene copolymer (PE-9-2) are shown in Table 5-2.
Using the obtained ethylene/1-pentene copolymer (PE-9-2) in place of the fossil fuel-derived ethylene/1-pentene copolymer (PE-9-0), the procedure of Reference Example 5-1 was carried out. (5-3) A film was produced according to film production. The physical properties of the obtained film are shown in Table 5-2.

[Example 27] (Ethylene/1-pentene copolymer: PE-9-3)
In the polymerization of Reference Example 5-2, as ethylene, an ethylene mixture containing 35% by weight of biomass-derived ethylene and 65% by weight of fossil fuel-derived ethylene was used instead of fossil fuel-derived ethylene, and as 1-pentene, fossil fuel-derived ethylene was used. Ethylene and A 1-pentene copolymer (PE-9-3) was obtained. The resin physical properties of the obtained ethylene/1-pentene copolymer (PE-9-3) are shown in Table 5-2.
Using the obtained ethylene/1-pentene copolymer (PE-9-3) in place of the fossil fuel-derived ethylene/1-pentene copolymer (PE-9-0), the procedure of Reference Example 5-1 was carried out. (5-3) A film was produced according to film production. The physical properties of the obtained film are shown in Table 5-2.

[Reference Example 6-1] (Fossil fuel-derived ethylene/4-methyl-1-pentene copolymer: PE-10-0)
(6-1) Preparation of catalyst Under a nitrogen atmosphere, 1 mol of commercially available anhydrous magnesium chloride was suspended in 2 liters of dehydrated hexane, and 6 mol of ethanol was added dropwise over 1 hour with stirring, followed by 1 hour at room temperature. I reacted. 2.6 mol of diethylaluminum chloride was added dropwise to this at room temperature, and stirring was continued for 2 hours. Next, after adding 6 moles of titanium tetrachloride, the system was heated to 80° C. and the reaction was carried out with stirring for 3 hours. The solid portion after the reaction was separated and washed repeatedly with purified hexane. Further, to 50 mmol of Ti in the solid suspended in purified hexane, 500 mmol of ethanol was added at room temperature, and the temperature was raised to 50° C. and the mixture was reacted for 1.5 hours. After the reaction, the solid portion was washed repeatedly with purified hexane to obtain a catalyst.

(6-2) Polymerization Using a continuous polymerization reactor with an internal volume of 200 liters, dehydrated and purified hexane was produced at 100 liters/hr, diethylaluminum chloride 7 mmol/hr, and ethyl aluminum sesquichloride 14 mmol/hr, obtained in the above (6-1). The obtained catalyst was continuously supplied at a rate of 0.6 mmol/hr in terms of Ti, and at the same time, ethylene was supplied at 13 kg/hr, 4-methyl-1-pentene at 19 kg/hr, and hydrogen at 45 l/hr in the polymerization vessel. ^Ethylene and -Methyl-1-pentene copolymer (PE-10-0) was obtained. The catalyst activity corresponded to 21,700 g-copolymer/mmol-Ti. Note that fossil fuel-derived ethylene was used as ethylene, and fossil fuel-derived 4-methyl-1-pentene was used as 4-methyl-1-pentene. The resin physical properties of the obtained ethylene/4-methyl-1-pentene copolymer (PE-10-0) are shown in Table 6-1.

(6-3) Production of film The ethylene/4-methyl-1-pentene copolymer (PE-10-0) obtained in (6-2) above is pelletized using an extruder and used for commercially available high-pressure polyethylene. A film having a width of 350 mm and a thickness of 30 μm was molded using a tubular film molding machine (manufactured by Modern Machinery). The molding conditions were a resin temperature of 180°C and a screw rotation speed of 100r. p. m. , the die diameter is 100 mm, and the die slit width is 0.7 mm.
The film obtained as described above was measured for haze, film impact strength, Elmendorf tear strength, and heat seal initiation temperature. The results obtained are shown in Table 6-1.

[Example 28] (Ethylene/4-methyl-1-pentene copolymer: PE-10-1)
In (6-2) polymerization of Reference Example 6-1, 4-methyl -1-Pentene contains 10% by weight of 4-methyl-1-pentene derived from biomass and 90% by weight of 4-methyl-1-pentene derived from fossil fuel instead of 4-methyl-1-pentene derived from fossil fuel. Ethylene/4-methyl-1-pentene copolymer (PE- 10-1) was obtained. The resin physical properties of the obtained ethylene/4-methyl-1-pentene copolymer (PE-10-1) are shown in Table 6-1.
Using the obtained ethylene/4-methyl-1-pentene copolymer (PE-10-1) in place of the fossil fuel-derived ethylene/4-methyl-1-pentene copolymer (PE-10-0). A film was produced in accordance with the method for producing the film (6-3) in Reference Example 6-1. The physical properties of the obtained film are shown in Table 6-1.

[Example 29] (Ethylene/4-methyl-1-pentene copolymer: PE-10-2)
In (6-2) polymerization of Reference Example 6-1, 4-methyl -1-Pentene contains 30% by weight of 4-methyl-1-pentene derived from biomass and 70% by weight of 4-methyl-1-pentene derived from fossil fuel instead of 4-methyl-1-pentene derived from fossil fuel. Ethylene/4-methyl-1-pentene copolymer (PE- 10-2) was obtained. The resin physical properties of the obtained ethylene/4-methyl-1-pentene copolymer (PE-10-2) are shown in Table 6-1.
Using the obtained ethylene/4-methyl-1-pentene copolymer (PE-10-2) in place of the fossil fuel-derived ethylene/4-methyl-1-pentene copolymer (PE-10-0). A film was produced in accordance with the method for producing the film (6-3) in Reference Example 6-1. The physical properties of the obtained film are shown in Table 6-1.

[Example 30] (ethylene/4-methyl-1-pentene copolymer: PE-10-3)
In (6-2) polymerization of Reference Example 6-1, 4-methyl -1-Pentene contains 35% by weight of 4-methyl-1-pentene derived from biomass and 65% by weight of 4-methyl-1-pentene derived from fossil fuel instead of 4-methyl-1-pentene derived from fossil fuel. Ethylene/4-methyl-1-pentene copolymer (PE- 10-3) was obtained. The resin physical properties of the obtained ethylene/4-methyl-1-pentene copolymer (PE-10-3) are shown in Table 6-1.
Using the obtained ethylene/4-methyl-1-pentene copolymer (PE-10-3) in place of the fossil fuel-derived ethylene/4-methyl-1-pentene copolymer (PE-10-0). A film was produced in accordance with the method for producing the film (6-3) in Reference Example 6-1. The physical properties of the obtained film are shown in Table 6-1.

[Reference Example 6-2] (Fossil fuel-derived ethylene/4-methyl-1-pentene copolymer: PE-11-0)
Ethylene/4-methyl-1-pentene copolymer was prepared in the same manner as in Reference Example 6-1 (6-1) to (6-2) except that the density and MFR were adjusted as shown in Table 6-2. A combined product (PE-11-0) was obtained. The resin physical properties of the obtained ethylene/4-methyl-1-pentene copolymer (PE-11-0) are shown in Table 6-2. A film was formed and evaluated in the same manner as in Reference Example 6-1 (6-3) except that the obtained ethylene/4-methyl-1-pentene copolymer (PE-11-0) was used. went. The physical properties of the obtained film are shown in Table 6-2.

[Example 31] (Ethylene/4-methyl-1-pentene copolymer: PE-11-1)
In the polymerization of Reference Example 6-2, an ethylene mixture containing 10% by weight of biomass-derived ethylene and 90% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 4-methyl-1-pentene was used as 4-methyl-1-pentene. , 4-methyl-1- containing 10% by weight of 4-methyl-1-pentene derived from biomass and 90% by weight of 4-methyl-1-pentene derived from fossil fuel in place of 4-methyl-1-pentene derived from fossil fuel. An ethylene/4-methyl-1-pentene copolymer (PE-11-1) was obtained in the same manner as in Reference Example 6-2 except that a pentene mixture was used. The resin physical properties of the obtained ethylene/4-methyl-1-pentene copolymer (PE-11-1) are shown in Table 6-2.
Using the obtained ethylene/4-methyl-1-pentene copolymer (PE-11-1) in place of the fossil fuel-derived ethylene/4-methyl-1-pentene copolymer (PE-11-0). A film was produced in accordance with the method for producing the film (6-3) in Reference Example 6-1. The physical properties of the obtained film are shown in Table 6-2.

[Example 32] (Ethylene/4-methyl-1-pentene copolymer: PE-11-2)
In the polymerization of Reference Example 6-2, an ethylene mixture containing 30% by weight of biomass-derived ethylene and 70% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 4-methyl-1-pentene was used as 4-methyl-1-pentene. , 4-methyl-1- containing 30% by weight of 4-methyl-1-pentene derived from biomass and 70% by weight of 4-methyl-1-pentene derived from fossil fuel in place of 4-methyl-1-pentene derived from fossil fuel. An ethylene/4-methyl-1-pentene copolymer (PE-11-2) was obtained in the same manner as in Reference Example 6-2 except that a pentene mixture was used. The resin physical properties of the obtained ethylene/4-methyl-1-pentene copolymer (PE-11-2) are shown in Table 6-2.
Using the obtained ethylene/4-methyl-1-pentene copolymer (PE-11-2) in place of the fossil fuel-derived ethylene/4-methyl-1-pentene copolymer (PE-11-0). A film was produced in accordance with the method for producing the film (6-3) in Reference Example 6-1. The physical properties of the obtained film are shown in Table 6-2.

[Example 33] (Ethylene/4-methyl-1-pentene copolymer: PE-11-3)
In the polymerization of Reference Example 6-2, an ethylene mixture containing 35% by weight of biomass-derived ethylene and 65% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 4-methyl-1-pentene was used as 4-methyl-1-pentene. , 4-methyl-1- containing 35% by weight of biomass-derived 4-methyl-1-pentene and 65% by weight of fossil fuel-derived 4-methyl-1-pentene in place of fossil fuel-derived 4-methyl-1-pentene. An ethylene/4-methyl-1-pentene copolymer (PE-11-3) was obtained in the same manner as in Reference Example 6-2 except that a pentene mixture was used. The resin physical properties of the obtained ethylene/4-methyl-1-pentene copolymer (PE-11-3) are shown in Table 6-2.
Using the obtained ethylene/4-methyl-1-pentene copolymer (PE-11-3) in place of the fossil fuel-derived ethylene/4-methyl-1-pentene copolymer (PE-11-0). A film was produced in accordance with the method for producing the film (6-3) in Reference Example 6-1. The physical properties of the obtained film are shown in Table 6-2.

[Reference Example 7-1] (Fossil fuel-derived ethylene/4-methyl-1-pentene copolymer: PE-12-0)
(7-1) Preparation of catalyst Under a nitrogen atmosphere, 1 mol of commercially available anhydrous magnesium chloride was suspended in 2 liters of dehydrated hexane, and 6 mol of ethanol was added dropwise over 1 hour with stirring, followed by 1 hour at room temperature. I reacted. 2.6 mol of diethylaluminum chloride was added dropwise to this at room temperature, and stirring was continued for 2 hours. Next, after adding 6 moles of Ti tetrachloride, the system was heated to 80° C. and the reaction was carried out with stirring for 3 hours. The solid portion after the reaction was separated and washed repeatedly with purified hexane. Furthermore, 500 mmol of ethanol was added at room temperature to 50 mmol of Ti in the solid suspended in purified hexane, and the mixture was heated to 80° C. and reacted for 1 hour. After the reaction, the temperature was lowered to room temperature, 150 mmol of triethylaluminum was added, and the reaction was carried out with stirring for 1 hour. The solid portion after the reaction was washed repeatedly with purified hexane to obtain a catalyst.

(7-2) Polymerization Using a continuous polymerization reactor with an internal volume of 200 liters, dehydrated and purified hexane at 100 liters/hr, ethylaluminum sesquichloride at 15 mmol/hr, and the catalyst obtained in (7-1) above converted into Ti. At the same time, 13 kg/hr of ethylene, 13 kg/hr of 4-methyl-1-pentene, and hydrogen were continuously supplied at a rate of 30 l/hr in the polymerization vessel. Copolymerization was carried out at a polymerization temperature of 165°C, a total pressure of 30 kg/cm ² , a residence time of 1 hour, and a copolymer concentration of 130 g/l with respect to the hexane solvent. A polymer (PE-12-0) was obtained. The catalyst activity corresponded to 13,000 g-copolymer/mmol-Ti. Note that fossil fuel-derived ethylene was used as ethylene, and fossil fuel-derived 4-methyl-1-pentene was used as 4-methyl-1-pentene. The resin physical properties of the obtained ethylene/4-methyl-1-pentene copolymer (PE-12-0) are shown in Table 7-1.

(7-3) Production of film The ethylene/4-methyl-1-pentene copolymer (PE-12-0) obtained in (7-2) above is pelletized using an extruder and used for commercially available high-pressure polyethylene. A film having a width of 350 mm and a thickness of 30 μm was molded using a tubular film molding machine (manufactured by Modern Machinery). The molding conditions were a resin temperature of 180°C and a screw rotation speed of 100r. p. m. , the die diameter is 100 mm, and the die slit width is 0.7 mm.
The film obtained as described above was measured for haze, film impact strength, Elmendorf tear strength, and heat-sealing start temperature. The results obtained are shown in Table 7-1.

[Example 34] (Ethylene/4-methyl-1-pentene copolymer: PE-12-1)
In (7-2) polymerization of Reference Example 7-1, 4-methyl -1-Pentene includes 10% by weight of 4-methyl-1-pentene derived from biomass and 90% by weight of 4-methyl-1-pentene derived from fossil fuel instead of 4-methyl-1-pentene derived from fossil fuel. Ethylene/4-methyl-1-pentene copolymer (PE- 12-1) was obtained. The resin physical properties of the obtained ethylene/4-methyl-1-pentene copolymer (PE-12-1) are shown in Table 7-1.
Using the obtained ethylene/4-methyl-1-pentene copolymer (PE-12-1) in place of the fossil fuel-derived ethylene/4-methyl-1-pentene copolymer (PE-12-0). A film was produced in accordance with the method for producing the film (7-3) in Reference Example 7-1. The physical properties of the obtained film are shown in Table 7-1.

