JP2023072470A - Propylene polymer obtained from biomass-derived propylene, and method for producing the propylene polymer - Google Patents

Abstract

To provide a propylene polymer that allows for reduction in environmental load (emission of greenhouse gases) in a life cycle from the production of the propylene polymer to its use and disposal, and a method for producing the polymer.SOLUTION: The present invention provides a propylene polymer that is a propylene homopolymer, or a copolymer of propylene and a specific olefin. The propylene included in the raw material of the propylene polymer is biomass-derived propylene.SELECTED DRAWING: None

Description

The present invention relates to a propylene-based polymer and a method for producing the polymer. More particularly, it relates to a propylene-based polymer obtained by polymerizing biomass-derived propylene, and a method for producing the polymer.

From the viewpoint of reducing the environmental burden (greenhouse gas generation) in the life cycle of plastic products from manufacturing to use and disposal, it is necessary to manufacture biomass-derived propylene, and to produce propylene-based polymers from raw materials containing biomass-derived propylene. (biomass-derived propylene-based polymer) is being studied (Patent Documents 1 and 2).

In addition, in order to widely disseminate materials containing polymers made from biomass-derived propylene, which has a low environmental impact, materials with adjusted biomass content are required in consideration of product prices, market needs, etc.

Examples of materials whose biomass degree is adjusted include, for example, a material in which pulverized recycled polypropylene is mixed with biomass-derived polypropylene (Patent Document 3), and the ratio of biomass-derived carbon is 70% or more and less than 100%. In addition, a material in which biomass-derived polyolefin chips and polyolefin chips made only of petroleum-based materials are mixed (Patent Document 4) is being studied.

Also, a propylene-based polymer composition containing biomass polyethylene and a propylene-based polymer having a biomass degree of 8.4 to 49 has been studied (Patent Document 5).

WO2007/055361 Japanese Patent Publication No. 2010-511634 Japanese Patent Publication No. 2014-508688 JP 2013-076192 A JP 2021-091881 A JP-A-10-237127 JP-A-9-031265 JP-A-2004-292683

However, Patent Documents 3 to 5 do not specifically consider the use of a propylene-based polymer using only biomass-derived propylene as a raw material propylene.

In addition, when adjusting the biomass degree by the method of Patent Document 5, the polymer composition must contain biomass polyethylene (10 to 49 parts by weight), so the propylene polymer alone does not contain polyethylene. There is concern that the performance derived from the propylene polymer alone, such as lower rigidity and lower heat deflection temperature under load, will be less likely to be exhibited compared to the propylene polymer composition.

The only structural difference between biomass-derived propylene and fossil fuel-derived propylene is that it contains a 14C isotope ( ^14C is present at a concentration of about ^10-12 relative to total carbon in biomass-derived olefins). The difference in the molecular structure of the propylene-based polymers made from these raw materials is only whether or not they have ¹⁴ C, and other than that, the molecular weight, molecular weight distribution, stereoregularity, stereoregularity distribution, composition, composition distribution, decane It is said that there is no difference in performance between a propylene-based polymer made of biomass-derived olefin and a conventional propylene-based polymer made of fossil fuel-derived olefin if the molecular structure such as the amount of soluble portion is the same. The performance of propylene-based polymers (for example, mechanical properties such as rigidity and impact resistance) depends on the stereoregularity of propylene-based polymers, molecular weight distribution, composition distribution (propylene/α-olefin random copolymer), rubber content ( Dependence on molecular structures other than 14C concentration (Patent Documents 6 to 8) such as propylene/ethylene block copolymer) is also considered to apply to propylene-based polymers containing structural units derived from biomass-derived olefins.

An object of the present invention is to provide a propylene-based polymer with reduced environmental load (greenhouse gas generation) in its life cycle from production to use and disposal, and to provide a method for producing the polymer. to provide.

As a result of intensive studies aimed at solving the above problems, the present inventors found that the above problems can be solved by using biomass-derived propylene as the propylene contained in the raw material of the propylene-based polymer. Arrived.

The present invention relates to the following [1] to [19].
[1] A propylene homopolymer or a propylene-based polymer that is a copolymer of propylene and at least one olefin (b) selected from the group consisting of ethylene and α-olefins having 4 to 8 carbon atoms, A propylene-based polymer in which the propylene contained in the raw material of the propylene-based polymer is biomass-derived propylene.

[2] the propylene-based polymer is a propylene homopolymer,
The propylene-based polymer according to [1], wherein the propylene homopolymer satisfies the following (i) to (ii).
(i) Melt flow rate (MFR) at 230°C and 2.16 kg load of 0.
01 g/10 min or more and 2,000 g/10 min or less (ii) The isotactic pentad fraction is 90.0% or more and 99.9% or less

[3] The propylene-based polymer according to [2], which is a propylene homopolymer having a biomass degree of 100% according to ASTM D 6866.

[4] The propylene-based polymer is a random copolymer of propylene and at least one olefin (b) selected from the group consisting of ethylene and α-olefins having 4 to 8 carbon atoms,
The random copolymer contains 90.0% by weight or more and 99.9% by weight or less of structural units derived from propylene and 0.1% by weight or more and 10.0% by weight or less of structural units derived from olefin (b). including
The propylene-based polymer according to [1], which satisfies the following (iii) to (iv).
(iii) Melt flow rate (MFR) at 230°C and 2.16 kg load of 0.01 g/10 min or more and 2,000 g/10 min or less (iv) Melting point of 100°C or more and 160°C or less

[5] A random copolymer of propylene having a biomass degree of 90% or more according to ASTM D 6866 and at least one olefin (b) selected from the group consisting of ethylene and α-olefins having 4 to 8 carbon atoms. The propylene-based polymer according to [4], which is

[6] The propylene-based polymer is a propylene/ethylene block copolymer,
The propylene/ethylene block copolymer is
A propylene homopolymer or a crystalline propylene/ethylene random copolymer containing 95% by weight or more and less than 100% by weight of structural units derived from propylene and 5% by weight or less of structural units derived from ethylene, the following (v)
(v) Intrinsic viscosity [η] of 0.8 (dl/g) or more and 3.0 (dl/g)
55% by weight or more and 95% by weight of the crystalline propylene-based polymer component (c) satisfying
Containing 20% by weight or more and 80% by weight or less of structural units derived from propylene and 20% by weight or more and 80% by weight of structural units derived from ethylene, the following (vi)
(vi) Intrinsic viscosity [η] of 1.0 (dl/g) or more and 10.0 (dl/g)
The propylene-based polymer according to [1], containing 5% by weight or more and 45% by weight or less of the propylene/ethylene random copolymer component (d) satisfying the above.

[7] The propylene-based polymer according to [6], which is a propylene/ethylene block copolymer having a biomass content of 61% or more and 100% or less according to ASTM D 6866.

[8] A method for producing a propylene-based polymer that is a propylene homopolymer or a copolymer of propylene and at least one olefin (b) selected from the group consisting of ethylene and α-olefins having 4 to 8 carbon atoms. and
including a step of supplying a raw material containing propylene to a polymerization vessel and polymerizing it with a polymerization catalyst;
A method for producing a propylene-based polymer, wherein the propylene contained in the raw material is biomass-derived propylene.

[9] The method for producing a propylene-based polymer according to [8], wherein the propylene-based polymer is a propylene homopolymer satisfying the following (i) to (ii).
(i) Melt flow rate (MFR) at 230°C and 2.16 kg load of 0.
01 g/10 min or more and 2,000 g/10 min or less (ii) The isotactic pentad fraction is 90.0% or more and 99.9% or less

[10] The propylene-based polymer satisfies the following (iii) to (iv), and at least one olefin (b) selected from the group consisting of propylene, ethylene, and an α-olefin having 4 to 8 carbon atoms. The method for producing a propylene-based polymer according to [8], which is a random copolymer.
(iii) Melt flow rate (MFR) at 230°C and 2.16 kg load of 0.01 g/10 min or more and 2,000 g/10 min or less (iv) Melting point of 100°C or more and 160°C or less

[11] The random copolymer contains 90.0% by weight or more and 99.9% by weight or less of structural units derived from propylene and 0.1% by weight or more and 0.1% by weight or more of structural units derived from at least one olefin (b). 0% by weight or less.

[12] The propylene-based polymer is a propylene/ethylene block copolymer,
The propylene/ethylene block copolymer is
A propylene homopolymer or a crystalline propylene/ethylene random copolymer containing 95% by weight or more and less than 100% by weight of structural units derived from propylene and 5% by weight or less of structural units derived from ethylene, the following (v)
(v) Intrinsic viscosity [η] of 0.8 (dl/g) or more and 3.0 (dl/g)
55% by weight or more and 95% by weight of the crystalline propylene-based polymer component (c) satisfying
Containing 20% by weight or more and 80% by weight or less of structural units derived from propylene and 20% by weight or more and 80% by weight of structural units derived from ethylene, the following (vi)
(vi) Intrinsic viscosity [η] of 1.0 (dl/g) or more and 10.0 (dl/g)
5% by weight or more and 45% by weight or less of the propylene/ethylene random copolymer component (d) satisfying
A raw material (1) containing propylene or propylene and ethylene is supplied to a polymerization vessel and polymerized with a polymerization catalyst,
A crystalline propylene-based polymer comprising a propylene homopolymer or a crystalline propylene/ethylene random copolymer containing 95% by weight or more and less than 100% by weight of structural units derived from propylene and 5% by weight or less of structural units derived from ethylene. A step (α) of producing component (c), and a raw material (2) containing propylene and ethylene is supplied to a polymerization vessel and polymerized with a polymerization catalyst to produce a propylene/ethylene random copolymer component (d). The method for producing a propylene-based polymer according to [8], comprising the step (β) of

[13] A resin composition containing the propylene homopolymer of [2] or [3].

[14] A resin composition containing a random copolymer of propylene according to [4] or [5] and at least one olefin (b) selected from the group consisting of ethylene and α-olefins having 4 to 8 carbon atoms. thing.

[15] A resin composition containing the propylene/ethylene block copolymer of [6] or [7].

[16] A molded article comprising the propylene homopolymer described in [2] or [3].

[17] Molded article comprising a random copolymer of propylene according to [4] or [5] and at least one olefin (b) selected from the group consisting of ethylene and α-olefins having 4 to 8 carbon atoms .