[Example 35] (Ethylene/4-methyl-1-pentene copolymer: PE-12-2)
In (7-2) polymerization of Reference Example 7-1, 4-methyl -1-Pentene contains 30% by weight of 4-methyl-1-pentene derived from biomass and 70% by weight of 4-methyl-1-pentene derived from fossil fuel instead of 4-methyl-1-pentene derived from fossil fuel. Ethylene/4-methyl-1-pentene copolymer (PE- 12-2) was obtained. The resin physical properties of the obtained ethylene/4-methyl-1-pentene copolymer (PE-12-2) are shown in Table 7-1.
Using the obtained ethylene/4-methyl-1-pentene copolymer (PE-12-2) in place of the fossil fuel-derived ethylene/4-methyl-1-pentene copolymer (PE-12-0). A film was produced in accordance with the method for producing the film (7-3) in Reference Example 7-1. The physical properties of the obtained film are shown in Table 7-1.

[Example 36] (Ethylene/4-methyl-1-pentene copolymer: PE-12-3)
In (7-2) polymerization of Reference Example 7-1, 4-methyl -1-Pentene contains 35% by weight of 4-methyl-1-pentene derived from biomass and 65% by weight of 4-methyl-1-pentene derived from fossil fuel instead of 4-methyl-1-pentene derived from fossil fuel. Ethylene/4-methyl-1-pentene copolymer (PE- 12-3) was obtained. The resin physical properties of the obtained ethylene/4-methyl-1-pentene copolymer (PE-12-3) are shown in Table 7-1.
Using the obtained ethylene/4-methyl-1-pentene copolymer (PE-12-3) in place of the fossil fuel-derived ethylene/4-methyl-1-pentene copolymer (PE-12-0). A film was produced in accordance with the method for producing the film (7-3) in Reference Example 7-1. The physical properties of the obtained film are shown in Table 7-1.

[Reference Example 7-2] (Fossil fuel-derived ethylene/4-methyl-1-pentene copolymer: PE-13-0)
Ethylene/4-methyl-1-pentene copolymer was prepared in the same manner as in Reference Example 7-1 (7-1) to (7-2) except that the density and MFR were adjusted as shown in Table 7-2. A combined product (PE-13-0) was obtained. The resin physical properties of the obtained ethylene/4-methyl-1-pentene copolymer (PE-13-0) are shown in Table 7-2. A film was formed in the same manner as in the production of (7-3) film in Reference Example 7-1, except that the obtained ethylene/4-methyl-1-pentene copolymer (PE-13-0) was used. , conducted an evaluation. The physical properties of the obtained film are shown in Table 7-2.

[Example 37] (Ethylene/4-methyl-1-pentene copolymer: PE-13-1)
In the polymerization of Reference Example 7-2, an ethylene mixture containing 10% by weight of biomass-derived ethylene and 90% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 4-methyl-1-pentene was used as 4-methyl-1-pentene. , 4-methyl-1- containing 10% by weight of 4-methyl-1-pentene derived from biomass and 90% by weight of 4-methyl-1-pentene derived from fossil fuel in place of 4-methyl-1-pentene derived from fossil fuel. An ethylene/4-methyl-1-pentene copolymer (PE-13-1) was obtained in the same manner as in Reference Example 7-2 except that a pentene mixture was used. The resin physical properties of the obtained ethylene/4-methyl-1-pentene copolymer (PE-13-1) are shown in Table 7-2.
Using the obtained ethylene/4-methyl-1-pentene copolymer (PE-13-1) in place of the fossil fuel-derived ethylene/4-methyl-1-pentene copolymer (PE-13-0). A film was produced in accordance with the method for producing the film (7-3) in Reference Example 7-1. The physical properties of the obtained film are shown in Table 7-2.

[Example 38] (Ethylene/4-methyl-1-pentene copolymer: PE-13-2)
In the polymerization of Reference Example 7-2, an ethylene mixture containing 30% by weight of biomass-derived ethylene and 70% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 4-methyl-1-pentene was used as 4-methyl-1-pentene. , 4-methyl-1- containing 30% by weight of 4-methyl-1-pentene derived from biomass and 70% by weight of 4-methyl-1-pentene derived from fossil fuel in place of 4-methyl-1-pentene derived from fossil fuel. An ethylene/4-methyl-1-pentene copolymer (PE-13-2) was obtained in the same manner as in Reference Example 7-2 except that a pentene mixture was used. The resin physical properties of the obtained ethylene/4-methyl-1-pentene copolymer (PE-13-2) are shown in Table 7-2.
Using the obtained ethylene/4-methyl-1-pentene copolymer (PE-13-2) in place of the fossil fuel-derived ethylene/4-methyl-1-pentene copolymer (PE-13-0). A film was produced in accordance with the method for producing the film (7-3) in Reference Example 7-1. The physical properties of the obtained film are shown in Table 7-2.

[Example 39] (Ethylene/4-methyl-1-pentene copolymer: PE-13-3)
In the polymerization of Reference Example 7-2, an ethylene mixture containing 35% by weight of biomass-derived ethylene and 65% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 4-methyl-1-pentene was used as 4-methyl-1-pentene. , 4-methyl-1- containing 35% by weight of biomass-derived 4-methyl-1-pentene and 65% by weight of fossil fuel-derived 4-methyl-1-pentene in place of fossil fuel-derived 4-methyl-1-pentene. An ethylene/4-methyl-1-pentene copolymer (PE-13-3) was obtained in the same manner as in Reference Example 7-2 except that a pentene mixture was used. The resin physical properties of the obtained ethylene/4-methyl-1-pentene copolymer (PE-13-3) are shown in Table 7-2.
Using the obtained ethylene/4-methyl-1-pentene copolymer (PE-13-3) in place of the fossil fuel-derived ethylene/4-methyl-1-pentene copolymer (PE-13-0). A film was produced in accordance with the method for producing the film (7-3) in Reference Example 7-1. The physical properties of the obtained film are shown in Table 7-2.

[Reference Example 8] (Fossil fuel-derived ethylene/1-butene copolymer: PE-14-0)
(8-1) Preparation of solid component In a reactor with an internal volume of 200 liters and equipped with a stirrer, 10 kg of silica (SiO ₂ : average particle size 12 μm) dried at 250°C for 10 hours in a nitrogen atmosphere was added to 66.5 liters of toluene. After suspending in water, the mixture was cooled to 0 to 5°C. To this suspension, 19.8 liters of a toluene solution of methylalumoxane (3.575 mmol/ml in terms of Al atoms) was diluted with 30.2 liters of toluene. A diluted toluene solution of methylalumoxane was added dropwise to this suspension over 1 hour. At this time, the temperature in the system was maintained at 0 to 5°C. Subsequently, the reaction was carried out at 0 to 5°C for 30 minutes, and then the temperature was raised to 95 to 100°C over about 1.5 hours, and the reaction was continued for 4 hours. Thereafter, the temperature was lowered, and the supernatant liquid was removed by decantation. After washing the solid component thus obtained four times with toluene, toluene was added to make a total volume of 140 liters to prepare a toluene slurry of the solid component. When a part of the obtained solid component was collected and its concentration was examined, it was found that the slurry concentration was 98.04 g/l and the Al concentration was 0.471 mol/l.

(8-2) Preparation of solid catalyst component A toluene slurry of 50.1 liters of toluene and 12.9 liters of the solid component prepared in (8-1) above was placed in a reactor with an internal volume of 150 liters equipped with a stirrer under a nitrogen atmosphere. (1265 g of solid components) was added. Next, in a 2-liter glass reactor under a nitrogen atmosphere, metallocene compound (A2) (metallocene compound (A-1) prepared in JP-A-2009-173798 Synthesis Example 1) dimethylsilylene (3-n-propylcyclopenta (dienyl) (cyclopentadienyl) zirconium dichloride) 5.72 g (14.65 mmol in terms of Zr atom) and metallocene compound (B2) (JP 2009-173798 No. 2009-173798 Metallocene compound (B-1) prepared in Synthesis Example 6 ) 9.00 g (16.52 mmol in terms of Zr atom) of isopropylidene (cyclopentadienyl-2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride) was collected (metallocene compound (A2)/metallocene The molar ratio of compound (B2) = 47/53) was dissolved in 2.0 liters of toluene, and the solution was pumped into the reactor. After pressure-feeding, the mixture was reacted for 1 hour at an internal temperature of 20 to 25°C, the supernatant liquid was removed by decantation, and the solid catalyst component was washed twice with hexane. Thereafter, hexane was added to make the total volume 50 liters to prepare a hexane slurry of the solid catalyst component. The metallocene compound (A2) can be synthesized, for example, as described in Synthesis Example 1 of JP-A No. 2009-173798, and the metallocene compound (B2) can be synthesized, for example, as described in Example 1 of JP-A-4-069394. It can be synthesized as described.

(8-3) Preparation of prepolymerized catalyst After cooling the hexane slurry of the solid catalyst component obtained in (8-2) above to 10.0°C, ethylene is continuously supplied into the system for several minutes under normal pressure. did. During this time, the temperature in the system was maintained at 10 to 15°C, and then 2.7 mol of diisobutylaluminum hydride and 84 ml of 1-hexene were added. After adding 1-hexene, ethylene supply was started at 1.82 kg/hr, and preliminary polymerization was carried out at a system internal temperature of 32 to 37°C. 43.0 ml of 1-hexene was added 58 minutes after the start of prepolymerization, 43.0 ml of 1-hexene was added 111 minutes after the start of prepolymerization, and when the ethylene supply reached 3827 g 153 minutes after the start of prepolymerization, ethylene was added. Supply has been stopped. Thereafter, the supernatant liquid was removed by decantation, and the solid catalyst component was washed three times with hexane, and then hexane was added to bring the total volume to 66 liters.
Next, a hexane solution of Chemistad 2500 (13.1 g) was pumped into the reactor at a system temperature of 34 to 36°C, and the temperature was then kept at 34 to 36°C for 1 hour, and Chemistad 2500 was added to the prepolymerization catalyst. carried it. Thereafter, the supernatant liquid was removed by decantation, and the prepolymerized catalyst was washed four times with hexane.
Next, 25 liters of the hexane slurry of the prepolymerized catalyst (5269 g of solid prepolymerized catalyst) was transferred to an evaporative dryer with an internal volume of 43 liters and equipped with a stirrer under a nitrogen atmosphere. After the liquid transfer, the pressure inside the dryer was reduced to -65 kPaG over about 3.5 hours, and when -65 kPaG was reached, it was vacuum dried for about 4.0 hours to remove hexane and volatile components of the prepolymerized catalyst. The pressure was further reduced to 100 kPaG, and when it reached -100 kPaG, it was vacuum dried for 6 hours to obtain a prepolymerized catalyst in which 3 g of polymer was polymerized per 1 g of solid catalyst component.
A part of the obtained prepolymerized catalyst component was dried and the composition was examined, and it was found that 0.50 mg of Zr atoms were contained per 1 g of the solid catalyst component.

(8-4) Polymerization In a fluidized bed gas phase polymerization reactor with an internal volume of 1.7 m ³ , the prepolymerized catalyst of (8-3) above was supplied at a rate of 0.023 mol/hr in terms of Zr atoms, and the total pressure was 2. Copolymerization was carried out under the following conditions: 0.0 MPaG, ethylene partial pressure of 1.2 MPaA, gas linear velocity in the reactor of 0.75 m/sec, polymerization temperature of 80° C., and residence time of 9.5 hours. Hydrogen, ethylene (5.5 kg/hr), and 1-butene (500 g/hr) were supplied so that the gas composition remained constant (hydrogen/ethylene ratio = 15.7, 1-butene/ethylene ratio = 0. 0334). Note that fossil fuel-derived ethylene was used as the ethylene, and fossil fuel-derived 1-butene was used as the 1-butene. The produced ethylene/1-butene copolymer (PE-14-0) was continuously extracted from the polymerization reactor and dried in a drying device.

(8-5) Production of film Irganox 1076 (manufactured by Ciba Specialty Chemicals) is added to the ethylene/1-butene copolymer (PE-14-0) obtained in (8-4) above as a heat-resistant stabilizer. and 0.1% by weight of Irgafos 168 (manufactured by Ciba Specialty Chemicals) using a single-screw 65mmφ extruder manufactured by Plako Co., Ltd. at a set temperature of 180°C and a screw rotation speed. 50r. p. m. After melt-kneading under the following conditions, the mixture was extruded into a strand, and a pellet-like ethylene/1-butene copolymer (PE-14-0) was obtained using a cutter. Table 8 shows the resin physical properties of the obtained ethylene/1-butene copolymer (PE-14-0). Further, Table 8 shows the results of extrusion lamination molding using the sample.

[Example 40] (Ethylene/1-butene copolymer: PE-14-1)
In (8-4) polymerization of Reference Example 8, as ethylene, an ethylene mixture containing 10% by weight of biomass-derived ethylene and 90% by weight of fossil fuel-derived ethylene was used instead of fossil fuel-derived ethylene, and as 1-butene, (8-1) of Reference Example 8 except that a 1-butene mixture containing 10% by weight of biomass-derived 1-butene and 90% by weight of fossil fuel-derived 1-butene was used instead of 1-butene derived from fossil fuel. In the same manner as in (8-4), an ethylene/1-butene copolymer (PE-14-1) was obtained.
Using the obtained ethylene/1-butene copolymer (PE-14-1) instead of the fossil fuel-derived ethylene/1-butene copolymer (PE-14-0), -5) According to film production, a pellet-shaped ethylene/1-butene copolymer (PE-14-1) was obtained, and the sample was extrusion laminated to produce a film. Table 8 shows the resin physical properties of the obtained ethylene/1-butene copolymer (PE-14-1) and the results of extrusion lamination.

[Example 41] (Ethylene/1-butene copolymer: PE-14-2)
In (8-4) polymerization of Reference Example 8, as ethylene, an ethylene mixture containing 30% by weight of biomass-derived ethylene and 70% by weight of fossil fuel-derived ethylene was used instead of fossil fuel-derived ethylene, and as 1-butene, (8-1) of Reference Example 8 except that a 1-butene mixture containing 30% by weight of biomass-derived 1-butene and 70% by weight of fossil fuel-derived 1-butene was used instead of 1-butene derived from fossil fuel. An ethylene/1-butene copolymer (PE-14-2) was obtained in the same manner as in ~(8-4).
(8 -5) According to film production, a pellet-shaped ethylene/1-butene copolymer (PE-14-2) was obtained, and the sample was extrusion laminated to produce a film. Table 8 shows the resin physical properties of the obtained ethylene/1-butene copolymer (PE-14-2) and the results of extrusion lamination.