[18] A molded article comprising the propylene/ethylene block copolymer of [6] or [7].

[19] A molded article made of the resin composition according to any one of [13] to [15].

According to the propylene-based polymer and the method for producing the polymer of the present invention, the environmental load (greenhouse gas generation) in the life cycle can be reduced.

The present invention will now be described in more detail.
[Biomass-derived olefin, biomass-derived carbon]
Biomass refers to any renewable natural raw material and its residues, such as of plant or animal origin, including fungi, yeasts, algae and bacteria, biomass-derived olefins (ethylene, α-olefins, etc.) Olefins obtained from this biomass. Biomass-derived carbon contains a certain amount of ¹⁴ C isotope as carbon (proportion of about 10 ⁻¹² ).

[Fossil fuel-derived olefins]
Fossil fuel refers to petroleum, coal, natural gas, shale gas, and other fossil fuels that have been fossilized by the volume and pressure of dead animals and plants over hundreds of millions of years. α-olefins such as ethylene, propylene, etc.) are olefins obtained from this fossil fuel. ¹⁴ C is not detected from fossil-derived carbon, since it is sufficiently longer than the 5,730-year half-life of the ¹⁴ C isotope.

[Propylene polymer (A)]
The propylene-based polymer (A) of the present invention mainly contains structural units derived from propylene (typically contains more than 50% by weight, preferably 60% by weight, of structural units derived from propylene). including above) is a polymer. Such a propylene-based polymer (A) is typically a propylene homopolymer (A1), or at least one olefin (b ) (Hereinafter, at least one olefin selected from the group consisting of ethylene and α-olefins having 4 to 8 carbon atoms is also simply referred to as olefin (b).) And a copolymer (A2) (hereinafter, propylene-based copolymer Also referred to as a polymer (A2).) and the like.

Examples of the propylene-based copolymer (A2) include random copolymers (A2-1) of propylene and olefin (b) (e.g., propylene/ethylene random copolymers, propylene/α-olefins (having 4 to 8 carbon atoms ) including random copolymers, propylene/ethylene/α-olefin (4 to 8 carbon atoms) random copolymers) (Hereinafter, random copolymers (A2-1) of propylene and olefin (b) Also referred to simply as a propylene-based random copolymer (A2-1).), containing 95% by weight or more and less than 100% by weight of structural units derived from propylene homopolymer or propylene and 5% by weight or less of structural units derived from ethylene. A crystalline propylene-based polymer component (c) comprising a crystalline propylene/ethylene random copolymer, 20% by weight or more and 80% by weight or less of structural units derived from propylene, and 20% by weight or more and 80% by weight of structural units derived from ethylene. and a propylene/ethylene block copolymer (A2-2) containing a propylene/ethylene random copolymer component (d) containing

Examples of α-olefins having 4 to 8 carbon atoms that can be a constituent unit of the propylene-based copolymer (A2) include 1-butene, 1-pentene, 1-hexene, 1-octene and 4-methyl-1-pentene. is mentioned. Among these α-olefins, 1-butene and 1-hexene are preferable from the viewpoint of ease of polymerization and mechanical strength of the resulting copolymer.

The propylene contained in the raw material of the propylene-based polymer (A) of the present invention is biomass-derived propylene (propylene is 100% by weight biomass-derived propylene).

When the propylene polymer (A) of the present invention contains an olefin (b) as a raw material (the propylene polymer (A) is a propylene random copolymer (A2-1) described later, propylene -In the case of a propylene-based copolymer (A2) such as an ethylene block copolymer (A2-2)), the olefin (b) may be only the biomass-derived olefin (b1), or a fossil fuel-derived olefin ( It may be b2) alone, or an olefin mixture containing the biomass-derived olefin (b1) and the fossil fuel-derived olefin (b2).
When the olefin (b) is a mixture of the biomass-derived olefin (b1) and the fossil fuel-derived olefin (b2), for example, 0.2% by weight or more and 99% by weight or less of the biomass-derived olefin (b1) and the fossil fuel It may be an olefin mixture containing 1% by weight or more and 99.8% by weight or less of the derived olefin (b2), and 1% by weight or more and 95% by weight or less of the biomass-derived olefin (b1) and 5% by weight of the fossil fuel-derived olefin (b2). % or more and 99% or less by weight, and may be an olefin mixture containing 5% or more and 90% or less by weight of the biomass-derived olefin (b1) and 10% or more and 95% or less by weight of the fossil fuel-derived olefin (b2). It may be an olefin mixture, or an olefin mixture containing 10% by weight or more and 69% by weight or less of the biomass-derived olefin (b1) and 31% by weight or more and 90% by weight or less of the fossil fuel-derived olefin (b2).

The propylene-based polymer (A) of the present invention is not particularly limited in its production method. The propylene-based polymer (A) of the present invention can be produced, for example, by the method for producing the propylene-based polymer (A) described below.

[Propylene homopolymer (A1)]
The propylene homopolymer (A1) of the present invention is a polymer containing only structural units derived from propylene, and contains only propylene as the starting material for the propylene homopolymer (A1). Therefore, the raw material propylene consists only of biomass-derived propylene. Therefore, the propylene homopolymer (A1) can contribute to reducing environmental load.

The propylene homopolymer (A1) of the present invention preferably satisfies any one of the following (i) to (ii), and more preferably satisfies both of the following (i) to (ii).
(i) Melt flow rate (MFR) at 230°C and 2.16 kg load is 0.01 g/10 min or more and 2,000 g/10 min or less, preferably 0.05 g/10 min or more and 1,000 g/ 10 minutes or less. When the melt flow rate (MFR) is within this range, the moldability and the performance of the molded products are excellent when processed into various molded products.

(ii) The isotactic pentad fraction is 90.0% or more and 99.9% or less, preferably 95.0% or more and 99.8% or less. When the isotactic pentad fraction is within this range, the performance of various molded articles is excellent. The isotactic pentad fraction is obtained from ¹³ C-NMR measurement of the polymer.

The propylene homopolymer (A1) of the present invention preferably has a biomass degree of 100% according to ASTM D 6866. The degree of biomass can be calculated by the following method using the following biomass-derived carbon concentration pMC (percent Modern Carbon) value.

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

The principle of determining the biomass-derived carbon concentration from the ¹⁴ C abundance ratio in carbon is, for example, "Evaluation of the biomass-derived degree of biomass plastic by measuring carbon 14 using AMS", Thermal measurement, 39 (4), 2012. , as described below.

Atmospheric carbon dioxide contains a certain proportion of carbon-14, and this proportion is maintained even when plants fix carbon dioxide. Carbon-14 is a radioactive isotope with a half-life of 5,730 years and decays at a constant rate. This is a method of estimating the number of years that have elapsed since a plant fixed carbon dioxide by measuring the concentration (proportion) of carbon-14 using this fact. It is believed that petroleum has been stored underground for a long period of one million years or more. Therefore, even if petroleum is of biological origin, all carbon 14 is decayed and not included. On the other hand, plants contain a certain proportion of carbon-14. Whether it is derived from fossil fuel or derived from 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 the dating method and comparing it with the current ratio of carbon 14 in plants. Become. This is the principle of the method for measuring the degree of biomass origin by measuring the carbon-14 concentration.

[Method for measuring biomass degree (biobased carbon content)]
Corrected by δ ¹³ C (measured ¹³ C concentration ( ¹³ C/ ¹² C) of sample carbon and expressed deviation from standard sample in 1000 minutes deviation (‰)) in accordance with ASTM D 6866-21 calculated using pMC obtained from The value for 2019-2021 described in ASTM D6866-21 (latest version) was used as the atmospheric correction factor (100.0 pMC).

The propylene homopolymer (A1) of the present invention may have a specific molecular weight distribution, may have a specific amount of residue such as a catalyst, and may have a specific amount of low-crystalline components. may be applied. For example, WO 2020/189676, JP 2020-090621, JP 2019-167499, JP 2019-137847, JP 2019-137848, WO 2016/159069, JP 2005- 171169, JP 2014-181317, JP 2002-317012, JP 2007-119760, International Publication No. 2005/097842, JP 2000-44630, JP 11-349635, JP 11- 100412, JP-A-8-85711, JP-A-8-73529, JP-A-2014-231604, International Publication No. 2008/088022, JP-A-2006-328300, JP-A-2011-26620, JP-A-10- No. 17610, JP-A-6-236709, International Publication No. 1997/045563, etc., and at least part of the propylene homopolymer described in the above-mentioned publications is added to the propylene homopolymer of the present invention so as to have the properties described in the above-mentioned publications. After preparing (A1), it can be used in place of the propylene homopolymer (A1).

The stereoregularity of the propylene homopolymer (A1) of the present invention is not particularly limited. or a propylene homopolymer having an atactic structure.

[Propylene random copolymer (A2-1)]
The propylene-based random copolymer (A2-1) of the present invention is a copolymer obtained by random copolymerization of propylene and olefin (b).
In the propylene-based random copolymer (A2-1), the structural unit derived from propylene is preferably 90.0% by weight or more and 99.9% by weight or less, more preferably 92.0% by weight or more and 99.0% by weight. and the structural unit derived from the olefin (b) is preferably 0.1% by weight or more and 10.0% by weight or less, more preferably 1.0% by weight or more and 8.0% by weight or less.

As the olefin (b) contained in the raw material of the propylene-based random copolymer (A2-1), ethylene, 1-butene, 1-butene, 1- Hexene is preferred.

Also in the propylene-based random copolymer (A2-1), the raw material propylene is composed only of biomass-derived propylene. Therefore, the propylene-based random copolymer (A2-1) can contribute to reducing environmental load.

Further, in the propylene-based random copolymer (A2-1), as described above, the olefin (b) may be only the biomass-derived olefin (b1) or only the fossil fuel-derived olefin (b2). or an olefin mixture containing a biomass-derived olefin (b1) and a fossil fuel-derived olefin (b2). Further, when the olefin (b) is an olefin mixture containing the biomass-derived olefin (b1) and the fossil fuel-derived olefin (b2), the olefin (b) is included as a raw material for the propylene-based polymer (A). It may be a mixture of the biomass-derived olefin (b1) and the fossil fuel-derived olefin (b2) in the weight proportions as described in the case where the

The propylene-based random copolymer (A2-1) of the present invention preferably satisfies any one of the following (iii) to (iv), and more preferably satisfies both of the following (iii) to (iv).
(iii) Melt flow rate (MFR) at 230° C. and 2.16 kg load is 0.01 g/10 min or more and 2,000 g/10 min or less, preferably 0.05 g/10 min or more and 1,000 g/ 10 minutes or less. When the melt flow rate (MFR) is within this range, the moldability and the performance of the molded products are excellent when processed into various molded products. The MFR is a value measured at a temperature of 230° C. and a load of 2.16 kg according to ASTM D1238E.