[Example 42] (Ethylene/1-butene copolymer: PE-14-3)
In (8-4) polymerization of Reference Example 8, as ethylene, an ethylene mixture containing 35% by weight of biomass-derived ethylene and 65% by weight of fossil fuel-derived ethylene was used instead of fossil fuel-derived ethylene, and as 1-butene, (8-1) of Reference Example 8, except that instead of fossil fuel-derived 1-butene, a 1-butene mixture containing 35% by weight of biomass-derived 1-butene and 65% by weight of fossil fuel-derived 1-butene was used. An ethylene/1-butene copolymer (PE-14-3) was obtained in the same manner as in ~(8-4).
Using the obtained ethylene/1-butene copolymer (PE-14-3) in place of the fossil fuel-derived ethylene/1-butene copolymer (PE-14-0), -5) According to film production, a pellet-shaped ethylene/1-butene copolymer (PE-14-3) was obtained, and the sample was subjected to extrusion lamination to produce a film. Table 8 shows the resin physical properties of the obtained ethylene/1-butene copolymer (PE-14-3) and the results of extrusion lamination.

[Reference Example 9-1] (Fossil fuel-derived ethylene/1-hexene copolymer: PE-15-0)
(9-1-1) Preparation of solid component 10 kg of silica (SiO ₂ : average particle size 12 μm) dried at 250°C for 10 hours in a nitrogen atmosphere was placed in 66.5 liters of a reactor with an internal volume of 200 liters equipped with a stirrer. The suspension was suspended in toluene and cooled to 0 to 5°C. 19.8 liters of a toluene solution of methylalumoxane (3.575 mmol/ml in terms of Al atoms) was diluted with 30.2 liters of toluene. A diluted toluene solution of methylalumoxane was added dropwise to this suspension over 1 hour. At this time, the temperature in the system was maintained at 0 to 5°C. Subsequently, the reaction was carried out at 0 to 5°C for 30 minutes, and then the temperature was raised to 95 to 100°C over about 1.5 hours, and then the reaction was continued at 95 to 100°C for 4 hours. Thereafter, the temperature was lowered, and the supernatant liquid was removed by decantation. After washing the solid component thus obtained four times with toluene, toluene was added to make a total volume of 140 liters to prepare a toluene slurry of the solid component. When a part of the obtained solid component was collected and its concentration was examined, it was found that the slurry concentration was 98.04 g/l and the Al concentration was 0.471 mol/l.

(9-2-1) Preparation of solid catalyst component A toluene slurry of 50.1 liters of toluene and the solid component prepared in (9-1-1) above was placed in a reactor with an internal volume of 150 liters and equipped with a stirrer under a nitrogen atmosphere. 12.9 liters (1265 g solids) were added. Next, in a 2-liter glass reactor under a nitrogen atmosphere, metallocene compound (A3) (metallocene compound (A-2) prepared in Synthesis Example 2 of JP-A-2009-197225), dimethylsilylene (3-n-propylcyclopenta (dienyl) (cyclopentadienyl) zirconium dichloride) 5.72 g (14.65 mmol in terms of Zr atom) and metallocene compound (B3) (JP 2009-197225 A) Metallocene compound (B-1) prepared in Synthesis Example 3 ) 9.00 g (16.52 mmol in terms of Zr atom) of isopropylidene (cyclopentadienyl-2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride) was collected (metallocene compound (A3)/metallocene The molar ratio of compound (B3) = 47/53) was dissolved in 2.0 liters of toluene, and the solution was pumped into the above reactor. After pressure-feeding, the mixture was reacted for 1 hour at an internal temperature of 20 to 25°C, the supernatant liquid was removed by decantation, and the solid catalyst component was washed twice with hexane. Thereafter, hexane was added to make the total volume 50 liters to prepare a hexane slurry of the solid catalyst component. The metallocene compound (A3) can be synthesized, for example, as described in Synthesis Example 2 of JP-A No. 2009-197225, and the metallocene compound (B3) can be synthesized, for example, as described in Example 1 of JP-A-4-069394. It can be synthesized as described.

(9-3-1) Preparation of prepolymerized catalyst After cooling the hexane slurry of the solid catalyst component obtained in (9-2-1) above to 10.0°C, ethylene was continuously introduced into the system under normal pressure. for several minutes. During this time, the temperature in the system was maintained at 10 to 15°C, and then 2.7 mol of diisobutylaluminum hydride and 84 ml of 1-hexene were added. After adding 1-hexene, ethylene supply was started at 1.82 kg/hr, and preliminary polymerization was carried out at a system internal temperature of 32 to 37°C. 43.0 ml of 1-hexene was added 58 minutes after the start of prepolymerization, 43.0 ml of 1-hexene was added 111 minutes after the start of prepolymerization, and when the ethylene supply reached 3827 g 153 minutes after the start of prepolymerization, ethylene was added. Supply has been stopped. Thereafter, the supernatant liquid was removed by decantation, and the solid catalyst component was washed three times with hexane, and then hexane was added to bring the total volume to 66 liters.
Next, a hexane solution of Chemistad 2500 (13.1 g) was pumped into the reactor at a system temperature of 34 to 36°C, and the temperature was then kept at 34 to 36°C for 1 hour, and Chemistad 2500 was added to the prepolymerization catalyst. It was carried. Thereafter, the supernatant liquid was removed by decantation, and the prepolymerized catalyst was washed four times with hexane.
Next, 25 liters of the hexane slurry of the prepolymerized catalyst (5269 g of solid prepolymerized catalyst) was transferred to an evaporative dryer with an internal volume of 43 liters and equipped with a stirrer under a nitrogen atmosphere. After the liquid transfer, the pressure inside the dryer was reduced to -65 kPaG over about 3.5 hours, and when -65 kPaG was reached, it was vacuum dried for about 4.0 hours to remove hexane and volatile components of the prepolymerized catalyst. The pressure was further reduced to 100 kPaG, and when it reached -100 kPaG, it was vacuum dried for 6 hours to obtain a prepolymerized catalyst in which 3 g of polymer was polymerized per 1 g of solid catalyst component.
A part of the obtained prepolymerized catalyst component was dried and the composition was examined, and it was found that 0.50 mg of Zr atoms were contained per 1 g of the solid catalyst component.

(9-4-1) Polymerization In a fluidized bed gas phase polymerization reactor with an internal volume of 1.7 m ³ , the prepolymerized catalyst of (9-3-1) above was supplied at a rate of 0.018 mol/hr in terms of Zr atoms. The copolymerization was carried out under the following conditions: a total pressure of 2.0 MPaG, a partial pressure of ethylene of 1.2 MPaA, a linear gas velocity in the reactor of 0.8 m/sec, a polymerization temperature of 80° C., and a residence time of 9.6 hours. Hydrogen, ethylene (5.7 kg/hr), and 1-hexene (350 g/hr) were supplied so that the gas composition was constant (hydrogen/ethylene ratio = 9.1, 1-hexene/ethylene ratio = 0. 0077). Note that fossil fuel-derived ethylene was used as ethylene, and fossil fuel-derived 1-hexene was used as 1-hexene. The produced ethylene/1-hexene copolymer (PE-15-0) was continuously extracted from the polymerization reactor and dried in a drying device.

(9-5-1) Production of film Irganox 1076 (Ciba Specialty) was added to the ethylene/1-hexene copolymer (PE-15-0) obtained in (9-4-1) above as a heat stabilizer. Chemicals Co., Ltd.) and Irgafos 168 (Ciba Specialty Chemicals Co., Ltd.) at a concentration of 0.1% by weight, and using a single-screw 65mmφ extruder manufactured by Plako Co., Ltd., the temperature was set at 180°C. , screw rotation speed 50 r. p. m. After melt-kneading under the following conditions, the mixture was extruded into strands, and pelletized ethylene/1-hexene copolymer (PE-15-0) was obtained using a cutter. The resin physical properties of the obtained ethylene/1-hexene copolymer (PE-15-0) are shown in Table 9-1. Furthermore, the results of extrusion lamination molding using the sample are shown in Table 9-1.

[Example 43] (Ethylene/1-hexene copolymer: PE-15-1)
In (9-4-1) polymerization of Reference Example 9-1, an ethylene mixture containing 10% by weight of biomass-derived ethylene and 90% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1 - Reference Example 9-1, except that a 1-hexene mixture containing 10% by weight of biomass-derived 1-hexene and 90% by weight of fossil fuel-derived 1-hexene was used instead of fossil fuel-derived 1-hexene as hexene. Ethylene/1-hexene copolymer (PE-15-1) was obtained in the same manner as in (9-1-1) to (9-4-1).
Using the obtained ethylene/1-hexene copolymer (PE-15-1) in place of the fossil fuel-derived ethylene/1-hexene copolymer (PE-15-0), the procedure of Reference Example 9-1 was carried out. (9-5-1) A pellet-shaped ethylene/1-hexene copolymer (PE-15-1) was obtained in accordance with the production of film, and the sample was subjected to extrusion lamination to produce a film. The resin physical properties of the obtained ethylene/1-hexene copolymer (PE-15-1) and the results of extrusion lamination are shown in Table 9-1.

[Example 44] (Ethylene/1-hexene copolymer: PE-15-2)
In (9-4-1) polymerization of Reference Example 9-1, an ethylene mixture containing 30% by weight of biomass-derived ethylene and 70% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1 - Reference Example 9-1, except that a 1-hexene mixture containing 30% by weight of biomass-derived 1-hexene and 70% by weight of fossil fuel-derived 1-hexene was used instead of fossil fuel-derived 1-hexene as hexene. Ethylene/1-hexene copolymer (PE-15-2) was obtained in the same manner as in (9-1-1) to (9-4-1).
Using the obtained ethylene/1-hexene copolymer (PE-15-2) in place of the fossil fuel-derived ethylene/1-hexene copolymer (PE-15-0), the procedure of Reference Example 9-1 was carried out. (9-5-1) Pellet-shaped ethylene/1-hexene copolymer (PE-15-2) was obtained in accordance with film production, and the sample was extrusion laminated to produce a film. The resin physical properties of the obtained ethylene/1-hexene copolymer (PE-15-2) and the results of extrusion lamination are shown in Table 9-1.

[Example 45] (Ethylene/1-hexene copolymer: PE-15-3)
In (9-4-1) polymerization of Reference Example 9-1, an ethylene mixture containing 35% by weight of biomass-derived ethylene and 65% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1 - Reference Example 9-1, except that a 1-hexene mixture containing 35% by weight of biomass-derived 1-hexene and 65% by weight of fossil fuel-derived 1-hexene was used instead of fossil fuel-derived 1-hexene as hexene. Ethylene/1-hexene copolymer (PE-15-3) was obtained in the same manner as in (9-1-1) to (9-4-1).
Using the obtained ethylene/1-hexene copolymer (PE-15-3) in place of the fossil fuel-derived ethylene/1-hexene copolymer (PE-15-0), the procedure of Reference Example 9-1 was carried out. (9-5-1) Pellet-shaped ethylene/1-hexene copolymer (PE-15-3) was obtained in accordance with film production, and the sample was extrusion laminated to produce a film. Table 9-1 shows the resin physical properties of the obtained ethylene/1-hexene copolymer (PE-15-3) and the results of extrusion lamination.

[Reference Example 9-2] (Fossil fuel-derived ethylene/1-hexene copolymer: PE-16-0)
(9-1-2) Preparation of solid component It was prepared in the same manner as in the preparation of (9-1-1) solid component in Reference Example 9-1.

(9-2-2) Preparation of solid catalyst component A toluene slurry of 31.3 liters of toluene and the solid component prepared in (9-1-2) above in a reactor with an internal volume of 150 liters and a stirrer under a nitrogen atmosphere. 8.3 liters (814 g solids) were added. Next, 3.27 g (8.38 mmol in terms of Zr atoms) of the metallocene compound (A3) described above and 6.32 g (11 mmol in terms of Zr atoms) of the above metallocene compound (B3) were placed in a 2-liter glass reactor under a nitrogen atmosphere. .57 mmol) was collected (molar ratio of metallocene compound (A3)/metallocene compound (B3) = 42/58), dissolved in 2.0 liters of toluene, and pumped into the above reactor. After pressure-feeding, the mixture was reacted for 1 hour at an internal temperature of 20 to 25°C, the supernatant liquid was removed by decantation, and the solid catalyst component was washed twice with hexane. Thereafter, hexane was added to make the total volume 50 liters to prepare a hexane slurry of the solid catalyst component.

(9-3-2) Preparation of prepolymerized catalyst After cooling the hexane slurry of the solid catalyst component obtained in (9-2-2) above to 10.0°C, ethylene was continuously introduced into the system under normal pressure. for several minutes. During this time, the temperature in the system was maintained at 10 to 15°C, and then 1.7 mol of diisobutylaluminum hydride and 53 ml of 1-hexene were added. After the addition of 1-hexene, ethylene supply was started at 1.67 kg/hr, and preliminary polymerization was carried out at a system internal temperature of 32 to 37°C. 28.0 ml of 1-hexene was added 35 minutes after the start of prepolymerization, 28.0 ml of 1-hexene was added 102 minutes after the start of prepolymerization, and when the ethylene supply reached 2450 g 139 minutes after the start of prepolymerization, ethylene was added. Supply has been stopped. Thereafter, the supernatant liquid was removed by decantation, and the solid catalyst component was washed three times with hexane, and then hexane was added to make the total volume 42 liters.
Next, a hexane solution of Chemistad 2500 (8.4 g) was pumped into the reactor at a system temperature of 34 to 36°C, and the temperature was then kept at 34 to 36°C for 1 hour, and Chemistad 2500 was added to the prepolymerization catalyst. carried it. Thereafter, the supernatant liquid was removed by decantation, and the prepolymerized catalyst was washed four times with hexane.
Next, 25 liters of the hexane slurry of the prepolymerized catalyst (3372 g of solid prepolymerized catalyst) was transferred to an evaporative dryer with an internal volume of 43 liters and equipped with a stirrer under a nitrogen atmosphere. After the liquid transfer, the pressure inside the dryer was reduced to -65 kPaG over about 3.5 hours, and when -65 kPaG was reached, it was vacuum dried for about 4.0 hours to remove hexane and volatile components of the prepolymerized catalyst. The pressure was further reduced to 100 kPaG, and when it reached -100 kPaG, it was vacuum dried for 6 hours to obtain a prepolymerized catalyst in which 3 g of polymer was polymerized per 1 g of solid catalyst component.
A part of the obtained prepolymerized catalyst component was dried and the composition was examined, and it was found that 0.50 mg of Zr atoms were contained per 1 g of the solid catalyst component.

(9-4-2) Polymerization In a fluidized bed type gas phase polymerization reactor with an internal volume of 1.7 m ³ , the prepolymerization catalyst of (9-3-2) above was supplied at a rate of 0.019 mol/hr in terms of Zr atoms. Copolymerization was carried out under the following conditions: a total pressure of 2.0 MPaG, a partial pressure of ethylene of 1.2 MPaA, a linear gas velocity in the reactor of 0.8 m/sec, a polymerization temperature of 70° C., and a residence time of 10.6 hours. Hydrogen, ethylene (5.5 kg/hr), and 1-hexene (520 g/hr) were supplied so that the gas composition was constant (hydrogen/ethylene ratio = 6.3, 1-hexene/ethylene ratio = 0. 0100). Note that fossil fuel-derived ethylene was used as ethylene, and fossil fuel-derived 1-hexene was used as 1-hexene. The produced ethylene/1-hexene copolymer (PE-16-0) is continuously extracted from the polymerization reactor and dried in a drying device. Obtained.

(9-5-2) Production of film Pellet-shaped ethylene/1-hexene copolymer (PE-16-0) was obtained in the same manner as in the production of film (9-5-1) in Reference Example 9-1. A film was manufactured by extrusion lamination using the sample. The resin physical properties of the obtained ethylene/1-hexene copolymer (PE-16-0) and the results of extrusion lamination are shown in Table 9-2.

[Example 46] (Ethylene/1-hexene copolymer: PE-16-1)
In (9-4-2) polymerization of Reference Example 9-2, an ethylene mixture containing 10% by weight of biomass-derived ethylene and 90% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1 - Reference Example 9-2, except that as hexene, a 1-hexene mixture containing 10% by weight of biomass-derived 1-hexene and 90% by weight of fossil fuel-derived 1-hexene was used instead of fossil fuel-derived 1-hexene. Ethylene/1-hexene copolymer (PE-16-1) was obtained in the same manner as in (9-1-2) to (9-4-2).
Using the obtained ethylene/1-hexene copolymer (PE-16-1) in place of the fossil fuel-derived ethylene/1-hexene copolymer (PE-16-0), the procedure of Reference Example 9-2 was carried out. (9-5-2) According to the production of film, a pellet-shaped ethylene/1-hexene copolymer (PE-16-1) was obtained, and the sample was subjected to extrusion lamination to produce a film. The resin physical properties of the obtained ethylene/1-hexene copolymer (PE-16-1) and the results of extrusion lamination are shown in Table 9-2.

[Example 47] (Ethylene/1-hexene copolymer: PE-16-2)
In (9-4-2) polymerization of Reference Example 9-2, an ethylene mixture containing 30% by weight of biomass-derived ethylene and 70% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1 - Reference Example 9-2, except that as hexene, a 1-hexene mixture containing 30% by weight of biomass-derived 1-hexene and 70% by weight of fossil fuel-derived 1-hexene was used instead of 1-hexene derived from fossil fuel. Ethylene/1-hexene copolymer (PE-16-2) was obtained in the same manner as in (9-1-2) to (9-4-2).
Using the obtained ethylene/1-hexene copolymer (PE-16-2) in place of the fossil fuel-derived ethylene/1-hexene copolymer (PE-16-0), the procedure of Reference Example 9-2 was carried out. (9-5-2) Pellet-shaped ethylene/1-hexene copolymer (PE-16-2) was obtained in accordance with film production, and the sample was extrusion laminated to produce a film. The resin physical properties of the obtained ethylene/1-hexene copolymer (PE-16-2) and the results of extrusion lamination are shown in Table 9-2.

[Example 48] (Ethylene/1-hexene copolymer: PE-16-3)
In (9-4-2) polymerization of Reference Example 9-2, an ethylene mixture containing 35% by weight of biomass-derived ethylene and 65% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1 - Reference Example 9-2, except that a 1-hexene mixture containing 35% by weight of biomass-derived 1-hexene and 65% by weight of fossil fuel-derived 1-hexene was used instead of fossil fuel-derived 1-hexene as hexene. Ethylene/1-hexene copolymer (PE-16-3) was obtained in the same manner as in (9-1-2) to (9-4-2).
Using the obtained ethylene/1-hexene copolymer (PE-16-3) in place of the fossil fuel-derived ethylene/1-hexene copolymer (PE-16-0), the procedure of Reference Example 9-2 was carried out. (9-5-2) According to the production of film, a pellet-shaped ethylene/1-hexene copolymer (PE-16-3) was obtained, and the sample was subjected to extrusion lamination to produce a film. The resin physical properties of the obtained ethylene/1-hexene copolymer (PE-16-3) and the results of extrusion lamination are shown in Table 9-2.

[Reference Example 10-1] (Fossil fuel-derived ethylene/1-hexene copolymer: PE-17-0)
(10-1-1) Preparation of solid component 90.5 liters of 10 kg of silica (SiO ₂ : average particle size 12 μm) dried at 250°C for 10 hours in a nitrogen atmosphere was placed in a reactor with an internal volume of 260 liters equipped with a stirrer. The suspension was suspended in toluene and cooled to 0 to 5°C. To this suspension, 45.5 liters of a toluene solution of methylalumoxane (3.0 mmol/ml in terms of Al atoms) was added dropwise over 30 minutes. At this time, the temperature in the system was maintained at 0 to 5°C. Subsequently, the reaction was carried out at 0 to 5°C for 30 minutes, and then the temperature was raised to 95 to 100°C over about 1.5 hours, and then the reaction was continued at 95 to 100°C for 4 hours. Thereafter, the temperature was lowered to room temperature, and the supernatant liquid was removed by decantation. After washing the solid component thus obtained twice with toluene, toluene was added to make a total volume of 129 liters to prepare a toluene slurry of the solid component. When a part of the obtained solid component was collected and its concentration was examined, it was found that the slurry concentration was 137.5 g/l and the Al concentration was 1.1 mol/l.

(10-2-1) Preparation of solid catalyst component A toluene slurry of 21.0 liters of toluene and the solid component prepared in (10-1-1) above was placed in a reactor with an internal volume of 114 liters and equipped with a stirrer under a nitrogen atmosphere. 15.8 liters (2400 g solids) were added. Meanwhile, 31.0 liters of toluene was charged in a reactor with an internal volume of 100 liters and equipped with a stirrer under a nitrogen atmosphere, and under stirring, a toluene solution (in terms of Zr atoms) of a metallocene compound (A4) represented by the following chemical formula (A4) was added. 8.25 mmol/l), followed by 2.0 liters of a toluene solution (2.17 mmol/l in terms of Zr atoms) of a metallocene compound (B4) represented by the following chemical formula (B4). The mixture was mixed for several minutes (metallocene compound (A4)/metallocene compound (B4) molar ratio = 95/5). Subsequently, the prepared mixed solution was pumped into the above-mentioned reactor filled with the toluene slurry of the solid component previously prepared in (10-1-1) above. After pressure-feeding, the mixture was reacted for 1 hour at an internal temperature of 20 to 25°C, the supernatant liquid was removed by decantation, and the solid catalyst component was washed three times with hexane. Thereafter, hexane was added to make the total volume 56 liters to prepare a hexane slurry of the solid catalyst component.

(10-3-1) Preparation of prepolymerized catalyst After cooling the hexane slurry of the solid catalyst component obtained in (10-2-1) above to 10°C, ethylene was continuously introduced into the system several times under normal pressure. Supplied for minutes. During this time, the temperature in the system was maintained at 10 to 15°C. Thereafter, 2.8 mol of triisobutylaluminum and 157 ml of 1-hexene were added. After the addition of 1-hexene, ethylene was again supplied at 1.8 kg/hr to start prepolymerization. 40 minutes after the start of prepolymerization, the temperature inside the system rose to 24°C, and thereafter the temperature inside the system was maintained at 24 to 26°C. 79.0 ml of 1-hexene was added 70 minutes after the start of prepolymerization, and 79.0 ml of 1-hexene was added 140 minutes later. 220 minutes after the start of prepolymerization, the supply of ethylene was stopped and the inside of the system was replaced with nitrogen to stop the prepolymerization. Thereafter, the supernatant liquid was removed by decantation. The prepolymerized catalyst thus obtained was washed six times with hexane to obtain a prepolymerized catalyst in which 2.87 g of polymer was polymerized per 1 g of the solid catalyst component. A part of the obtained prepolymerized catalyst component was dried and the composition was examined, and it was found that 0.72 mg of Zr atoms were contained per 1 g of the solid catalyst component.

(10-4-1) Polymerization In a completely stirred mixing type polymerization tank with an internal volume of 290 liters, the solvent hexane was added at 45 liters/hr, and the prepolymerized catalyst obtained in (10-3-1) above was converted into Zr atoms. 0.44 mmol/hr, triisobutylaluminum at 20.0 mmol/hr, ethylene at 6.6 kg/hr, and 1-hexene at a rate of 500 g/hr. Note that fossil fuel-derived ethylene was used as ethylene, and fossil fuel-derived 1-hexene was used as 1-hexene. The polymer slurry was continuously extracted from the polymerization tank so that the amount of solvent in the polymerization tank was constant, and polymerization was carried out under the conditions of a total pressure of 0.8 MPa-G, a polymerization temperature of 80° C., and a residence time of 2.6 hr. Unreacted ethylene is substantially removed from the polymer slurry continuously withdrawn from the polymerization tank in a flash drum. Thereafter, hexane in the polymer slurry was removed using a solvent separator and dried to obtain an ethylene/1-hexene copolymer (PE-17-0). The resin physical properties of the obtained ethylene/1-hexene copolymer (PE-17-0) are shown in Table 10-1.

(10-5-1) Production of film Irganox 1076 (Ciba Specialty) was added to the ethylene/1-hexene copolymer (PE-17-0) obtained in (10-4-1) above as a heat-resistant stabilizer. Chemicals Co., Ltd.) and Irgafos 168 (Ciba Specialty Chemicals Co., Ltd.) at a concentration of 0.1% by weight, and using a single-screw 65mmφ extruder manufactured by Plako Co., Ltd., the temperature was set at 180°C. , screw rotation speed 50 r. p. m. After melt-kneading under the following conditions, the mixture was extruded into strands, and pelletized ethylene/1-hexene copolymer (PE-17-0) was obtained using a cutter. The resin physical properties of the obtained ethylene/1-hexene copolymer (PE-17-0) are shown in Table 10-1. In addition, Table 10-1 shows the results of extrusion lamination molding using this sample.

[Example 49] (Ethylene/1-hexene copolymer: PE-17-1)
In (10-4-1) polymerization of Reference Example 10-1, an ethylene mixture containing 10% by weight of biomass-derived ethylene and 90% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1 - Reference Example 10-1, except that a 1-hexene mixture containing 10% by weight of biomass-derived 1-hexene and 90% by weight of fossil fuel-derived 1-hexene was used instead of fossil fuel-derived 1-hexene as hexene. An ethylene/1-hexene copolymer (PE-17-1) was obtained in the same manner as in (10-1-1) to (10-4-1).
Using the obtained ethylene/1-hexene copolymer (PE-17-1) in place of the fossil fuel-derived ethylene/1-hexene copolymer (PE-17-0), the procedure of Reference Example 10-1 was carried out. (10-5-1) A pellet-shaped ethylene/1-hexene copolymer (PE-17-1) was obtained in accordance with the procedure for producing a film, and the sample was subjected to extrusion lamination to produce a film. The resin physical properties of the obtained ethylene/1-hexene copolymer (PE-17-1) and the results of extrusion lamination are shown in Table 10-1.

[Example 50] (Ethylene/1-hexene copolymer: PE-17-2)
In (10-4-1) polymerization of Reference Example 10-1, an ethylene mixture containing 30% by weight of biomass-derived ethylene and 70% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1 - Reference Example 10-1, except that a 1-hexene mixture containing 30% by weight of biomass-derived 1-hexene and 70% by weight of fossil fuel-derived 1-hexene was used instead of fossil fuel-derived 1-hexene as hexene. Ethylene/1-hexene copolymer (PE-17-2) was obtained in the same manner as in (10-1-1) to (10-4-1).
Using the obtained ethylene/1-hexene copolymer (PE-17-2) in place of the fossil fuel-derived ethylene/1-hexene copolymer (PE-17-0), the procedure of Reference Example 10-1 was carried out. (10-5-1) Pellet-shaped ethylene/1-hexene copolymer (PE-17-2) was obtained in accordance with film production, and the sample was extrusion laminated to produce a film. The resin physical properties of the obtained ethylene/1-hexene copolymer (PE-17-2) and the results of extrusion lamination are shown in Table 10-1.

[Example 51] (Ethylene/1-hexene copolymer: PE-17-3)
In (10-4-1) polymerization of Reference Example 10-1, an ethylene mixture containing 35% by weight of biomass-derived ethylene and 65% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1 - Reference Example 10-1, except that a 1-hexene mixture containing 35% by weight of biomass-derived 1-hexene and 65% by weight of fossil fuel-derived 1-hexene was used instead of fossil fuel-derived 1-hexene as hexene. Ethylene/1-hexene copolymer (PE-17-3) was obtained in the same manner as in (10-1-1) to (10-4-1).
Using the obtained ethylene/1-hexene copolymer (PE-17-3) in place of the fossil fuel-derived ethylene/1-hexene copolymer (PE-17-0), the procedure of Reference Example 10-1 was carried out. (10-5-1) Pellet-shaped ethylene/1-hexene copolymer (PE-17-3) was obtained in accordance with film production, and the sample was extrusion laminated to produce a film. The resin physical properties of the obtained ethylene/1-hexene copolymer (PE-17-3) and the results of extrusion lamination are shown in Table 10-1.

[Reference Example 10-2] (Fossil fuel-derived ethylene/1-hexene copolymer: PE-18-0)
(10-1-2) Preparation of solid component It was prepared in the same manner as in the preparation of (10-1-1) solid component in Reference Example 10-1.