(iv) a melting point of 100° C. or higher and 160° C. or lower, preferably 115° C. or higher and 155° C. or lower; When the melting point is within this range, excellent transparency, sealability and flexibility are obtained. The above melting points are values measured using a differential scanning calorimeter according to JIS-K7121.

The propylene-based random copolymer (A2-1) of the present invention preferably has a biomass degree according to ASTM D 6866 of 90% or more, more preferably 92% or more. Further, the biomass degree of the propylene-based random copolymer (A2-1) may be 100%.

The propylene-based random copolymer (A2-1) may have a specific molecular weight distribution, may have a specific amount of low-crystalline components, or may be subjected to electron beam irradiation. For example, JP-A-4-202409, JP-A-6-239935, JP-A-9-272718, JP-A-10-130336, JP-A-11-021318, JP-A-11-106433, JP-A-11-349635 , WO 99/001486, JP 2000-178320, JP 2001-058380, WO 2000/020473, JP 2002-275330, JP 2002-363308, JP 2006-52314 No., JP-A-2006-57010, etc., and at least part of the propylene-based random copolymer described in the above-mentioned publications is added to the propylene-based random copolymer (A2-1) of the present invention so as to have the properties described in the above-mentioned publications. can be prepared and used in place of the propylene-based random copolymer (A2-1).

[Propylene/ethylene block copolymer (A2-2)]
The propylene/ethylene block copolymer (A2-2) of the present invention contains 95% by weight or more and less than 100% by weight of structural units derived from a propylene homopolymer or propylene and 5% by weight or less of structural units derived from ethylene. A crystalline propylene-based polymer component (c) comprising a crystalline propylene/ethylene random copolymer, 20% by weight or more and 80% by weight or less of structural units derived from propylene, and 20% by weight or more and 80% by weight of structural units derived from ethylene. % and a propylene/ethylene random copolymer component (d).

The crystalline propylene-based polymer component (c) contained in the propylene/ethylene block copolymer (A2-2) preferably satisfies the following (v).
(v) The intrinsic viscosity [η] of the crystalline propylene-based polymer component (c) is 0.8 (dl/g) or more and 3.0 (dl/g).

The content of the crystalline propylene-based polymer component (c) in the propylene/ethylene block copolymer (A2-2) is preferably 55% to 95% by weight, more preferably 65% to 90% by weight. It is below.

The propylene/ethylene random copolymer component (d) contained in the propylene/ethylene block copolymer (A2-2) preferably satisfies the following (vi).
(vi) The intrinsic viscosity [η] of the propylene/ethylene random copolymer component (d) is 1.0 (dl/g) or more and 10.0 (dl/g).

The content of the propylene/ethylene random copolymer component (d) in the propylene/ethylene block copolymer (A2-2) is preferably 5% by weight or more and 45% by weight or less, more preferably 10% by weight or more and 35% by weight. % by weight or less.

Also in the propylene/ethylene block copolymer (A2-2), the raw material propylene is composed only of biomass-derived propylene. Therefore, the propylene/ethylene block copolymer (A2-2) can contribute to reducing environmental load.

Also, in the propylene/ethylene block copolymer (A2-2), as described above, the ethylene corresponding to the olefin (b) may be only biomass-derived ethylene or only fossil fuel-derived ethylene. Alternatively, it may be an olefin mixture containing biomass-derived ethylene and fossil fuel-derived ethylene. Further, when the ethylene is an olefin mixture containing biomass-derived ethylene and fossil fuel-derived ethylene, the weight as described in the case where the olefin (b) is contained as a raw material of the propylene-based polymer (A) A mixture of biomass-derived ethylene and fossil fuel-derived ethylene (for example, an olefin mixture containing 0.2% to 99% by weight of biomass-derived ethylene and 1% to 99.8% by weight of fossil fuel-derived ethylene ).

In the propylene/ethylene block copolymer (A2-2) of the present invention, the biomass degree according to ASTM D 6866 is preferably 61% or more and 100% or less, more preferably 69% or more and 100% or less. be.

The propylene/ethylene block copolymer (A2-2) may have a specific molecular weight distribution, may have a specific amount of residue such as a catalyst, and may have a specific amount of low-crystalline components. The propylene/ethylene random copolymer may have a specific amount/specific molecular weight (intrinsic viscosity)/specific ethylene content, and may contain two or more propylene/ethylene random copolymers. Electron beam irradiation may be applied. For example, JP-A-9-286881, JP-A-2001-19826, JP-A-2002-030127, JP-A-2002-30128, JP-A-2004-292683, JP-A-2005-298706, JP-A-2006-28449 , JP 2006-124452, JP 2006-124453, JP 2006-152111, JP 2006-8983, WO 2006/068308, WO 2007/116709, JP 2009-84305 No., International Publication No. 2010/032793, JP 2011-190408, JP 8-217823, JP 10-182764, JP 10-330430, WO 1999/065965, JP 2001- 233923, JP-A-2005-120388, JP-A-2015-178568, etc., and at least a part of the propylene-ethylene block copolymer of the present invention is added so as to have the properties described in the above-mentioned publications. After preparing the ethylene block copolymer (A2-2), it can be used in place of the propylene/ethylene block copolymer (A2-2).

[Method for producing propylene-based polymer (A)]
The propylene-based polymer (A) of the present invention can be produced by polymerizing raw materials containing propylene consisting only of biomass-derived propylene and optionally containing olefin (b) using a polymerization catalyst.

The propylene-based polymer (A) of the present invention can be preferably produced by a production method comprising a step of supplying a propylene-containing raw material consisting only of biomass-derived propylene to a polymerization vessel and polymerizing the raw material with a polymerization catalyst. .

Olefins (propylene, ethylene, α-olefins having 4 to 8 carbon atoms) used as raw materials for producing the propylene-based polymer (A) can be produced, for example, by the following method.

Biomass-derived olefins (biomass-derived propylene, biomass-derived ethylene, biomass-derived α-olefins having 4 to 8 carbon atoms) can be produced by known methods.

Methods for producing biomass-derived propylene include, for example, the method described in International Publication No. 2007/055361, in which ethanol obtained from biomass is used as a raw material; The method described in WO2016/184893 produced from any bio-renewable source, such as plants or animals, including fungi, yeast, algae and bacteria, bio-renewable Examples include the method described in International Publication No. WO 2016/184894 in which a feedstock is thermally cracked to produce it.

Methods for producing biomass-derived ethylene include, for example, the method described in WO 2007/055361 or WO 2008/062709, in which biomass-derived ethanol is used as a raw material, or the method described in WO 2008/062709, in which residues of renewable natural raw materials are used as raw materials. The method described in WO 2008/67627 for production as a bio-renewable Examples include the method described in International Publication No. 2016/184893 or International Publication No. 2016/184894, which is produced by thermally cracking a raw material.

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

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

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

The biomass-derived olefins described above may be those produced by known methods other than those described above or methods based on known methods. When ethylene or propylene is used as a raw material for production, biomass-derived ethylene is used as ethylene, and biomass-derived propylene is used as propylene.

Fossil fuel-derived olefins (fossil fuel-derived propylene, fossil fuel-derived ethylene, fossil fuel-derived C4-8 α-olefins) 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 pyrolysis and fractional distillation of naphtha obtained in the process of petroleum refining, as posted on the website of the Japan Petrochemical Industry Association (Petrochemical Complex Exploring (2) Naphtha cracking plant [searched on September 1, 2021], Internet <URL: https://www.jpca.or.JP/studies/junior/tour02.html>).

A fossil fuel-derived α-olefin having 4 to 8 carbon atoms can be produced by a known synthesis method using, for example, fossil fuel-derived propylene or fossil fuel-derived ethylene as a raw material. Examples of the method for producing 1-butene derived from fossil fuel include the methods described in JP-A-58-146518 and International Publication No. 1989/000553, and the method for producing 1-hexene derived from fossil fuel includes: Examples include methods described in JP-A-7-149672 and JP-A-8-183747, and methods for producing 1-octene derived from fossil fuels include, for example, JP-A-2009-072666, International Publication No. 2008/ The method described in No. 088178 and the like can be mentioned.

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

An olefin mixture containing the above-mentioned biomass-derived olefin (b1) and fossil fuel-derived olefin (b2) in a desired ratio (for example, biomass-derived olefin (b1) 0.2 wt% or more and 99 wt% or less and fossil fuel-derived olefin ( b2) Olefin mixture containing 1% by weight or more and 99.8% by weight or less) can be prepared by mixing the biomass-derived olefin (b1) and the fossil fuel-derived olefin (b2) in a desired specific ratio.

In addition, the α-olefin having 4 to 8 carbon atoms as a raw material for the propylene-based polymer (A) is a biomass-derived α-olefin having 4 to 8 carbon atoms and a fossil fuel-derived α-olefin having 4 to 8 carbon atoms. - if it is an olefin mixture, any bio-renewable, e.g. plant or animal, including light naphtha derived from fossil fuels and fungi, yeasts, algae and bacteria, e.g. as described in WO 2016/184893 Naphtha obtained as a raw material is mixed at a desired specific ratio, this mixture is put into a thermal cracking furnace, and ethylene and propylene are taken out from a cracked gas fractionator to prepare. Using the propylene mixture of biomass-derived propylene and fossil fuel-derived propylene or the ethylene mixture of biomass-derived ethylene and fossil fuel-derived ethylene obtained as a raw material, it can be produced by a known method or a method according to the known method. A naphtha cracking unit including a thermal cracking furnace and a cracked gas fractionation unit in series is called an "ethylene cracker" in the petrochemical industry.

In the method for producing the propylene-based polymer (A) of the present invention, a raw material containing propylene introduced into a polymerization vessel is polymerized. A liquid phase polymerization method may be used, or a gas phase polymerization method may be used. Moreover, such polymerization may be carried out by combining a plurality of these polymerization methods.