(10-2-2) Preparation of solid catalyst component A toluene slurry of 18.6 liters of toluene and the solid component prepared in (11-1-2) above was placed in a reactor with an internal volume of 114 liters and equipped with a stirrer under a nitrogen atmosphere. 7.9 liters (1200 g solids) were added. Meanwhile, 14.5 liters of toluene was charged into a reactor with an internal volume of 100 liters and equipped with a stirrer under a nitrogen atmosphere, and under stirring, a toluene solution of the metallocene compound (A4) described above (7.81 mmol/l in terms of Zr atoms) was added. Then, 2.0 liters of the toluene solution (2.17 mmol/l in terms of Zr atoms) of the metallocene compound (B4) mentioned above was added and mixed for several minutes (metallocene compound (A4)/metallocene compound (B4) molar ratio = 85/15). Subsequently, the prepared mixed solution was pumped into the above-mentioned reactor filled with the toluene slurry of the solid component previously prepared in (11-1-2) above. After pressure-feeding, the mixture was reacted for 1 hour at an internal temperature of 20 to 25°C. Thereafter, the supernatant liquid was removed by decantation. After washing the solid catalyst component thus obtained three times with hexane, hexane was added to make a total volume of 30 liters to prepare a hexane slurry of the solid catalyst component.

(10-3-2) Preparation of prepolymerized catalyst After cooling the hexane slurry of the solid catalyst component obtained in (10-2-2) above to 10°C, ethylene was continuously introduced into the system several times under normal pressure. Supplied for minutes. During this time, the temperature in the system was maintained at 10 to 15°C. Thereafter, 1.6 mol of triethylaluminum and 80 ml of 1-hexene were added. After the addition of 1-hexene, ethylene was supplied again at 1.8 kg/hr to start prepolymerization. Twenty-five minutes after the start of prepolymerization, the temperature inside the system rose to 24°C, and thereafter the temperature inside the system was maintained at 24 to 26°C. 39.0 ml of 1-hexene was added 35 minutes after the start of prepolymerization, and 39.0 ml of 1-hexene was added 60 minutes later.
Eighty-five minutes after the start of prepolymerization, the supply of ethylene was stopped, and the atmosphere in the system was replaced with nitrogen to stop the prepolymerization. Thereafter, the supernatant liquid was removed by decantation. The prepolymerized catalyst thus obtained was washed four times with hexane to obtain a prepolymerized catalyst in which 2.93 g of polymer was polymerized per 1 g of the solid catalyst component. A part of the obtained prepolymerized catalyst component was dried and the composition was examined, and it was found that 0.72 mg of Zr atoms were contained per 1 g of the solid catalyst component.

(10-4-2) Polymerization In a fully stirred mixing type polymerization tank with an internal volume of 290 liters, the solvent hexane was added at 45 liters/hr, and the prepolymerized catalyst obtained in (10-3-2) above was converted into Zr atoms. 0.1 mmol/hr, triisobutylaluminum at 20.0 mmol/hr, ethylene at 5 kg/hr, and 1-hexene at 1900 g/hr. Note that fossil fuel-derived ethylene was used as ethylene, and fossil fuel-derived 1-hexene was used as 1-hexene. The polymer slurry was continuously extracted from the polymerization tank so that the amount of solvent in the polymerization tank was constant, and polymerization was carried out under the conditions of a total pressure of 1 MPa-G, a polymerization temperature of 65° C., and a residence time of 2.7 hr. Unreacted ethylene is substantially removed from the polymer slurry continuously withdrawn from the polymerization tank in a flash drum. Thereafter, hexane in the polymer slurry was removed using a solvent separator and dried to obtain an ethylene/1-hexene copolymer (PE-18-0).

(10-5-2) Production of film Pellet-shaped ethylene/1-hexene copolymer (PE-18-0) was obtained in the same manner as in the production of film (10-5-1) in Reference Example 10-1. A film was manufactured by extrusion lamination using the sample. The resin physical properties of the obtained ethylene/1-hexene copolymer (PE-18-0) and the results of extrusion lamination are shown in Table 10-2.

[Example 52] (Ethylene/1-hexene copolymer: PE-18-1)
In (10-4-2) polymerization of Reference Example 10-2, an ethylene mixture containing 10% by weight of biomass-derived ethylene and 90% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1 - Reference Example 10-2, except that a 1-hexene mixture containing 10% by weight of biomass-derived 1-hexene and 90% by weight of fossil fuel-derived 1-hexene was used instead of fossil fuel-derived 1-hexene as hexene. An ethylene/1-hexene copolymer (PE-18-1) was obtained in the same manner as in (10-1-2) to (10-4-2).
Using the obtained ethylene/1-hexene copolymer (PE-18-1) in place of the fossil fuel-derived ethylene/1-hexene copolymer (PE-18-0), the procedure of Reference Example 10-2 was carried out. (10-5-2) Pellet-shaped ethylene/1-hexene copolymer (PE-18-1) was obtained in accordance with the procedure for producing a film, and the sample was subjected to extrusion lamination to produce a film. The resin physical properties of the obtained ethylene/1-hexene copolymer (PE-18-1) and the results of extrusion lamination are shown in Table 10-2.

[Example 53] (Ethylene/1-hexene copolymer: PE-18-2)
In (10-4-2) polymerization of Reference Example 10-2, an ethylene mixture containing 30% by weight of biomass-derived ethylene and 70% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1 - Reference Example 10-2, except that a 1-hexene mixture containing 30% by weight of biomass-derived 1-hexene and 70% by weight of fossil fuel-derived 1-hexene was used instead of fossil fuel-derived 1-hexene as hexene. Ethylene/1-hexene copolymer (PE-18-2) was obtained in the same manner as in (10-1-2) to (10-4-2).
Using the obtained ethylene/1-hexene copolymer (PE-18-2) in place of the fossil fuel-derived ethylene/1-hexene copolymer (PE-18-0), the procedure of Reference Example 10-2 was carried out. (10-5-2) Pellet-shaped ethylene/1-hexene copolymer (PE-18-2) was obtained in accordance with film production, and the sample was extrusion laminated to produce a film. The resin physical properties of the obtained ethylene/1-hexene copolymer (PE-18-2) and the results of extrusion lamination are shown in Table 10-2.

[Example 54] (Ethylene/1-hexene copolymer: PE-18-3)
In (10-4-2) polymerization of Reference Example 10-2, an ethylene mixture containing 35% by weight of biomass-derived ethylene and 65% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1 - Reference Example 10-2, except that a 1-hexene mixture containing 35% by weight of biomass-derived 1-hexene and 65% by weight of fossil fuel-derived 1-hexene was used instead of fossil fuel-derived 1-hexene as hexene. Ethylene/1-hexene copolymer (PE-18-3) was obtained in the same manner as in (10-1-2) to (10-4-2).
Using the obtained ethylene/1-hexene copolymer (PE-18-3) in place of the fossil fuel-derived ethylene/1-hexene copolymer (PE-18-0), the procedure of Reference Example 10-2 was carried out. (10-5-2) Pellet-shaped ethylene/1-hexene copolymer (PE-18-3) was obtained in accordance with film production, and the sample was extrusion laminated to produce a film. The resin physical properties of the obtained ethylene/1-hexene copolymer (PE-18-3) and the results of extrusion lamination are shown in Table 10-2.

[Reference Example 11-1] (Fossil fuel-derived ethylene polymer: PE-19-0)
(11-1-1) Preparation of solid catalyst component 31.0 liters of toluene was charged into a reactor at room temperature (20 to 25°C) that was sufficiently purged with nitrogen, and the solid MAO component was .15 mol (9.34 liters) was added, and the suspension was stirred for 10 minutes. 21.0 mmol of metallocene compound (A5) represented by the following chemical formula (A5) was dissolved in 2.40 liters of toluene solution, added to the reactor, and stirred for 10 minutes. Subsequently, 21.0 mmol of a metallocene compound (A6) represented by the following chemical formula (A6) was added and stirred for 60 minutes to obtain a solid catalyst component. Note that in chemical formula (A6), tBu means tertiary-butyl.

(11-2-1) Polymerization In the first polymerization tank, 53.0 l/hr of hexane was added, 0.034 mmol/hr of the solid catalyst component obtained in the above (11-1-1) in terms of zirconium atoms, 11.7 mmol/hr of triisobutylaluminum, 7.50 kg/hr of ethylene, 39.4 Nl/hr of hydrogen molecules, Adecapronic L-71 (trade name, manufactured by ADEKA Co., Ltd., hereinafter referred to as L-71) While continuously supplying 0.600 g/hr of 0.600 g/hr and continuously withdrawing the contents of the polymerization tank so that the liquid level in the polymerization tank remained constant, the polymerization temperature was 75.0°C, the reaction pressure was 0.400 MPaG, and the average Polymerization was carried out under conditions of a residence time of 2.60 hr to obtain an ethylene polymer (X3-1). Note that fossil fuel-derived ethylene was used as ethylene. Unreacted ethylene and hydrogen molecules were substantially removed from the contents continuously extracted from the first polymerization tank in a flash drum maintained at an internal pressure of 0.030 MPaG and a temperature of 40.0°C.
Thereafter, the contents were continuously transferred to the second polymerization tank along with 130 l/hr of hexane, 9.40 kg/hr of ethylene, 15.7 Nl/hr of hydrogen molecules, 0.740 g/hr of L-71, and 700 g/hr of 1-hexene. Subsequently, polymerization was carried out under the conditions of a polymerization temperature of 75.0° C., a reaction pressure of 0.570 MPaG, and an average residence time of 1.05 hr, to obtain a polymer (Y3-1). Note that fossil fuel-derived ethylene was used as ethylene, and fossil fuel-derived 1-hexene was used as 1-hexene. In the second polymerization tank as well, the contents of the polymerization tank were continuously extracted so that the liquid level in the polymerization tank remained constant. In order to prevent unintended polymerization such as the formation of a polymer containing a large amount of 1-hexene, methanol was supplied at 2.50 l/hr to the contents extracted from the second polymerization tank to deactivate the polymerization catalyst. . Thereafter, hexane and unreacted monomers in the contents were removed using a solution separation device, and the contents were dried.
An ethylene polymer (PE-19-0) was obtained by mixing 45% by mass of the polymer (X3-1) and 55% by mass of the polymer (Y3-1).
6-[3-(3-t-butyl-4-hydroxy-5-methyl)propoxy]-2, as an antioxidant to 100 parts by mass of the obtained ethylene polymer (PE-19-0). 0.12 parts by mass of 4,8,10-tetra-t-butylbenz[d,f][1,3,2]-dioxaphosphepine and 0.03 parts by mass of calcium stearate were blended. Thereafter, using a single-screw extruder (screw diameter 65 mmφ, L/D = 28) manufactured by TOMY Co., Ltd., the pellets were granulated at a set temperature of 200°C and a resin extrusion rate of 50 kg/hr. 19-0). The resin physical properties of the obtained ethylene polymer (PE-19-0) are shown in Table 11-1.

(11-3-1) Production of film A film was produced using the ethylene polymer (PE-19-0) obtained in (11-2-1) above, and the obtained physical properties are shown in Table 11-1. Shown below.

[Example 55] (Ethylene polymer: PE-19-1)
In (11-2-1) polymerization of Reference Example 11-1, an ethylene mixture containing 10% by weight of biomass-derived ethylene and 90% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1 - Reference Example 11-1, except that a 1-hexene mixture containing 10% by weight of biomass-derived 1-hexene and 90% by weight of fossil fuel-derived 1-hexene was used instead of fossil fuel-derived 1-hexene as hexene. An ethylene polymer (PE-19-1) was obtained in the same manner as in (11-1-1) to (11-2-1). The resin physical properties of the obtained ethylene polymer (PE-19-1) are shown in Table 11-1.
Using the obtained ethylene polymer (PE-19-1) in place of the fossil fuel-derived ethylene polymer (PE-19-0), the (11-3-1) film of Reference Example 11-1 was produced. A film was prepared according to the method of manufacture. The physical properties of the obtained film are shown in Table 11-1.

[Example 56] (Ethylene polymer: PE-19-2)
In (11-2-1) polymerization of Reference Example 11-1, an ethylene mixture containing 30% by weight of biomass-derived ethylene and 70% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1 - Reference Example 11-1, except that a 1-hexene mixture containing 30% by weight of biomass-derived 1-hexene and 70% by weight of fossil fuel-derived 1-hexene was used instead of fossil fuel-derived 1-hexene as hexene. An ethylene polymer (PE-19-2) was obtained in the same manner as in (11-1-1) to (11-2-1). The resin physical properties of the obtained ethylene polymer (PE-19-2) are shown in Table 11-1.
Using the obtained ethylene polymer (PE-19-2) in place of the fossil fuel-derived ethylene polymer (PE-19-0), the (11-3-1) film of Reference Example 11-1 A film was prepared according to the manufacturing method of . The physical properties of the obtained film are shown in Table 11-1.

[Example 57] (Ethylene polymer: PE-19-3)
In (11-2-1) polymerization of Reference Example 11-1, an ethylene mixture containing 35% by weight of biomass-derived ethylene and 65% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1 - Reference Example 11-1 except that a 1-hexene mixture containing 35% by weight of biomass-derived 1-hexene and 65% by weight of fossil fuel-derived 1-hexene was used instead of fossil fuel-derived 1-hexene as hexene. An ethylene polymer (PE-19-3) was obtained in the same manner as in (11-1-1) to (11-2-1). The resin physical properties of the obtained ethylene polymer (PE-19-3) are shown in Table 11-1.
Using the obtained ethylene polymer (PE-19-3) in place of the fossil fuel-derived ethylene polymer (PE-19-0), the (11-3-1) film of Reference Example 11-1 A film was prepared according to the manufacturing method of . The physical properties of the obtained film are shown in Table 11-1.

[Reference Example 11-2] (Fossil fuel-derived ethylene polymer: PE-20-0)
(11-1-2) Preparation of solid catalyst component It was prepared in the same manner as in the preparation of (11-1-1) solid catalyst component in Reference Example 11-1.

(11-2-2) Polymerization In the first polymerization tank, hexane was added at 38.5 l/hr, the solid catalyst component obtained in (11-1-2) was added at 0.035 mmol/hr in terms of zirconium atoms, Triisobutylaluminum was continuously supplied at 8.5 mmol/hr, ethylene at 7.30 kg/hr, hydrogen molecules at 27.9 Nl/hr, and L-71 at 0.600 g/hr, and the liquid level in the polymerization tank was kept constant. Polymerization was carried out under the conditions of polymerization temperature of 74.9°C, reaction pressure of 0.390 MPaG, and average residence time of 3.48 hr while the contents of the polymerization tank were continuously withdrawn to maintain a constant content, and ethylene polymer (X3-2) was obtained. I got it. Note that fossil fuel-derived ethylene was used as ethylene. Unreacted ethylene and hydrogen molecules were substantially removed from the contents continuously extracted from the first polymerization tank in a flash drum maintained at an internal pressure of 0.030 MPaG and a temperature of 40.0°C.
Thereafter, the contents were continuously transferred to the second polymerization tank along with 93.5 l/hr of hexane, 8.70 kg/hr of ethylene, 14.6 Nl/hr of hydrogen molecules, 0.740 g/hr of L-71, and 580 g/hr of 1-hexene. Subsequently, polymerization was carried out under the conditions of a polymerization temperature of 74.7° C., a reaction pressure of 0.550 MPaG, and an average residence time of 1.40 hr to obtain a polymer (Y3-2). Note that fossil fuel-derived ethylene was used as ethylene, and fossil fuel-derived 1-hexene was used as 1-hexene. Also in the second polymerization tank, the contents of the polymerization tank were continuously extracted so that the liquid level in the polymerization tank remained constant. In order to prevent unintended polymerization such as the formation of a polymer containing a large amount of 1-hexene, methanol was supplied at 2.50 l/hr to the contents extracted from the second polymerization tank to deactivate the polymerization catalyst. . Thereafter, hexane and unreacted monomers in the contents were removed using a solution separator, and the contents were dried.
An ethylene polymer (PE-20-0) was obtained by mixing 45% by mass of the polymer (X3-2) and 55% by mass of the polymer (Y3-2).
6-[3-(3-t-butyl-4-hydroxy-5-methyl)propoxy]-2, as an antioxidant to 100 parts by mass of the obtained ethylene polymer (PE-20-0). 0.12 parts by mass of 4,8,10-tetra-t-butylbenz[d,f][1,3,2]-dioxaphosphepine and 0.03 parts by mass of calcium stearate were blended. Thereafter, using a single-screw extruder (screw diameter 65 mmφ, L/D = 28) manufactured by TOMY Co., Ltd., the pellets were granulated at a set temperature of 200°C and a resin extrusion rate of 50 kg/hr. 20-0). The resin physical properties of the obtained ethylene polymer (PE-20-0) are shown in Table 11-2.

(11-3-2) Production of film A film was produced using the ethylene polymer mixture (PE-20-0) obtained in (11-2-2) above, and the obtained physical properties are shown in Table 11- Shown in 2.

[Example 58] (Ethylene polymer: PE-20-1)
In (11-2-2) polymerization of Reference Example 11-2, an ethylene mixture containing 10% by weight of biomass-derived ethylene and 90% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1 - Reference Example 11-2, except that as hexene, a 1-hexene mixture containing 10% by weight of biomass-derived 1-hexene and 90% by weight of fossil fuel-derived 1-hexene was used instead of 1-hexene derived from fossil fuel. An ethylene polymer (PE-20-1) was obtained in the same manner as in (11-1-2) to (11-2-2). The resin physical properties of the obtained ethylene polymer (PE-20-1) are shown in Table 11-2.
Using the obtained ethylene polymer (PE-20-1) in place of the fossil fuel-derived ethylene polymer (PE-20-0), the (11-3-2) film of Reference Example 11-2 was produced. A film was prepared according to the manufacturing method of . The physical properties of the obtained film are shown in Table 11-2.

[Example 59] (Ethylene polymer: PE-20-2)
In (11-2-2) polymerization of Reference Example 11-2, an ethylene mixture containing 30% by weight of biomass-derived ethylene and 70% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1 - Reference Example 11-2, except that a 1-hexene mixture containing 30% by weight of biomass-derived 1-hexene and 70% by weight of fossil fuel-derived 1-hexene was used instead of fossil fuel-derived 1-hexene as hexene. An ethylene polymer (PE-20-2) was obtained in the same manner as in (11-1-2) to (11-2-2). The resin physical properties of the obtained ethylene polymer (PE-20-2) are shown in Table 11-2.
Using the obtained ethylene polymer (PE-20-2) in place of the fossil fuel-derived ethylene polymer (PE-20-0), the (11-3-2) film of Reference Example 11-2 was produced. A film was prepared according to the manufacturing method of . The physical properties of the obtained film are shown in Table 11-2.

[Example 60] (Ethylene polymer: PE-20-3)
In (11-2-2) polymerization of Reference Example 11-2, an ethylene mixture containing 35% by weight of biomass-derived ethylene and 65% by weight of fossil fuel-derived ethylene was used as ethylene instead of fossil fuel-derived ethylene, and 1 - Reference Example 11-2, except that a 1-hexene mixture containing 35% by weight of biomass-derived 1-hexene and 65% by weight of fossil fuel-derived 1-hexene was used instead of fossil fuel-derived 1-hexene as hexene. An ethylene polymer (PE-20-3) was obtained in the same manner as in (11-1-2) to (11-2-2). The resin physical properties of the obtained ethylene polymer (PE-20-3) are shown in Table 11-2.
Using the obtained ethylene polymer (PE-20-3) in place of the fossil fuel-derived ethylene polymer (PE-20-0), the (11-3-2) film of Reference Example 11-2 was produced. A film was prepared according to the method of manufacture. The physical properties of the obtained film are shown in Table 11-2.

[Reference Example 12] (Fossil fuel-derived ethylene/1-octene copolymer: PE-21-0)
(12-1) Polymerization Dehydrated and purified n-hexane was added to one feed port of a continuous polymerization vessel with a volume of 136 liters at a rate of 10.2 liters/hr. A hexane solution of di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride (0.1 mmol/l) at a rate of 0.2 l/hr (5 mmol/l as aluminum atoms) l) at a rate of 0.02 l/hr, and a hexane solution of triisobutylaluminum (2 mmol/l) at a rate of 2.1 l/hr (total hexane 12.5 l/hr). At the same time, ethylene was supplied at a rate of 4 kg/hr and hydrogen at a rate of 10 l/hr to another supply port of the continuous polymerization reactor, and 1-octene was continuously supplied to another supply port at a rate of 2 kg/hr. , polymerization temperature 150°C, total pressure 3Mpa-G, residence time approximately 75 minutes, stirring rotation speed 250r. p. m. Continuous solution polymerization was carried out under the following conditions. Note that fossil fuel-derived ethylene was used as ethylene, and fossil fuel-derived 1-octene was used as 1-octene.
The hexane solution of ethylene/1-octene copolymer (PE-21-0) produced in the polymerization vessel is continuously fed at a flow rate of approximately 22.4 l/hr through an outlet provided on the side wall of the polymerization vessel. The jacket was led to a connecting pipe heated with 8 kg/cm ² steam. A hexane solution of ethylene/1-octene copolymer (PE-21-0) heated to 170°C in a connecting pipe with a steam jacket is heated to 170°C in a connecting pipe so as to maintain a solution volume of about 28 liters in the polymerization tank. By adjusting the opening degree of a liquid level control valve provided at the terminal end, the liquid was continuously sent to the flash tank through a double pipe inner pipe heated with 10 kg/cm ² steam. Immediately after the liquid level control valve, there is a supply port through which methanol, which is a catalyst deactivator, is injected, and the methanol is injected as a 1.0 vol% hexane diluted solution at a rate of 12 l/hr to join the hexane solution. I let it happen. During transfer to the flash tank, the solution temperature and pressure adjustment valve opening are set so that the pressure in the flash tank is maintained at 0.04 MPa-G and the temperature of the steam section in the flash tank is maintained at approximately 180°C. Ta. Table 12 shows the resin physical properties of the obtained ethylene/1-octene copolymer (PE-21-0).

(12-2) Production of film Using the ethylene/1-octene copolymer (PE-21-0) obtained in (12-1) above, a single layer with a thickness of 40 μm and a width of 320 mm was formed under the following molding conditions. produced a film.
<Molding conditions>
A 50mmφ inflation molding machine manufactured by Modern Machinery was used, a barrier type screw was used, the die was 100mmφ (diameter) and 2.0mm (lip width), the air ring was a 2-gap type, and the extrusion rate was 28.8kg/hr. Molding was carried out at a take-up speed of 20 m/min.
Total haze, internal haze, dart impact strength, and Elmendorf tear strength (MD and TD) were measured using the molded films. Table 12 shows the physical properties of the obtained film.

[Example 61] (Ethylene/1-octene copolymer: PE-21-1)
In (12-1) polymerization of Reference Example 12, as ethylene, an ethylene mixture containing 10% by weight of biomass-derived ethylene and 90% by weight of fossil fuel-derived ethylene was used instead of fossil fuel-derived ethylene, and as 1-octene, (12-1) of Reference Example 12, except that instead of fossil fuel-derived 1-octene, a 1-octene mixture containing 10% by weight of biomass-derived 1-octene and 90% by weight of fossil fuel-derived 1-octene was used. In the same manner as above, an ethylene/1-octene copolymer (PE-21-1) was obtained. Table 12 shows the resin physical properties of the obtained ethylene/1-octene copolymer (PE-21-1).
(12 -2) A film was produced according to the film manufacturing procedure. Table 12 shows the physical properties of the obtained film.

[Example 62] (Ethylene/1-octene copolymer: PE-21-2)
In (12-1) polymerization of Reference Example 12, as ethylene, an ethylene mixture containing 30% by weight of biomass-derived ethylene and 70% by weight of fossil fuel-derived ethylene was used instead of fossil fuel-derived ethylene, and as 1-octene, (12-1) of Reference Example 12 except that a 1-octene mixture containing 30% by weight of biomass-derived 1-octene and 70% by weight of fossil fuel-derived 1-octene was used instead of fossil fuel-derived 1-octene. In the same manner as above, an ethylene/1-octene copolymer (PE-21-2) was obtained. Table 12 shows the resin physical properties of the obtained ethylene/1-octene copolymer (PE-21-2).
(12 -2) A film was produced according to the film manufacturing procedure. Table 12 shows the physical properties of the obtained film.

[Example 63] (Ethylene/1-octene copolymer: PE-21-3)
In (12-1) polymerization of Reference Example 12, as ethylene, an ethylene mixture containing 35% by weight of biomass-derived ethylene and 65% by weight of fossil fuel-derived ethylene was used instead of ethylene derived from fossil fuel, and as 1-octene, (12-1) of Reference Example 12 except that a 1-octene mixture containing 35% by weight of biomass-derived 1-octene and 65% by weight of fossil fuel-derived 1-octene was used instead of fossil fuel-derived 1-octene. In the same manner as above, an ethylene/1-octene copolymer (PE-21-3) was obtained. Table 12 shows the resin physical properties of the obtained ethylene/1-octene copolymer (PE-21-3).
(12 -2) A film was produced according to the film manufacturing procedure. Table 12 shows the physical properties of the obtained film.

[Reference Example 13] (Fossil fuel-derived ethylene/1-octene copolymer: PE-22-0)
(13-1) Polymerization A hexane slurry of TMAO-341 (manufactured by Tosoh Finechem) ( A hexane solution of di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride (0.1 mmol/l) was added at a rate of 0.2 l/hr (5 mmol/l as aluminum atoms). l) at a rate of 0.02 l/hr, and a hexane solution of triisobutylaluminum (2 mmol/l) at a rate of 2.1 l/hr (total hexane 10.4 l/hr). At the same time, ethylene was supplied at a rate of 4.5 kg/hr and hydrogen at a rate of 30 l/hr to another supply port of the continuous polymerization reactor, and 1-octene was supplied to another supply port at a rate of 2.5 kg/hr. The polymerization temperature was 130°C, the total pressure was 3MPa-G, the residence time was 70 minutes, and the stirring speed was 250r. p. m. Continuous solution polymerization was carried out under the following conditions. Note that fossil fuel-derived ethylene was used as ethylene, and fossil fuel-derived 1-octene was used as 1-octene.
The hexane solution of ethylene/1-octene copolymer (PE-22-0) produced in the polymerization vessel was continuously discharged at a flow rate of 24 l/hr through a discharge port provided on the side wall of the polymerization vessel. The jacket part was led to a connecting pipe heated with 8 kg/cm ² steam. A hexane solution of ethylene/1-octene copolymer heated to 170°C in a steam-jacketed connecting pipe is placed in a liquid at the end of the connecting pipe to maintain a solution volume of approximately 28 liters in the polymerization tank. By adjusting the opening degree of the level control valve, the liquid was continuously sent to the flash tank through the double pipe inner pipe heated with 10 kg/cm ² steam. Immediately after the liquid level control valve, there is a supply port through which methanol, which is a catalyst deactivator, is injected, and the methanol is injected as a 1.0 vol% hexane diluted solution at a rate of 12 l/hr to join the hexane solution. I let it happen. During transfer to the flash tank, the solution temperature and pressure adjustment valve opening were set so that the pressure in the flash tank was maintained at 0.04 MPa-G and the temperature of the steam section in the flash tank was maintained at 180°C. . Table 13 shows the resin physical properties of the obtained ethylene/1-octene copolymer (PE-22-0).

(13-2) Production of film The ethylene/1-octene copolymer (PE-22-0) obtained in (13-1) above and high-pressure low-density polyethylene were processed using a 65 mmφ single-screw extruder (manufactured by Plako Co., Ltd.). ) at a set temperature of 180°C and a screw rotation speed of 50r. p. m. The resin composition was melt-kneaded to obtain a resin composition of 80% by weight to 20% by weight, and then extruded into a strand shape and made into pellets using a cutter.
The obtained pellets were placed on the substrate using a 65 mmφ extruder and a Sumitomo Heavy Industries laminator having a T-die with a die width of 500 mm, with an air gap of 130 mm, a resin temperature under the die of 295°C, and a take-up speed of 80 m/min. A film was formed by extrusion lamination under these conditions to a thickness of 25 μm. Using the formed film, heat seal strength and peel distance by hot tack test were measured. The results obtained are shown in Table 13.

[Example 64] (Ethylene/1-octene copolymer: PE-22-1)
In (13-1) polymerization of Reference Example 13, as ethylene, an ethylene mixture containing 10% by weight of biomass-derived ethylene and 90% by weight of fossil fuel-derived ethylene was used instead of fossil fuel-derived ethylene, and as 1-octene, (13-1) of Reference Example 13, except that instead of fossil fuel-derived 1-octene, a 1-octene mixture containing 10% by weight of biomass-derived 1-octene and 90% by weight of fossil fuel-derived 1-octene was used. In the same manner as above, an ethylene/1-octene copolymer (PE-22-1) was obtained. Table 13 shows the resin physical properties of the obtained ethylene/1-octene copolymer (PE-22-1).
Using the obtained ethylene/1-octene copolymer (PE-22-1) instead of the fossil fuel-derived ethylene/1-octene copolymer (PE-22-0), -2) A film was produced according to the film manufacturing procedure. Table 13 shows the physical properties of the obtained film.