An inert organic solvent is usually used as the polymerization solvent used in the liquid phase polymerization method. Examples of inert organic solvents include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons; aromatic hydrocarbons; Mixtures of these and the like are included. Among these, aliphatic hydrocarbons are preferred. Moreover, when a slurry polymerization method is employed 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 the propylene-based polymer (A) of the present invention, a raw material containing propylene introduced into a polymerization vessel is polymerized using a polymerization catalyst. As the polymerization catalyst, a polymerization catalyst generally used for polymerization of olefins containing propylene can be used. Such polymerization catalysts include, for example, Ziegler-Natta catalysts, metallocene catalysts, etc., each comprising a titanium catalyst component and an organoaluminum compound.

As the Ziegler-Natta catalyst, for the purpose of producing a highly stereoregular polymer, a solid titanium catalyst component containing an internal donor (internal electron donor), an organic aluminum compound, and an external donor are usually used. (external electron donor) is used. As such a Ziegler-Natta catalyst, for example, an olefin polymerization catalyst comprising a magnesium chloride-supported solid titanium catalyst containing carboxylic acid esters as an internal donor, an organoaluminum compound, and an organosilicon compound as an external donor can be used. (for example, olefin polymerization catalysts described in JP-A-08-003215 and JP-A-08-143620). Also, the Ziegler-Natta catalyst may be used in the form of a prepolymerized catalyst obtained by prepolymerizing raw material olefin or the like.

In the Ziegler-Natta catalyst, the solid titanium catalyst component or the prepolymerized catalyst obtained from the solid titanium catalyst component is usually about 1×10 ⁻⁵ to 1×10 −5 -1 titanium atoms per liter polymerization volume. It is used in an amount of millimolar, preferably from about 1×10 ^-4 to 0.1 millimolar.

In the Ziegler-Natta catalyst, the organosilicon compound is generally used in an amount of about 0.001 mol to 10 mol, preferably 0.01 mol to 5 mol, per 1 mol of aluminum atoms in the organoaluminum compound.

In the Ziegler-Natta catalyst, the amount of the organoaluminum compound is usually about 1 to 2000 mol, preferably about 2 to 500 mol, per 1 mol of the titanium atom in the polymerization system in terms of aluminum atoms in the compound. used in

When a raw material containing propylene is polymerized using a Ziegler-Natta catalyst, the prepolymerization catalyst described above may enable polymerization without adding an organosilicon compound and/or an organoaluminum compound. When the catalyst for olefin polymerization is formed from the prepolymerization catalyst, the organosilicon compound and the organoaluminum compound, these organosilicon compounds and organoaluminum compounds can suitably be used in the amounts described above.

In addition, if hydrogen is used in the polymerization of a raw material containing propylene, the molecular weight of the resulting propylene-based polymer (A) can be adjusted, resulting in a polymer having a higher MFR than when hydrogen is not added. can get.

In the method for producing the propylene-based polymer (A) of the present invention, the starting material containing propylene is usually polymerized at a temperature of about 20 to 150° C., preferably about 50 to 100° C., under normal pressure to 100 kg/cm ² , preferably. is performed under a pressure of about 2-50 kg/cm ² .

In the method for producing the propylene-based polymer (A) of the present invention, the polymerization may be carried out in any of a batch system, a semi-continuous system and a continuous system. Moreover, the polymerization may be carried out in two or more stages by changing the polymerization conditions.

The propylene homopolymer (A1), the propylene random copolymer (A2-1), and the propylene/ethylene block copolymer (A2-2) described above are produced by the method for producing the propylene-based polymer (A) of the present invention. ) and other propylene copolymers (A2) can be produced.

The polymerization catalyst (catalyst component, electron donor, etc.) used in the method for producing the propylene-based polymer (A) of the present invention includes not only the above-mentioned polymerization catalysts, but also conventionally known propylene-based polymers. The olefin polymerization catalyst (catalyst component, electron donor, etc.) used can be used without restriction.

Ziegler-Natta catalysts used in the method for producing the propylene polymer (A) of the present invention include, for example, JP-A-8-034814, JP-A-8-034813, JP-A-9-048814, JP-A-9- 048813, JP9-104709, JP8-231630, JP9-328513, JP9-278819, JP9-208615, JP9-031119, JP10-007716 No., JP-A-10-007715, JP-A-9-165414, JP-A-10-030004, JP-A-10-147611, JP-A-10-147610, JP-A-10-158317, JP-A-10-265519 , JP-A-10-060041, JP-A-11-012322, JP-A-11-035620, JP-A-10-316713, JP-A-11-035618, JP-A-11-035622, JP-A-10-287710, JP-A-11-106421, JP-A-11-147907, JP-A-11-158210, JP-A-11-217407, JP-A-11-222504, JP-A-11-302314, JP-A-11-322828, JP 11-116615, JP 2000-026521, JP 2000-026522, JP 2000-044620, JP 2000-344818, JP 2001-106718, JP 2002-097237, JP 2003-026719, JP-A-2003-192718, JP-A-2004-002742, JP-A-2005-112920, JP-A-2005-187550, JP-A-2005-213367, JP-A-2005-126703, JP-A-2006 -199975, JP 2014-051669, JP 2013-227582, JP 2012-233195, JP 2008-024751, JP 2010-111755, JP 2013-249445, JP 2010- 248469, WO 2006/077946, WO 2006/077945, WO 2008/010459, WO 2009/057747, the polymerization catalyst described in WO 2009/069483 (catalyst component , electron donors, etc.).

Examples of the metallocene catalyst used in the method for producing the propylene-based polymer (A) of the present invention include WO 2001/27124, WO 2004/87775, WO 2006/25540, WO 2006/68308, International Publication No. 2006/126610, International Publication No. 2014/050816, International Publication No. 2014/050817, and International Publication No. 2014/142111.

[Method for Producing Propylene Homopolymer (A1)]
The propylene homopolymer (A1) can be prepared, for example, according to the method for producing the propylene-based polymer (A) described above (polymerization conditions such as polymerization catalyst, etc.). mixture) is supplied to a polymerization reactor, and this raw material is polymerized with a polymerization catalyst.

As described above, the propylene homopolymer (A1) contains only propylene as its raw material olefin, and the propylene consists only of biomass-derived propylene.

The propylene homopolymer (A1) desirably satisfies the above-mentioned (i) that the MFR is within a specific range. In order to make the MFR within this specific range, for example, the ratio of propylene and hydrogen supplied to the polymerization reactor may be appropriately adjusted (generally, the higher the concentration of hydrogen relative to propylene, the higher the melt flow rate (MFR) becomes larger).

The propylene homopolymer (A1) desirably satisfies the above-mentioned (ii) that the isotactic pentad fraction is within a specific range. In order to set the isotactic pentad fraction within a specific range, for example, the type of polymerization catalyst and the type of electron donor used for polymerization may be appropriately selected.

As the polymerization conditions for the propylene homopolymer (A1), the same conditions as those for the above-described propylene-based polymer (A) can be employed. In addition, as the polymerization conditions, known polymerization conditions for propylene-based polymers or conforming to known polymerization conditions may be employed.
For example, the polymerization of propylene introduced into the polymerization vessel may be carried out by a liquid phase polymerization method such as a bulk polymerization method, a solution polymerization method or a suspension (slurry) polymerization method, or may be carried out by a gas phase polymerization method. good. Moreover, such polymerization may be carried out by combining a plurality of these polymerization methods.

In addition, such polymerization is batch polymerization in which the concentration of propylene supplied to the polymerization vessel and the concentration of hydrogen added as necessary are discontinuously changed in one polymerization vessel; two or more polymerization vessels are connected in parallel by piping. , the polymerization conditions of each polymerization vessel (temperature, pressure, propylene concentration, concentration of hydrogen added as necessary, catalyst to be used/catalyst supply amount, type/supply amount of external electron donor, organoaluminum compound type and supply amount, ratio of the volume of the polymerization vessel to the volume of the liquid substance, etc.) can be set arbitrarily; temperature, pressure, propylene concentration, hydrogen concentration, type and supply amount of external electron donor, type and supply amount of organoaluminum compound, ratio of volume of polymerization vessel to volume of liquid substance, etc.) Any of the catalyst supplied to the second polymerization vessel and continuous polymerization in which the amount of catalyst supplied per hour is arbitrarily set may be selected.

Further, in the method for producing the propylene homopolymer (A1), for example, No., JP-A-2004-175933 and JP-A-2020-090621 can be employed.

[Method for Producing Propylene-Based Random Copolymer (A2-1)]
The propylene-based random copolymer (A2-1) contains propylene and an olefin (b), for example, according to the method for producing the propylene-based polymer (A) described above (polymerization conditions such as a polymerization catalyst). It can be produced by supplying a raw material (a raw material satisfying the above condition (I)) to a polymerization vessel and subjecting the raw material to random copolymerization using a polymerization catalyst.

The description of preferred aspects of the raw material (e.g., aspects of the olefin (b)) is the same as described in the section on the propylene-based random copolymer (A2-1).

The propylene-based random copolymer (A2-1) preferably satisfies the above-mentioned (iii) that the MFR is within a specific range. In order to make the MFR within this specific range, for example, the ratio of the olefin (propylene, olefin (b)), which is the raw material to be supplied to the polymerization reactor, and hydrogen may be appropriately adjusted (the hydrogen concentration with respect to propylene is high the higher the melt flow rate (MFR) generally.).

The propylene-based random copolymer (A2-1) preferably satisfies the above-mentioned (iv) that the melting point is within a specific range. In order to set the melting point within a specific range, for example, the ratio between propylene and the olefin (b) contained in the raw material may be appropriately adjusted (the higher the ratio of olefin (b) to propylene, the lower the melting point). ), the type of polymerization catalyst, and the type of electron donor used for polymerization may be appropriately selected.

As the polymerization conditions for the propylene-based random copolymer (A2-1), the same conditions as those for the above-described propylene-based polymer (A) can be employed. In addition, as the polymerization conditions, known polymerization conditions for propylene-based polymers or conforming to known polymerization conditions may be employed.
For example, the polymerization of the raw material containing propylene introduced into the polymerization vessel may be carried out by a liquid phase polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension (slurry) polymerization method, or by a gas phase polymerization method. You may Moreover, such polymerization may be carried out by combining a plurality of these polymerization methods.