[Example 65] (Ethylene/1-octene copolymer: PE-22-2)
In (13-1) polymerization of Reference Example 13, as ethylene, an ethylene mixture containing 30% by weight of biomass-derived ethylene and 70% by weight of fossil fuel-derived ethylene was used instead of fossil fuel-derived ethylene, and as 1-octene, (13-1) of Reference Example 13 except that a 1-octene mixture containing 30% by weight of biomass-derived 1-octene and 70% by weight of fossil fuel-derived 1-octene was used instead of 1-octene derived from fossil fuel. In the same manner as above, an ethylene/1-octene copolymer (PE-22-2) was obtained. Table 13 shows the resin physical properties of the obtained ethylene/1-octene copolymer (PE-22-2).
Using the obtained ethylene/1-octene copolymer (PE-22-2) in place of the fossil fuel-derived ethylene/1-octene copolymer (PE-22-0), -2) A film was produced according to the film manufacturing procedure. Table 13 shows the physical properties of the obtained film.

[Example 66] (Ethylene/1-octene copolymer: PE-22-3)
In (13-1) polymerization of Reference Example 13, as ethylene, an ethylene mixture containing 35% by weight of biomass-derived ethylene and 65% by weight of fossil fuel-derived ethylene was used instead of fossil fuel-derived ethylene, and as 1-octene, (13-1) of Reference Example 13, except that instead of fossil fuel-derived 1-octene, a 1-octene mixture containing 35% by weight of biomass-derived 1-octene and 65% by weight of fossil fuel-derived 1-octene was used. In the same manner as above, an ethylene/1-octene copolymer (PE-22-3) was obtained. Table 13 shows the resin physical properties of the obtained ethylene/1-octene copolymer (PE-22-3).
Using the obtained ethylene/1-octene copolymer (PE-22-3) in place of the fossil fuel-derived ethylene/1-octene copolymer (PE-22-0), -2) A film was produced according to the film manufacturing procedure. Table 13 shows the physical properties of the obtained film.

From the results in Tables 1 to 13, the ethylene polymer (A) of the present invention, the ethylene polymer mixture (A3), the resin composition containing the ethylene polymer (A), and the ethylene polymer mixture (A3) The resin composition containing the above has performance equivalent to that of the existing fossil fuel-derived ethylene polymer, which has a large environmental impact, and whose raw material is a fossil fuel-derived olefin, and the resin composition containing the ethylene polymer. On the other hand, in the ethylene polymer (A) of the present invention, any desired biomass-derived carbon can be used without diluting the biomass-derived ethylene polymer obtained using only biomass-derived olefin as a raw material with a fossil fuel-derived ethylene polymer. The concentration can be any desired degree of biomass. According to the present invention, it is possible to reduce the environmental load, hold down costs, and promote the spread of ethylene polymers that have the effect of reducing the environmental load.

Claims (32)

An ethylene polymer that is an ethylene homopolymer or a copolymer of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms, and the following (I) to (II) An ethylene polymer that satisfies the following requirements.
(I) At least one olefin (a) selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms contained in the raw material of the ethylene polymer contains 0.2% by weight of the biomass-derived olefin (a1) It is an olefin mixture containing 1% to 99.8% by weight of fossil fuel-derived olefin (a2) and 1% to 99.8% by weight of fossil fuel-derived olefin (a2) (the total of biomass-derived olefin (a1) and fossil fuel-derived olefin (a2) %).
(II) The biomass-derived carbon concentration of the ethylene polymer is 0.2 pMC (%) or more and 99.0 pMC (%) or less. The ethylene polymer according to claim 1, which further satisfies the following (I-1) and (i) to (ii).
(I-1) Ethylene contained in the raw material of the ethylene polymer contains 0.2% to 99% by weight of biomass-derived ethylene and 1% to 99.8% by weight of fossil fuel-derived ethylene It is a mixture (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight).
(i) Density of ethylene polymer is 0.890g/cm ³ to 0.970g/cm ³
(ii) Melt flow rate (MFR) of ethylene polymer at 190°C and 2.16 kg load is 0.01 g/10 minutes to 1500 g/10 minutes The ethylene polymer according to claim 2, having a biomass degree of 1% or more and 99% or less according to ASTM D 6866. An ethylene homopolymer that satisfies the following (iii) to (iv), or a copolymer of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms (X1) 20% by mass or more 80% by mass or less,
(iii) Density d _x1 is 0.890g/cm ³ ~0.970g/cm ³
(iv) Melt flow rate (MFR) at 190°C and 2.16 kg load is 0.01 g/10 minutes to 1,500 g/10 minutes Ethylene homopolymer or ethylene that satisfies the following (v) to (vi) and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms. and the polymer (Y1) is 100% by weight),
(v) Density d _y1 is 0.890g/cm ³ ~0.960g/cm ³
(vi) MFR at 190℃ and 2.16kg load is 0.01g/10 minutes to 500g
/10 minutes Meet (vii) to (viii) below,
(vii) Density is 0.890g/cm ³ ~0.970g/cm ³
(viii) MFR at 190 ° C. and 2.16 kg load is 0.01 g / 10 minutes to 60.0 g / 10 minutes, and satisfies at least one condition selected from the following (iii') and (iv'),
(iii') The density of the polymer (X1) is greater than the density of the polymer (Y1).
(iv') The MFR of the polymer (X1) is larger than the MFR of the polymer (Y1).
Ethylene contained in the raw materials of the ethylene homopolymer and the ethylene/α-olefin copolymer is (I-1) 0.2% to 99% by weight of biomass-derived ethylene and 1% by weight of fossil fuel-derived ethylene; The ethylene polymer according to claim 1, which is an ethylene mixture containing 99.8% by weight or less (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight). The ethylene polymer according to claim 4, having a biomass degree of 1% or more and 99% or less according to ASTM D 6866. The ethylene polymer contains 5% by weight or more and 95% by weight or less of a copolymer (X2) of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms, and ethylene and a carbon number A mixture of 5% by weight or more and 95% by weight or less of a copolymer (Y2) with at least one olefin selected from the group consisting of 3 to 20 α-olefins (however, a mixture of the above polymer (X2) and the above polymer (Y2) is a copolymer (A2-2) of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms.
_{The ratio (d X2 /d Y2 ) of the} density d
The ratio of the intrinsic viscosity [η _X2 ] of _the copolymer (X2) to the intrinsic viscosity [η _Y2 ] of the copolymer ( _Y2 ) ([η
The above copolymer (X2) satisfies the following (ix) to (xii),
(ix) Density d _X2 is 0.890g/cm ³ ~0.940g/cm ³
(x) Intrinsic viscosity [η _X2 ] measured in decalin at 135°C is 1.0 to 10.0 dl/g
(xi) Temperature at the maximum peak position of the endothermic curve measured by differential scanning calorimeter (Tm (°C))
and density (d _x2 ) satisfy Tm<400×d _x2 −250.
(xii) The decane soluble portion (W (wt%)) and the density (d _x2 ) at room temperature satisfy W<80×exp(-100(d _x2 -0.88))+0.1.
The above copolymer (Y2) satisfies the following (xiii) to (xv),
(xiii) Density d _Y2 is 0.910g/cm ³ ~0.970g/cm ³
(xiv) Intrinsic viscosity [η _Y2 ] measured in decalin at 135°C is 0.5 to 2.0 dl/g
(xv) Temperature at the maximum peak position of the endothermic curve measured by differential scanning calorimeter (Tm (°C))
and density (d _Y2 ) satisfy Tm>138×d _Y2 −6.
The density of the copolymer (A2-2) is in the range of 0.890 to 0.955 g/cm ³ ,
The melt flow rate (MFR) of the copolymer (A2-2) at 190 ° C. and 2.16 kg load satisfies the range of 0.1 to 100 g / 10 minutes,
The ethylene contained in the copolymer (X2) contained in the copolymer (A2-2) and the raw material of the copolymer (Y2) is (I-1) 0.2% by weight or more of biomass-derived ethylene 99 % by weight or less and fossil fuel-derived ethylene from 1% to 99.8% by weight (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight), according to claim 1. ethylene polymer. The ethylene polymer according to claim 6, having a biomass degree of 1% or more and 99% or less according to ASTM D 6866. The ethylene polymer according to claim 6,
Low-density polyethylene (D) produced by a high-pressure radical method that satisfies the following (xvi) to (xvii),
(xvi) Melt flow rate (MFR) at 190°C and 2.16 kg load from 0.1 g/10 minutes to 50 g/10 minutes (xvii) Molecular weight distribution (Mw/Mn) obtained by GPC measurement and the above MFR satisfies the following relationship.
Mw/Mn≧7.5×log(MFR)-1.2
The weight ratio (A2-2):(D) of the ethylene polymer (A2-2) and the high-pressure radical-processed low-density polyethylene (D) is within the range of 99:1 to 60:40.
Ethylene polymer mixture. The ethylene polymer satisfies the following (xviii) to (xxii),
The ethylene contained in the raw material of the ethylene polymer includes (I-1) 0.2% to 99% by weight of biomass-derived ethylene and 1% to 99.8% by weight of fossil fuel-derived ethylene; The ethylene polymer according to claim 1, which is an ethylene mixture (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight).
(xviii) The content of methyl branches and ethyl branches measured by ¹³ C-NMR [M _{Me + Et} (mol%)] and the content of all branches measured by ¹³ C-NMR [M _all ( mol%)] [M _Me+Et /M _all ] is in the range of 0.30 to 1.00.
(xix) MFR at 190°C and 2.16 kg load is 0.1 g/10 minutes to 100 g/10 minutes (xx) Density is 0.890 g/cm ³ to 0.970 g/cm ³
(xxi) The ratio [MT/η * (g/P)] of the melt tension at 190° ^C [MT (g)] and the shear viscosity [η ^* (P)] at 200°C and an angular velocity of 1.0 rad/sec is It is in the range of 1.50×10 ⁻⁴ to 9.00×10 ⁻⁴ .
(xxii) The zero shear viscosity [η ₀ (P)] at 200°C and the weight average molecular weight (Mw) measured by the GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-1) .
0.01×10 ^-13 ×Mw ^3.4 ≦η ₀ ≦4.50×10 ^-13 ×Mw ^3.4 (Eq-1) The ethylene polymer according to claim 9, having a biomass degree of 1% or more and 99% or less according to ASTM D 6866. The above ethylene polymer satisfies the following (xxiii) to (xxviii),
The ethylene contained in the raw material of the ethylene polymer contains (I-1) 0.2% to 99% by weight of biomass-derived ethylene and 1% to 99.8% by weight of fossil fuel-derived ethylene; The ethylene polymer according to claim 1, which is an ethylene mixture (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight).
(xxiii) MFR at 190°C and 2.16 kg load is 0.1 g/10 minutes to 100 g/10 minutes (xxiv) Density is 0.890 g/cm ³ to 0.970 g/cm ³
(xxv) The ratio [MT/η * (g/P)] of the melt tension at 190° ^C [MT (g)] and the shear viscosity [η ^* (P)] at 200°C and an angular velocity of 1.0 rad/sec is It is in the range of 2.50×10 ⁻⁴ to 9.00×10 ⁻⁴ .
(xxvi) Sum of the number of methyl branches per 1000 carbon atoms [A (/1000C)] and the number of ethyl branches [B (/1000C)] measured by ¹³ C-NMR [(A+B) (/1000C)] is 1.8 or less (xxvii) The zero shear viscosity [η ₀ (P)] at 200°C and the weight average molecular weight (Mw) measured by the GPC-viscosity detector method (GPC-VISCO) are expressed by the following relational expression (Eq -2) is satisfied.
0.01×10 ^-13 ×Mw ^3.4 ≦η ₀ ≦4.50×10 ^-13 ×Mw ^3.4 (Eq-2)
(xxviii) The molecular weight at the maximum weight fraction (peak top M) in the molecular weight distribution curve obtained by GPC measurement is 1.0×10 ^4.30 to 1.0×10 ^4.50 The ethylene polymer according to claim 11, having a biomass degree of 1% to 99% according to ASTM D 6866. The ethylene polymer is a copolymer of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms, satisfying the following (xxix) to (xxxii),
The ethylene contained in the raw material of the copolymer includes (I-1) 0.2% to 99% by weight of biomass-derived ethylene and 1% to 99.8% by weight of fossil fuel-derived ethylene; The ethylene polymer according to claim 1, which is a mixture (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight).
(xxix) MFR at 190℃ and 2.16 kg load is 0.1 g/10 minutes to 100 g/10 minutes (xxx) Density is 0.890 g/cm ³ to 0.970 g/cm ³
(xxxi) Sum of the number of methyl branches per 1000 carbon atoms [A (/1000C)] and the number of ethyl branches [B (/1000C)] measured by ¹³ C-NMR [(A+B) (/1000C)] is 1.8 or less (xxxii) The intrinsic viscosity [[η] (dl/g)] measured in decalin at 135°C and the weight average molecular weight (Mw) measured by GPC-viscosity detector method (GPC-VISCO) satisfies the following relational expression (Eq-3).
0.80×10 ^-4 ×Mw ^0.776 ≦[η]≦1.65×10 ^-4 ×Mw ^0.776 (Eq-3) The ethylene polymer according to claim 13, having a biomass degree of 1% to 99% according to ASTM D 6866. The ethylene polymer satisfies the following (xxxiii) to (xxxv): 30% by mass or more and 85% by mass or less of an ethylene polymer (X3);
(xxxiii) Intrinsic viscosity ([η _X3 ]) measured in decalin at 135°C is 0.50 dl/g to 1.50 dl/g
(xxxiv) The ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) measured by GPC is 4.0 to 8.0.
(xxxv) Density d _X3 is 0.940g/cm ³ ~0.980g/cm ³
A copolymer (Y3) of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms, which satisfies the following (xxxvi) to (xxxviii): 15% by mass or more and 70% by mass or less ( However, the ethylene polymer (A2-3) is a mixture of the polymer (X3) and the polymer (Y3) (the total of which is 100% by mass),
(xxxvi) Intrinsic viscosity ([η _Y3 ]) measured in decalin at 135°C is 2.0 dl/g to 8.0 dl/g
(xxxvii) The ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) measured by GPC is 5.0 to 15.0.
(xxxviii) Density d _Y3 is 0.910g/cm ³ ~0.950g/cm ³ (However, density d _X3 ≧density d _Y3 )
The ethylene polymer (A2-3) satisfies the following (xxxix) to (xxxxi),
(xxxix) MFR at 190℃ and 2.16 kg load is 0.01 g/10 minutes to 20 g/10 minutes (xxxx) Density is 0.930 g/cm ³ to 0.960 g/cm ³
(xxxxi) The amount of components eluted at 85°C or lower by cross-fractionation chromatography (CFC) is 10% by mass or less The ethylene polymer (X3) and copolymer (Y3) contained in the above ethylene polymer (A2-3) The ethylene contained in the raw material of (I-1) is an ethylene mixture containing 0.2% to 99% by weight of biomass-derived ethylene and 1% to 99.8% by weight of fossil fuel-derived ethylene. (The total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight), the ethylene polymer according to claim 1. The ethylene polymer according to claim 15, having a biomass degree of 1% to 99% according to ASTM D 6866. The ethylene polymer is a copolymer of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms, satisfying the following (xxxxxii) to (xxxxiv),
The ethylene contained in the raw material of the copolymer includes (I-1) 0.2% to 99% by weight of biomass-derived ethylene and 1% to 99.8% by weight of fossil fuel-derived ethylene; The ethylene polymer according to claim 1, which is a mixture (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight).
(xxxxxii) MFR at 190°C and 2.16 kg load is 0.1 g/10 minutes to 100 g/10 minutes (xxxxiii) Density is 0.890 g/cm ³ to 0.925 g/cm ³
(xxxxiv) The ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) measured by GPC is 1.50 to 3.00. The ethylene polymer according to claim 17, having a biomass degree of 1% to 99% according to ASTM D 6866. At least one olefin selected from the group consisting of ethylene homopolymer, or ethylene and α-olefin having 3 to 20 carbon atoms, with a biomass-derived carbon concentration of 0.2 pMC (%) or more and 99.0 pMC (%) or less A method for producing an ethylene polymer that is a copolymer with
Including the step of supplying a raw material containing ethylene to a polymerization vessel and polymerizing it with a polymerization catalyst,
At least one olefin (a) selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms contained in the raw material contains 0.2% by weight or more and 99% by weight or less of biomass-derived olefin (a1) and fossil fuels. An olefin mixture containing 1% to 99.8% by weight of fuel-derived olefin (a2) (the total of biomass-derived olefin (a1) and fossil fuel-derived olefin (a2) is 100% by weight), ethylene-based Method for producing polymers. The ethylene polymer satisfies the following (i) to (ii),
(i) Density is 0.890g/cm ³ to 0.970g/cm ³
(ii) Melt flow rate (MFR) at 190°C and 2.16 kg load is 0.1 g/10 min to 200 g/10 min. It is an ethylene mixture containing 0.2% to 99% by weight of derived ethylene and 1% to 99.8% by weight of fossil fuel-derived ethylene (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight). ), the method for producing an ethylene polymer according to claim 19. a step (x1) of polymerizing 20% by mass or more and 80% by mass or less of an ethylene polymer (X1) that satisfies the following (iii) to (iv);
(iii) Density is 0.890g/cm ³ to 0.970g/cm ³
(iv) Melt flow rate (MFR) at 190°C and 2.16 kg load is 0.01 g/10 minutes to 1,500 g/10 minutes Ethylene polymer (Y1) that satisfies the following (v) to (vi) 80% by mass or less and 20% by mass or more (however, the total of the polymer (X1) and the polymer (Y1) is 100% by weight) (y1),
(v) Density is 0.890g/cm ³ ~0.960g/cm ³
(vi) MFR at 190°C and 2.16 kg load is 0.01 g/10 min to 500 g/10 min. 1) It is an ethylene mixture containing 0.2% to 99% by weight of biomass-derived ethylene and 1% to 99.8% by weight of fossil fuel-derived ethylene (the total of biomass-derived ethylene and fossil fuel-derived ethylene 100% by weight),
The ethylene polymer obtained through the above steps (x1) and (y1) satisfies the following (vii) to (viii),
(vii) Density is 0.890g/cm ³ ~0.970g/cm ³
(viii) The method for producing an ethylene polymer according to claim 19, wherein the MFR at 190° C. and a load of 2.16 kg is 0.01 g/10 minutes to 60.0 g/10 minutes. The ethylene polymer is a copolymer (A2-2) of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms,
The method for producing the copolymer (A2-2) includes:
A copolymer (X2) of 5% by weight or more, which satisfies the following (ix) to (xii) by polymerizing ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms.95 A step (x2) of producing % by weight or less;
(ix) Density d _X2 is 0.890g/cm ³ ~0.940g/cm ³
(x) Intrinsic viscosity [η _X2 ] measured in decalin at 135°C is 1.0 to 10.0 dl/g
(xi) The temperature (Tm (°C)) and density (d _X2 ) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter satisfy Tm<400×d _X2 -250.
(xii) The decane soluble portion (W (wt%)) and the density (d _x2 ) at room temperature satisfy W<80×exp(-100(d _x2 -0.88))+0.1.
A copolymer (Y2) of 5% by weight or more 95 that satisfies the following (xiii) to (xv) by polymerizing ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms. a step (y2) of producing % by weight or less;
(xiii) Density d _Y2 is 0.910g/cm ³ ~0.970g/cm ³
(xiv) Intrinsic viscosity [η _Y2 ] measured in decalin at 135°C is 0.5 to 2.0 dl/g
(xv) The temperature (Tm (°C)) and density (d _Y2 ) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter satisfy Tm>138×d _Y2 -6.
_{The ratio (d X2 /d Y2 ) of the} density d
The ratio of the intrinsic viscosity [η _X2 ] of _the copolymer (X2) to the intrinsic viscosity [η _Y2 ] of the copolymer ( _Y2 ) ([η
Ethylene contained in the raw materials supplied to the polymerization vessel in each step (x2) and (y2) above is (I-1) 0.2% to 99% by weight of biomass-derived ethylene and 1% by weight of fossil fuel-derived ethylene % or more and 99.8% by weight or less (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight),
The density of the obtained copolymer (A2-2) is in the range of 0.890 to 0.955 g/cm ³ ,
The copolymer (A2-2) has an MFR of 0.1 to 10 at 190°C and a load of 2.16 kg.
The method for producing an ethylene polymer according to claim 19, which satisfies the range of 0 g/10 minutes. A copolymer (A2-2) of ethylene and at least one olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms, obtained by the production method according to claim 22;
Low-density polyethylene (D) produced by a high-pressure radical method that satisfies the following (xvi) to (xvii),
(xvi) MFR is 0.1 g/10 min to 50 g/10 min (xvii) If the molecular weight distribution (Mw/Mn) measured by GPC and MFR are Mw/Mn≧7.5×log(MFR)-1. 2
Melt and knead the ethylene polymer (A2-2) and high pressure radical low density polyethylene (D) so that the weight ratio is in the range of 99:1 to 60:40,
A method for producing an ethylene polymer mixture containing an ethylene polymer (A2-2) and a high-pressure radical process low density polyethylene (D). The ethylene polymer satisfies the following (xviii) to (xxii),
(xviii) The content of methyl branches and ethyl branches measured by ¹³ C-NMR [M _{Me + Et} (mol%)] and the content of all branches measured by ¹³ C-NMR [M _all ( mol%)] [M _Me+Et /M _all ] is in the range of 0.30 to 1.00.
(xix) MFR at 190°C and 2.16 kg load is 0.1 g/10 minutes to 100 g/10 minutes (xx) Density is 0.890 g/cm ³ to 0.970 g/cm ³
(xxi) The ratio [MT/η * (g/P)] of the melt tension at 190° ^C [MT (g)] and the shear viscosity [η ^* (P)] at 200°C and an angular velocity of 1.0 rad/sec is It is in the range of 1.50×10 ⁻⁴ to 9.00×10 ⁻⁴ .
(xxii) The zero shear viscosity [η ₀ (P)] at 200°C and the weight average molecular weight (Mw) measured by the GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-1) .
0.01×10 ^-13 ×Mw ^3.4 ≦η ₀ ≦4.50×10 ^-13 ×Mw ^3.4 (Eq-1)
The ethylene contained in the raw material supplied to the polymerization vessel contains (I-1) 0.2% to 99% by weight of biomass-derived ethylene and 1% to 99.8% by weight of fossil fuel-derived ethylene; The method for producing an ethylene polymer according to claim 19, which is an ethylene mixture (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight). The ethylene polymer satisfies the following (xxiii) to (xxviii),
(xxiii) MFR at 190°C and 2.16 kg load is 0.1 g/10 minutes to 100 g/10 minutes (xxiv) Density is 0.890 g/cm ³ to 0.970 g/cm ³
(xxv) The ratio [MT/η * (g/P)] of the melt tension at 190° ^C [MT (g)] and the shear viscosity [η ^* (P)] at 200°C and an angular velocity of 1.0 rad/sec is It is in the range of 2.50×10 ⁻⁴ to 9.00×10 ⁻⁴ .
(xxvi) Sum of the number of methyl branches per 1000 carbon atoms [A (/1000C)] and the number of ethyl branches [B (/1000C)] measured by ¹³ C-NMR [(A+B) (/1000C)] is 1.8 or less (xxvii) The zero shear viscosity [η ₀ (P)] at 200°C and the weight average molecular weight (Mw) measured by the GPC-viscosity detector method (GPC-VISCO) are expressed by the following relational expression (Eq -2) is satisfied.
0.01×10 ^-13 ×Mw ^3.4 ≦η ₀ ≦4.50×10 ^-13 ×Mw ^3.4 (Eq-2)
(xxviii) The molecular weight at the maximum weight fraction (peak top M) in the molecular weight distribution curve obtained by GPC measurement is 1.0×10 ^4.30 to 1.0×10 ^4.50
The ethylene contained in the raw material supplied to the polymerization vessel contains (I-1) 0.2% to 99% by weight of biomass-derived ethylene and 1% to 99.8% by weight of fossil fuel-derived ethylene; The method for producing an ethylene polymer according to claim 19, which is an ethylene mixture (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight). The ethylene polymer satisfies the following (xxix) to (xxxii),
(xxix) MFR at 190℃ and 2.16 kg load is 0.1 g/10 minutes to 100 g/10 minutes (xxx) Density is 0.890 g/cm ³ to 0.970 g/cm ³
(xxxi) Sum of the number of methyl branches per 1000 carbon atoms [A (/1000C)] and the number of ethyl branches [B (/1000C)] measured by ¹³ C-NMR [(A+B) (/1000C)] is 1.8 or less (xxxii) The intrinsic viscosity [[η] (dl/g)] measured in decalin at 135°C and the weight average molecular weight (Mw) measured by GPC-viscosity detector method (GPC-VISCO) satisfies the following relational expression (Eq-3).
0.80×10 ^-4 ×Mw ^0.776 ≦[η]≦1.65×10 ^-4 ×Mw ^0.776 (Eq-3)
The ethylene contained in the raw material supplied to the polymerization vessel contains (I-1) 0.2% to 99% by weight of biomass-derived ethylene and 1% to 99.8% by weight of fossil fuel-derived ethylene; The method for producing an ethylene polymer according to claim 19, which is an ethylene mixture (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight). a step (x3) of polymerizing 30% by mass or more and 85% by mass or less of an ethylene polymer (X3) that satisfies the following (xxxiii) to (xxxv);
(xxxiii) Intrinsic viscosity ([η _X3 ]) measured in decalin at 135°C is 0.50 dl/g to 1.50 dl/g
(xxxiv) The ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) measured by GPC is 4.0 to 8.0.
(xxxv) Density d _X3 is 0.940g/cm ³ ~0.980g/cm ³
Contains 15% by mass or more and 70% by mass or less of an ethylene polymer (Y3) that satisfies the following (xxxvi) to (xxxviii) (however, the total of the polymer (X3) and the polymer (Y3) is 100% by mass or more % by mass),
(xxxvi) Intrinsic viscosity ([η _Y3 ]) measured in decalin at 135°C is 2.0 dl/g to 8.0 dl/g
(xxxvii) The ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) measured by GPC is 5.0 to 15.0.
(xxxviii) Density d _Y3 is 0.910g/cm ³ ~0.950g/cm ³ (However, density d _X3 ≧density d _Y3 )
Ethylene contained in the raw materials supplied to the polymerization vessel in steps (x3) and (y3) above is (I-1) 0.2% to 99% by weight of biomass-derived ethylene and 1% by weight of fossil fuel-derived ethylene. It is an ethylene mixture containing 99.8% by weight or less (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight),
The ethylene polymer (A2-3) obtained through the above steps (x3) and (y3) satisfies the following (xxxix) to (xxxxi),
(xxxix) MFR at 190℃ and 2.16 kg load is 0.01 g/10 minutes to 20 g/10 minutes (xxxx) Density is 0.930 g/cm ³ to 0.960 g/cm ³
(xxxxi) The method for producing an ethylene polymer according to claim 19, wherein the amount of components eluted at 85° C. or lower by cross fractionation chromatography (CFC) is 10% by mass or less. The ethylene polymer satisfies the following (xxxxxii) to (xxxxiv),
(xxxxxii) MFR at 190°C and 2.16 kg load is 0.1 g/10 minutes to 100 g/10 minutes (xxxxiii) Density is 0.860 g/cm ³ to 0.925 g/cm ³
(xxxxiv) The ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) measured by GPC is 1.50 to 3.00.
The ethylene contained in the raw material supplied to the polymerization vessel contains (I-1) 0.2% to 99% by weight of biomass-derived ethylene and 1% to 99.8% by weight of fossil fuel-derived ethylene; The method for producing an ethylene polymer according to claim 19, which is an ethylene mixture (the total of biomass-derived ethylene and fossil fuel-derived ethylene is 100% by weight). A resin composition comprising the ethylene polymer according to any one of claims 1 to 7 and 9 to 18. A resin composition comprising the ethylene polymer mixture according to claim 8. A molded article made of the ethylene polymer according to any one of claims 1 to 7 and 9 to 18. A molded article comprising the ethylene polymer mixture according to claim 8.