In addition, such polymerization is batch polymerization in which the concentration of propylene and olefin (b) supplied to the polymerization vessel and the concentration of hydrogen added as necessary are discontinuously changed in one polymerization vessel; The polymerization reactors were connected in parallel by piping, and the polymerization conditions for each reactor (temperature, pressure, concentration of propylene and olefin (b), concentration of hydrogen added as necessary, catalyst to be used/catalyst supply amount, external type and supply amount of electron donor, type and supply amount of organoaluminum compound, ratio of volume of polymerization vessel to volume of liquid substance, etc.); Connected in series, the polymerization conditions of each polymerization vessel (temperature, pressure, concentration of propylene and olefin (b), hydrogen concentration, type and supply amount of external electron donor, type and supply amount of organoaluminum compound, volume of polymerization vessel and the volume ratio of the liquid substance, etc.), the catalyst supplied to the first polymerization vessel, and the continuous polymerization in which the amount of catalyst supplied per hour is arbitrarily set.

Further, in the method for producing the propylene-based random copolymer (A2-1), for example, JP-A-63-069809, JP-A-11-12310, JP-A-11-12308, JP-A-2001-48915, JP-A-2001-48915, Polymerization methods described in JP-A-2004-175976, JP-A-2004-175933, and JP-A-2020-090621 can be employed.

[Method for Producing Propylene/Ethylene Block Copolymer (A2-2)]
The propylene/ethylene block copolymer (A2-2) can be prepared, for example, according to the method for producing the propylene-based polymer (A) described above (polymerization conditions such as a polymerization catalyst).
A raw material (1) containing propylene or propylene and ethylene is supplied to a polymerization vessel and polymerized with a polymerization catalyst,
A crystalline propylene-based polymer comprising a propylene homopolymer or a crystalline propylene/ethylene random copolymer containing 95% by weight or more and less than 100% by weight of structural units derived from propylene and 5% by weight or less of structural units derived from ethylene. A step (α) of preparing component (c), and supplying raw material (2) containing propylene and ethylene to a polymerization vessel and polymerizing with a polymerization catalyst to prepare propylene/ethylene random copolymer component (d). It can be produced by a production method including the step (β) of

In the method for producing the propylene/ethylene block copolymer (A2-2), the propylene contained in the raw materials (1) and (2) must be composed of only biomass-derived propylene.

Descriptions of preferred aspects (e.g. aspects of ethylene) regarding the raw materials (raw materials (1) and (2)) are the same as those described in the section on the propylene/ethylene block copolymer (A2-2).

In the method for producing the propylene/ethylene block copolymer (A2-2), the step (α) of producing the crystalline propylene-based polymer component (c) is usually carried out as the first polymerization step, followed by the second polymerization step. As the polymerization step, the step (β) of preparing the propylene/ethylene random copolymer component (d) is carried out.

In the step (α), the crystalline propylene-based polymer component (c) contained in the propylene/ethylene block copolymer (A2-2) is prepared. The crystalline propylene-based polymer component (c) preferably satisfies the above-mentioned (v) that the intrinsic viscosity is within a specific range. When the crystalline propylene-based polymer component (c) is a propylene homopolymer, propylene is supplied to the polymerization reactor as a starting material for the polymer. At that time, in order to make the intrinsic viscosity [η] satisfy (v), for example, the ratio of hydrogen and propylene supplied to the polymerization vessel may be appropriately adjusted (the ratio of hydrogen to propylene is Generally, the higher the intrinsic viscosity, the smaller the [η]). When the crystalline propylene-based polymer component (c) is a propylene/ethylene random copolymer, propylene and ethylene are supplied to the polymerization vessel as starting materials for the polymer. At that time, in order that the intrinsic viscosity [η] satisfies (v), for example, the ratio of hydrogen and propylene supplied to the polymerization vessel should be appropriately adjusted as in the case of producing a propylene homopolymer. should be adjusted to Further, when the crystalline propylene-based polymer component (c) is a propylene/ethylene random copolymer, the desired value of 95% by weight or more and less than 100% by weight of structural units derived from propylene is added to the polymerization vessel. The ratio of supplied propylene and ethylene may be appropriately adjusted.

Further, the step (α) for producing the crystalline propylene-based polymer component (c) may be carried out by one-stage polymerization carried out in one polymerization vessel, but two-stage polymerization carried out in two or more polymerization vessels. The above polymerization may be carried out, and when the polymerization is carried out in two or more stages, the polymerization conditions in each stage may be the same or different.

In the step (β), 20% by weight or more and 80% by weight or less of the structural units derived from propylene and 20% by weight or more and 80% by weight or less of the structural units derived from ethylene contained in the propylene/ethylene block copolymer (A2-2). Propylene and ethylene are supplied to a polymerization vessel to produce a propylene/ethylene random copolymer component (d) containing. In order to make the proportion of structural units derived from propylene and the proportion of structural units derived from ethylene within the above-described desired values, the proportion of propylene and ethylene supplied to the polymerization reactor may be adjusted appropriately. Further, it is desirable that the propylene/ethylene random copolymer component (d) satisfies the above-mentioned (vi) that the intrinsic viscosity is within a specific range. In order to make the intrinsic viscosity [η] satisfy (vi), for example, the ratio of hydrogen and propylene supplied to the polymerization reactor may be adjusted appropriately.

The step (β) of producing the propylene/ethylene random copolymer component (d) may be carried out by one-stage polymerization carried out in one polymerization vessel, but two-stage polymerization carried out in two or more polymerization vessels may be carried out. Polymerization may be carried out in stages or more, and in the case of carrying out polymerization in two or more stages, the polymerization conditions in each stage may be the same or different.

In order to bring the ratio of the crystalline propylene-based polymer component (c) and the propylene/ethylene random copolymer component (d) into the desired range, for example, the crystalline propylene-based polymer component (c) is polymerized. The polymerization activity in the step (α), the residence time of the polymerized particles in the polymerization vessel, etc. are appropriately adjusted, and the polymerization activity in the step (β) of polymerizing the propylene/ethylene random copolymer component (d) and the polymerization vessel of the polymerized particles. The internal retention time and the like may be appropriately adjusted.

As the polymerization conditions for the propylene/ethylene block copolymer (A2-2), the same conditions as those for the above-described propylene-based polymer (A) can be employed. In addition, as the polymerization conditions, known polymerization conditions for propylene-based polymers or conforming to known polymerization conditions may be employed.
For example, the polymerization of the raw material containing propylene introduced into the polymerization vessel may be carried out by a liquid phase polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension (slurry) polymerization method, or by a gas phase polymerization method. You may Moreover, such polymerization may be carried out by combining a plurality of these polymerization methods.

In addition, such polymerization is batch polymerization in which the concentration of propylene and ethylene supplied to the polymerization vessel and the concentration of hydrogen added as necessary are changed discontinuously in one polymerization vessel; two or more polymerization vessels are used. Connected in parallel with piping, the polymerization conditions of each polymerization vessel (temperature, pressure, concentration of propylene and ethylene, concentration of hydrogen added as necessary, catalyst to be used, amount of catalyst supplied, type of external electron donor, supply amount, type and supply amount of organoaluminum compound, ratio of the volume of the polymerization vessel to the volume of the liquid substance, etc.); Polymerization conditions of the polymerization vessel (temperature, pressure, concentration of propylene and ethylene, concentration of hydrogen, type and supply amount of external electron donor, type and supply amount of organoaluminum compound, ratio of volume of polymerization vessel to volume of liquid substance, etc.) may be arbitrarily set, and any of the catalyst supplied to the first polymerization vessel and the continuous polymerization in which the catalyst supply amount per hour may be arbitrarily set may be selected.

Further, in the method for producing the propylene/ethylene block copolymer (A2-2), for example, JP-A-63-069809, JP-A-63-305115, JP-A-1-201309, JP-A-8-231661 , JP-A-8-231662, JP-A-11-12310, JP-A-2004-175976, JP-A-2004-175933, JP-A-2014-214202, JP-A-2016-84387, JP-A-2020-090621 The polymerization methods described can be employed.

[Resin composition]
The propylene-based polymer (A) obtained as described above in the present invention replaces part or all of the fossil-fuel-derived propylene-based polymer obtained using only a fossil-fuel-derived olefin as a raw material, and is a propylene-based polymer. It can be used as a resin composition containing Depending on the purpose, such a resin composition further contains, as a propylene polymer, a propylene polymer obtained from an olefin mixture containing a biomass-derived olefin and a fossil fuel-derived olefin as a raw material. good too. Further, the resin composition may contain only the propylene-based polymer (A) as the propylene-based polymer, or may contain the propylene-based polymer (A) and the fossil fuel as the propylene-based polymer. Mixtures with derived propylene-based polymers may also be included. As the resin composition of the present invention, the following resin compositions can be exemplified.

[Resin composition containing propylene homopolymer (A1)]
In a resin composition containing a conventionally known propylene homopolymer, part or all of the conventionally known propylene homopolymer is replaced with the propylene homopolymer (A1) of the present invention, and the propylene homopolymer (A1) is included. As a resin composition, this resin composition can be used.

When replacing the conventionally known propylene homopolymer with the propylene homopolymer (A1), stereoregularity, average molecular weight, molecular weight distribution, catalyst residue, molecular structure other than the presence or absence of ¹⁴ C isotope, and contained components If the properties of the polymer are the same, the performance of the resin composition can be the same even after the replacement. This replacement makes it possible to reduce the environmental load (reduce greenhouse gas emissions) in the life cycle of the polymer, from manufacture, processing, use, and disposal.

The resin composition containing the propylene homopolymer (A1) is a resin composition containing two or more propylene homopolymers (A1) different in MFR or intrinsic viscosity, and different in average stereoregularity (pentad fraction). A resin composition containing two or more propylene homopolymers (A1), a resin composition containing a propylene homopolymer (A1) and a propylene random copolymer, a propylene homopolymer (A1) and a propylene/ethylene block copolymer a resin composition containing a polymer, a resin composition containing a propylene homopolymer (A1) and an ethylene-based polymer, a resin composition containing a propylene homopolymer (A1) and a nucleating agent, a propylene homopolymer ( Examples include a resin composition containing A1) and a filler.

As the resin composition containing the propylene homopolymer (A1), for example, WO 2002/074855, WO 2019/00418, JP 2002-20560, JP 11-255987, JP 2019 -137847, JP 2019-137848, JP 2020-158787, International Publication No. 2020/091051, JP 2019-172730, International Publication No. 2017/195787, JP 2017-218509, International Publication No. 2016/159069, JP-A-2000-319463, JP-A-2000-302925, JP-A-2004-315582, JP-A-2004-2655, JP-A-1-156353, JP-A-2003-41072 In the resin composition containing a propylene homopolymer, examples of the propylene homopolymer include a resin composition using the propylene homopolymer (A1) of the present invention. The propylene homopolymer contained in these resin compositions may be only the propylene homopolymer (A1), but may be a mixture of the propylene homopolymer (A1) and the fossil fuel-derived propylene homopolymer. good too. When the resin composition contains an ethylene-based polymer, the ethylene-based polymer may contain a biomass-derived ethylene-based polymer as the ethylene-based polymer, the raw material of which is biomass-derived ethylene.

[Resin composition containing propylene-based random copolymer (A2-1)]
In a resin composition containing a conventionally known propylene-based random copolymer that is a random copolymer of propylene and an olefin (b), a part or all of the conventionally-known propylene-based random copolymer is added to the resin composition of the present invention. A resin composition containing the propylene-based random copolymer (A2-1) can be substituted by the propylene-based random copolymer (A2-1), and this resin composition can be used.

When replacing conventionally known propylene-based random copolymers with propylene-based random copolymers (A2-1), stereoregularity, average molecular weight, molecular weight distribution, catalyst residue, etc., molecular structure other than the presence or absence of ¹⁴ C isotope If the properties of these polymers such as the components and components are the same, the performance of the resin composition can be the same even after the replacement. This replacement makes it possible to reduce the environmental load (reduce greenhouse gas emissions) in the life cycle of the polymer, from manufacture, processing, use, and disposal.

The resin composition containing the propylene random copolymer (A2-1) includes, for example, a resin composition containing the propylene random copolymer (A2-1) and a propylene homopolymer, an olefin (b) (ethylene and at least one olefin selected from the group consisting of α-olefins having 4 to 8 carbon atoms). A resin composition containing a polymer (A2-1) and a propylene/ethylene block copolymer, a resin composition containing a propylene-based random copolymer (A2-1) and another resin such as an ethylene-based polymer, A propylene-based random copolymer (A2-1) and various additives such as antioxidants, ultraviolet absorbers, lubricants, nucleating agents, antistatic agents, flame retardants, pigments, dyes, and inorganic or organic fillers. and a resin composition containing

Examples of the resin composition containing the propylene-based random copolymer (A2-1) include JP-A-5-311017, JP-A-8-283491, JP-A-9-20846, JP-A-9-194537, JP 10-168252, JP 2000-159946, JP 2001-172402, JP 2001-151960, JP 2002-275333, JP 2005-112884, JP 2006-036828, JP 2001-31804, WO 2015/137262, and JP-A-2019-049001, the propylene-based random copolymer of the present invention is used as the propylene-based random copolymer in the resin composition containing the propylene-based random copolymer. A resin composition using the copolymer (A2-1) may be mentioned. The propylene-based random copolymer contained in these resin compositions may be only the propylene-based random copolymer (A2-1), but the propylene-based random copolymer (A2-1) and fossil fuel It may be a mixture of derived propylene-based random copolymers. When the resin composition contains an ethylene-based polymer, the ethylene-based polymer may contain a biomass-derived ethylene-based polymer whose raw material is biomass-derived ethylene as the ethylene-based polymer. .

[Resin Composition Containing Propylene/Ethylene Block Copolymer (A2-2)]
In a propylene resin composition containing a conventionally known propylene/ethylene block copolymer, part or all of a conventionally known propylene/ethylene block copolymer is replaced with the propylene/ethylene block copolymer of the present invention (A2- 2) to obtain a resin composition containing the propylene/ethylene block copolymer (A2-2), and this resin composition can be used.

When replacing a conventionally known propylene/ethylene block copolymer with a propylene/ethylene block copolymer (A2-2), stereoregularity, average molecular weight, molecular weight distribution, comonomer species, comonomer amount, Composition distribution, ethylene content of propylene/ethylene random copolymer (content of structural units derived from ethylene), molecular weight (intrinsic viscosity), content of each of these components in the block copolymer as a whole, ¹⁴ C isotope If the properties of these polymers, such as the molecular structure and components other than the presence or absence of , are the same, the performance of the resin composition can be the same even after replacement. This replacement makes it possible to reduce the environmental load (reduce greenhouse gas emissions) in the life cycle of the polymer, from manufacture, processing, use, and disposal.

Examples of the resin composition containing the propylene/ethylene block copolymer (A2-2) include a resin composition containing the propylene/ethylene block copolymer (A2-2) and a propylene homopolymer, a propylene/ethylene block copolymer A resin composition containing the coalescence (A2-2) and a propylene random copolymer, and two or more propylene-ethylene random copolymers with different ethylene contents, molecular weights (intrinsic viscosities), etc. in the block copolymer. Resin composition containing ethylene block copolymer (A2-2), resin composition containing propylene/ethylene block copolymer (A2-2) and other resin such as ethylene-based copolymer, propylene/ethylene block Resin composition containing copolymer (A2-2) and specific additive, propylene/ethylene block copolymer (A2-2) and talc, short glass fiber, short carbon fiber, long glass fiber, long carbon fiber and resin compositions containing fillers such as

Examples of the resin composition containing the propylene/ethylene block copolymer (A2-2) include JP-A-6-157867, JP-A-7-179719, JP-A-9-3296, JP-A-9-71712, JP 9-165477, JP 2005-264032, JP 2005-264033, WO 2005/001276, JP 2008-163320, WO 2010/050509, WO 2014/073510 No., International Publication No. 2015/005239, International Publication No. 2019/139125, International Publication No. 2020/175138, International Publication No. 2019/139125, International Publication No. 2020/175138. Examples of resin compositions containing coalescence include resin compositions using the propylene/ethylene block copolymer (A2-2) of the present invention for at least part or all of the propylene/ethylene block copolymer. The propylene/ethylene block copolymer contained in these resin compositions may be only the propylene/ethylene block copolymer (A2-2), but the propylene/ethylene block copolymer (A2-2) and a mixture of a fossil fuel-derived propylene/ethylene block copolymer. When the resin composition contains an ethylene-based polymer, the ethylene-based polymer may contain a biomass-derived ethylene-based polymer whose raw material is biomass-derived ethylene as the ethylene-based polymer. .

[Long fiber reinforced polypropylene resin]
Conventionally known long fiber reinforced propylene resins, for example, long fiber reinforced polypropylene described in JP-A-2005-82786, WO 2006/02809, WO 2006/043620, and WO 2006/028091 In the resin (manufacturing method), part or all of the propylene-based polymer can be replaced with the propylene-based polymer (A) of the present invention to use as a long-fiber-reinforced polypropylene resin. When replacing a propylene-based polymer, stereoregularity, average molecular weight, molecular weight distribution, comonomer type, comonomer amount, composition distribution, etc. of the propylene-based polymer, ethylene content and molecular weight (intrinsic viscosity) of the propylene-ethylene random copolymer If the properties of the polymer, such as the content of the entire resin and the molecular structure other than the presence or absence of the ¹⁴ C isotope, and the contained components, are the same, the performance of the resin composition can be the same even after the replacement. This replacement makes it possible to reduce the environmental load (reduce greenhouse gas emissions) in the life cycle of the polymer, from manufacture, processing, use, and disposal.

The propylene-based polymer contained in the resin composition may be the propylene-based polymer (A) alone, or may be a mixture of the propylene-based polymer (A) and the fossil fuel-derived propylene-based polymer. .

[Other ingredients]
The propylene-based polymer (A) or the resin composition containing the propylene-based polymer (A) of the present invention may contain other components such as the following additives.

<Additive>
The propylene-based polymer (A) or the resin composition containing the propylene-based polymer (A) of the present invention may contain additives. Such additives include, for example, stabilizers such as heat stabilizers, weather stabilizers, and light stabilizers, chloride absorbents, fillers such as inorganic fillers, α crystal nucleating agents, β crystal nucleating agents, softening agents, 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, carbon Organic fillers such as black include wood flour, cellulose, polyester fiber, nylon fiber, kenaf fiber, bamboo fiber, jude fiber, rice flour, starch, corn starch, and the like. Among these inorganic fillers, talc, magnesium sulfate fiber, glass fiber, and carbon fiber are preferred. When these inorganic fillers are used as components of the resin composition containing the propylene-based polymer (A), the content of the inorganic filler 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 preferably used, and typical examples thereof include fatty acid amides, monoglycerides, etc. Among them, fatty acid amides are 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 Among them, oleic acid amide, stearic acid amide, erucic acid amide and dimers of erucic acid amide are preferred, and erucic acid amide is more preferred. . These can be used individually by 1 type or in mixture of 2 or more types.

<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, known carbon black can be used without particular limitation. The average particle size of carbon black is also not limited, but its primary particles are preferably 10 to 40 nm.

<Aluminum flake>
The aluminum flakes can be produced by a known method. Specifically, for example, it can be produced by pulverizing or grinding materials such as atomized powder, aluminum foil, vapor-deposited aluminum foil, etc., using an apparatus such as a ball mill, an attritor, a stamp mill, or the like. In particular, aluminum flakes obtained by grinding aluminum powder (atomized powder) obtained by an atomizing method with a ball mill are preferable. The purity of aluminum is not particularly limited, and it may be an alloy 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 diameter of the aluminum flakes is preferably 5-90 μm, more preferably 10-70 μm. Aluminum flakes may be used singly or in combination of two or more.

[denaturation]
The propylene-based polymer (A) or the resin composition containing the propylene-based polymer (A) of the present invention is modified by a known method with a modifying compound such as an α,β-unsaturated carboxylic acid or an acid anhydride thereof. may Such modification is performed, for example, by dissolving the propylene-based polymer (A) or the propylene-based polymer (A) and α,β-unsaturated carboxylic acid and/or its acid anhydride in a solvent, or The reaction can be carried out in the presence of a radical generator in the melt-kneaded state of the resin composition.

As the α,β-unsaturated carboxylic acid and its acid anhydride, those having 20 or less carbon atoms, particularly those having 4 to 16 carbon atoms are suitable, and specifically, acrylic acid, methacrylic acid, ethacrylic acid, and malein. acids, fumaric acid, itaconic acid, citraconic acid, 3,6-endomethylene-2,3,4,6-tetrahydrocis-phthalic acid and anhydrides thereof.

[Molded body]
Conventionally known propylene-based polymers (propylene homopolymers, propylene-based random copolymers obtained by random copolymerization of propylene and olefin (b), propylene copolymers such as propylene/ethylene block copolymers) Part or all of the propylene polymer (A) (propylene homopolymer (A1), propylene random copolymer (A2-1), propylene copolymer such as propylene/ethylene block copolymer (A2-2) The molded article of the present invention can be obtained by replacing with coalescence (A2)) and molding the replaced polymer. Further, the molded article of the present invention can be obtained by molding a resin composition containing a propylene-based polymer in which a part or all of the conventional propylene-based polymer is replaced with the propylene-based polymer (A).

When replacing a conventionally known propylene-based polymer with the propylene-based polymer (A), stereoregularity, average molecular weight, molecular weight distribution, type of comonomer, amount of comonomer, molecular structure other than the presence or absence of ¹⁴ C isotope, etc. If the properties of these polymers are the same, the performance of the molded article can be the same even after replacement. This replacement makes it possible to reduce the environmental load (reduce greenhouse gas emissions) in the life cycle of the polymer, from manufacture, processing, use, and disposal.

The propylene-based polymer (A) of the present invention (propylene homopolymer (A1), propylene-based random copolymer (A2-1), propylene copolymer such as propylene/ethylene block copolymer (A2-2) ( A2)) and a resin composition containing a propylene-based polymer (A) can be subjected to injection molding, extrusion molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, injection stretch blow molding, press molding (compression molding). , vacuum molding, calendar molding, foam molding, injection foam molding, foam blow molding, blow molding, and other known molding methods can be used to form various molded bodies.

<Injection molding>
The propylene-based polymer (A) and the resin composition containing the propylene-based polymer (A) of the present invention can be molded into molded articles for various uses by injection molding.
As a method of injection molding, for example, JP-A-9-3296, JP-A-9-71712, JP-A-9-165477, JP-A-2004-83608, JP-A-2004-256606, JP-A-2005-264032 , JP 2005-264033, JP 2005-325333, JP 2006-307038, WO 2010/074001, WO 2010/050509, WO 2014/073510, WO 2015 /005239, International Publication No. 2019/139125, International Publication No. 2019/139125, International Publication No. 2020/175138, International Publication No. 2019/139125, International Publication No. 2020/175138, JP 2021-025015 and injection molding of the propylene-based polymer or the resin composition containing the propylene-based polymer.

<Injection foam molding>
The propylene-based polymer (A) of the present invention and a resin composition containing the propylene-based polymer (A) can be formed into molded articles for various uses by injection foam molding.
Methods of injection foam molding include, for example, JP-A-2002-79545, JP-A-2004-359877, JP-A-2006-159898, JP-A-2004-307665, JP-A-2008-144022, and JP-A-2008-163320. No., JP 2014-181317, JP 2015-10102, International Publication No. 2016068164, JP 2017-217833, JP 2017-218509, JP 2019-89891, JP 2020-152781 A method of injection foam molding of the described propylene-based polymer or a resin composition containing the propylene-based polymer can be mentioned.

<Blow molding>
The propylene-based polymer (A) and the resin composition containing the propylene-based polymer (A) of the present invention can be made into moldings for various uses by hollow molding.
As a method of blow molding, for example, the propylene described in WO 2011/090101, WO 2015/137268, JP 2015-168788, WO 2015/137262, JP 2020-090616 and a method of blow molding a resin composition containing a propylene-based polymer or a propylene-based polymer.

<Foam blow molding>
The propylene-based polymer (A) of the present invention and a resin composition containing the propylene-based polymer (A) can be formed into molded articles for various uses by foam blow molding.
The method of foam blow molding includes, for example, a method of foam blow molding of a propylene-based polymer or a resin composition containing a propylene-based polymer described in WO 2011/118281.

<Injection stretch blow molding>
The propylene-based polymer (A) of the present invention and a resin composition containing the propylene-based polymer (A) can be molded into molded articles for various uses by injection stretch blow molding.
As a method of injection stretch blow molding, for example, the propylene-based polymer described in WO 2015/137268, WO 2019/139125, WO 2019/139125, WO 2020/175138 or A method of injection stretch blow molding of a resin composition containing a propylene-based polymer is mentioned.

<Compression molding>
The propylene-based polymer (A) of the present invention and a resin composition containing the propylene-based polymer (A) can be formed into molded articles for various uses by compression molding.
The method of compression molding includes, for example, a method of compression molding a propylene-based polymer or a resin composition containing a propylene-based polymer described in JP-A-2009-84393.

Examples of molded articles produced by the molding method include the following.
<Tube, tube>
The propylene-based polymer (A) of the present invention and a resin composition containing the propylene-based polymer (A) can be molded into tubes and pipes for various purposes by molding methods such as extrusion molding. A tube or pipe can be produced, for example, by a method of forming a tube or pipe from a propylene-based polymer or a resin composition containing a propylene-based polymer described in JP-A-2012-96828.

<Biaxially stretched film>
Biaxially stretched films for various applications can be formed by biaxially stretching the propylene-based polymer (A) of the present invention and a resin composition containing the propylene-based polymer (A). Biaxially stretched film, for example, JP-A-1-156353, JP-A-7-76641, JP-A-2002-275333, JP-A-2004-315582, JP-A-2006-299229, JP-A-2020-105358, JP 2004-175932, WO 2016/159044, WO 2016/017752, WO 2010/087328, JP 2010-219329, JP 2008-133351, JP 2006-143975 No., JP-A-2006-282761, JP-A-2016-187933, JP-A-2016-187934, JP-A-2017-177699, JP-A-2017-177726, the propylene-based polymer described in JP-A-2017-177727 Alternatively, it can be produced by a method of forming a biaxially stretched molded film from a resin composition containing a propylene-based polymer. Incidentally, such a biaxially stretched film may be a single layer or a laminate.

<Unstretched film>
By forming a non-stretched film from the propylene-based polymer (A) of the present invention and a resin composition containing the propylene-based polymer (A), a non-stretched film for use in various applications can be formed. Non-stretched films, for example, JP-A-2002-338762, JP-A-7-233290, JP-A-8-85711, JP-A-9-208629, JP-A-9-272718, JP-A-11-106433, JP 2002-317012, WO 2021/025142, JP 2006-52314, JP 2000-119480, JP 2001-261921, WO 2019/189486, JP 2009-161590, Unstretched film from a propylene-based polymer or a resin composition containing a propylene-based polymer described in WO 2014/030594, WO 2016/158982, JP-A-2015-193181, and JP-A-2020-114908 It can be produced by a method of molding. In addition, such a non-stretched film may be a single layer or a laminate.

<Sheet/Vacuum molding>
By sheet-molding the propylene-based polymer (A) of the present invention and a resin composition containing the propylene-based polymer (A), sheets for various purposes can be molded. Further, such a sheet can be further vacuum-formed to obtain a vacuum-formed body for use in various applications. Sheets and vacuum formed bodies, for example, JP-A-2005-97548, JP-A-2002-284942, JP-A-7-33920, JP-A-2001-2859, JP-A-2015-124362, International Publication No. 2016/114393 No., JP-A-2010-168052, and JP-A-2014-169446, a method for forming a sheet from a propylene-based polymer or a resin composition containing a propylene-based polymer, and a vacuum formed body from the obtained sheet. It can be produced by the method of Such sheets and vacuum-formed bodies may be single layers or laminates.

<Foam sheet>
By forming a foam sheet from the propylene-based polymer (A) of the present invention and a resin composition containing the propylene-based polymer (A), a foam sheet for use in various applications can be formed. The foamed sheet is formed from a resin composition containing a propylene-based polymer or a propylene-based polymer described in, for example, JP-A-2018-109104, WO-2006/054715, and JP-A-2009-221473. method. In addition, such a foam sheet may be a single layer or a laminate.

<Extrusion laminate product>
By subjecting the propylene-based polymer (A) of the present invention and a resin composition containing the propylene-based polymer (A) to extrusion lamination molding, an extrusion laminated product for use in various applications can be produced. The extrusion laminate product can be produced, for example, by a method for producing an extrusion laminate product from a propylene-based polymer or a resin composition containing a propylene-based polymer described in JP-A-2-281055 and JP-A-2017-132134. The laminate layer of such an extrusion laminate product may be a single layer or a laminate.

<Fiber/non-woven fabric>
The propylene-based polymer (A) of the present invention and the resin composition containing the propylene-based polymer (A) can be filament-formed, for example, by a winder to obtain fibers used for various purposes. Nonwovens for various applications can be obtained by molding or spunbond molding. The fiber or nonwoven fabric is, for example, a resin composition containing a propylene-based polymer or a propylene-based polymer described in JP-A-2009-84708, JP-A-2002-105828, JP-A-7-157922, and JP-A-2006-169273. It can be produced by a method for producing fibers or non-woven fabrics from materials.

<Shrink film>
From the propylene-based polymer (A) of the present invention and a resin composition containing the propylene-based polymer (A), for example, a shrink film for various purposes can be produced by stretching film molding. Shrink films are described, for example, in JP-A-10-168252, JP-A-2002-363308, JP-A-10-152531, JP-A-2001-171001, JP-A-2010-189473, and JP-A-2000-159946. It can be produced by a method for producing a shrink film from a propylene-based polymer or a resin composition containing a propylene-based polymer. In addition, such a shrink film may be a single layer or a laminate.

<Separator>
Separators for various applications can be produced from the propylene-based polymer (A) of the present invention and a resin composition containing the propylene-based polymer (A), for example, by stretching film molding. The separator is, for example, a method of producing a separator from a propylene-based polymer or a resin composition containing a propylene-based polymer described in JP-A-2020-114909, WO2014/065331, and WO2010/079784. can be produced by The resin layer that constitutes the separator may be a single layer or multiple layers.

<Application>
Molded articles obtained from the propylene-based polymer (A) of the present invention and a resin composition containing the propylene-based polymer (A) by the above-described method can be used for automobile parts, containers for food and medical applications, and food applications. and packaging materials for electronic materials.

Automobile parts include, for example, automobile exterior parts such as bumpers, side moldings, and aerodynamic undercovers; automobile interior parts such as instrument panels and interior trim; exterior plate parts such as fenders, door panels, and steps; engine covers, fans, and fans. parts around the engine such as a shroud; and the like.

Containers for food and medical applications include, for example, tableware, retort containers, freezer storage containers, retort pouches, microwave heat-resistant containers, frozen food containers, frozen dessert cups, cups, food containers such as beverage bottles, retort containers, and bottles. Containers, blood transfusion sets, medical bottles, medical containers, medical hollow bottles, medical bags, infusion bags, blood storage bags, infusion bottles, chemical 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, confectionery packaging, oxygen absorber packaging, retort food packaging, freshness Retaining film, pharmaceutical packaging, cell culture bag, cell inspection film, bulb packaging, seed packaging, vegetable/mushroom cultivation film, heat-resistant vacuum-formed container, prepared dish container, prepared dish lid, commercial wrap film, home use wrapping film, baking carton, etc.

When the molded article of the present invention is a film, sheet, tape, or the like, its uses include, for example, protective films for polarizing plates, protective films for liquid crystal panels, protective films for optical parts, protective films for lenses, and electrical parts.・Protective films for electrical appliances, protective films for mobile phones, protective films for personal computers, masking films, films for capacitors, reflective films, laminates (including glass), radiation-resistant films, γ-ray-resistant films, porous films, etc. etc.

Other uses of the molded article of the present invention include, for example, housings for home electric appliances, hoses, tubes, wire covering materials, insulators for high-voltage wires, tubes for spraying cosmetics and perfumes, medical tubes, infusion tubes, pipes, and wires. Harnesses, interior materials for motorcycles, railway vehicles, aircraft, ships, instrument panel skins, door trim skins, rear package trim skins, ceiling skins, rear pillar skins, seat back garnishes, console boxes, armrests, airbag case lids, shift knobs , assist grips, side step mats, reclining covers, seats in the trunk, seat belt buckles, molding materials such as inner/outer moldings, roof moldings, belt moldings, automotive sealing materials such as door seals and body seals, glass run channels, mud kicking plates, step mats, number plate housings, hose members for automobiles, air duct hoses, air duct covers, air intake pipes, air dam skirts, timing belt cover seals, bonnet cushions, door cushions and other automotive interior and exterior materials, damping tires , static and dynamic 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 packing, furniture・Surface material for footwear, clothing, bags, building materials, building sealing materials, waterproof sheets, building material sheets, building gaskets, window films for building materials, iron core protection members, gaskets, doors, door frames, window frames, rims, Baseboards, opening frames, flooring materials, ceiling materials, wallpaper, health goods (e.g. non-slip mats/sheets, fall prevention films/mats/sheets), health equipment components, shock absorbing pads, protectors/protective equipment (e.g. : helmets, guards), sports goods (e.g. sports grips, protectors), sports protective gear, rackets, mouth guards, balls, golf balls, transport equipment (e.g. impact-absorbing grips for transportation, impact-absorbing sheets), damping Pallets, shock-absorbing dampers, insulators, shock-absorbing materials for footwear, shock-absorbing foams, shock-absorbing materials such as shock-absorbing films, grip materials, miscellaneous goods, toys, shoe soles, shoe soles, shoe midsoles and inner soles, Soles, sandals, suction cups, toothbrushes, flooring materials, gymnastics mats, electric tool components, agricultural equipment components, heat dissipation materials, transparent substrates, soundproofing materials, cushioning materials, electrical cables, shape memory materials, medical gaskets, medical caps, medicines Stoppers, gaskets, packing materials for high-temperature processing such as boiling and 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, OA printer legs, FAX legs, sewing machine legs, motor support mats, precision equipment and OA equipment support members such as audio vibration-proof materials, heat-resistant packing for OA, animal cages , beakers, graduated cylinders and other physics and chemistry experiment equipment, optical measurement cells, costume cases, clear cases, clear files, clear sheets, desk mats, and fibers, such as nonwoven fabrics, elastic nonwoven fabrics, fibers, waterproof fabrics, Breathable fabrics and cloths, paper diapers, sanitary products, sanitary products, filters, bag filters, dust collection filters, air cleaners, hollow fiber filters, water purification filters, gas separation membranes, and the like.

In the molded article made of a conventional propylene-based polymer, the composition containing the propylene-based polymer, and the molded article made of the composition, part or all of the propylene-based polymer is replaced with the propylene-based polymer (A) of the present invention. can be replaced with Such replacement can reduce the environmental load (greenhouse gas generation) in the life cycle of the propylene-based polymer from production to utilization and disposal.

EXAMPLES The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these Examples as long as it does not exceed the gist of the invention.

<Conditions for measuring various physical properties>
The physical properties of polymers and molded articles described in Reference Examples, Examples, etc. were measured under the following conditions.

(1) Measurement of ¹⁴ C concentration (pMC (percent Modern Carbon)) It was measured as follows according to ASTM D 6866-21.
The sample was combusted to generate carbon dioxide ( _CO2 ) and the carbon dioxide was purified in a vacuum line. Purified carbon dioxide was reduced with hydrogen using iron as a catalyst to produce graphite.
Graphite was packed into a cathode with an inner diameter of 1 mm using a hand press, which was then fitted into a wheel and attached to a measuring device ( ¹⁴ C-AMS dedicated device based on a tandem accelerator (manufactured by NEC)). Using this measurement device, ¹⁴ C count, ¹³ C concentration ( ¹³ C/ ¹² C), and ¹⁴ C concentration ( 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 carried out at the same time.
¹⁴ C concentration (pMC) refers to the ratio of ¹⁴ C concentration of sample carbon to standard modern carbon.

(2) Biomass-derived carbon concentration (pMC (%))
The biomass-derived carbon concentration was obtained by rounding off the ¹⁴ C concentration (pMC) measured as described above to two decimal places according to ASTM D 6866-21.

(3) Biomass degree (%) (biobased carbon content (%))
Corrected by δ ¹³ C (measured ¹³ C concentration ( ¹³ C/ ¹² C) of sample carbon and expressed deviation from standard sample in 1000 minutes deviation (‰)) in accordance with ASTM D 6866-21 calculated using pMC obtained from The value of biomass degree (%) is an integer value rounded off to one decimal place. The value for 2019-2021 described in ASTM D6866-21 (latest version) was used as the atmospheric correction factor (100.0 pMC). It should be noted that there is a possibility that the concentration of ¹⁴ C in the atmosphere will decrease (change) year by year in the future. From now on, when the value of the atmospheric correction factor described in ASTM D6866 (latest version) is changed from 100.0 pMC, the value described in ASTM D6866 in the year in which the propylene-based polymer related to the present invention was manufactured will be used as the atmospheric correction factor. and When the manufacturing year of the raw material for manufacturing the biomass-derived olefin is unknown, the atmospheric correction factor was set to 100.0 pMC.

(4) Melt flow rate (MFR: [g/10 minutes])
Measured with a 2.16 kg load according to ASTM D1238E. The measurement temperature was 230°C. When measuring the MFR of a polymer (for example, a propylene homopolymer) to be the crystalline propylene-based polymer component (c) of the propylene/ethylene block copolymer, Irganox manufactured by Ciba-Geigy was used as an antioxidant. Measurement was carried out by adding 1000 ppm of 1010 and 1000 ppm of Irgafos 168 manufactured by Ciba-Geigy.

(5) Isotactic pentad fraction (mmmm: [%])
The pentad fraction is one of the indicators of stereoregularity of a polymer, and is a value obtained by examining its microtacticity. The isotactic pentad fraction (mmmm: [%]) of the propylene-based polymer was determined by carbon nuclear magnetic resonance spectroscopy ( ¹³ C-NMR), and assigned ¹³ C- It was calculated from the peak intensity ratio of the NMR spectrum.
< ¹³ C-NMR measurement device and measurement conditions>
Measurement device: AVANCE III 500 type nuclear magnetic resonance device (with cryoprobe) (manufactured by Bruker Biospin)
Measurement nucleus: 13C (125MHz)
Measurement mode: single pulse proton broadband decoupling pulse width: 45°
Points: 64k
Measurement range: 240 ppm (-60 to 180 ppm)
Repeat time: 5.5 seconds Accumulation times: 256 times Measurement solvent: ortho-dichlorobenzene/benzene-d6 (4/1 v/v)
Sample concentration: ca. 50 mg/0.6 mL
Measurement temperature: 120°C
Window function: exponential (BF: 0.5Hz)
Chemical shift standard: mmmm (21.59 ppm)

(6) Content of structural units derived from ethylene in the propylene polymer (weight (%))
The measurement conditions are the same as those for (5) measurement of isotactic pentad fraction.
From the spectrum obtained by the measurement, the ratio of the monomer chain distribution (triad (triad) distribution) is determined according to the following document (1), and the copolymer (for example, propylene / ethylene random copolymer) The molar fraction (mol%) of structural units derived from ethylene (hereinafter referred to as E (mol%)) and the molar fraction (mol%) of structural units derived from propylene (hereinafter referred to as P (mol%)) are Calculated.
The obtained E (mol%) and P (mol%) were converted to weight% according to the following formula (1), and the content (% by weight) of the structural unit derived from ethylene in the above Dinsol and Dsol of the propylene-based polymer ) (hereinafter referred to as E (wt %)) was calculated.
Reference (1): Kakugo, M.; Naito, Y.; Mizunuma, K.; Miyatake, T., Carbon-13 NMR determination of monomer sequence distribution in ethylene-propylene copolymers prepared with delta-titanium trichloride-diethylaluminum chloride. 1982,
15, (4), 1150-1152
E (wt%) = E (mol%) x 28 x 100/[P (mol%) x 42 + E (mol%) x 28] (1)

(7) Content of structural units derived from α-olefin having 4 to 8 carbon atoms in propylene-based polymer (% by weight)
The measurement conditions were the same as those for isotactic pentad fraction measurement.
From the spectrum obtained by the measurement, the chemical shift standard was appropriately determined according to the α-olefin species used as the copolymerization component of propylene, and calculated based on these.

(8) Mw/Mn
By gel permeation chromatography (GPC) method, by analyzing the chromatogram obtained by measuring with the following equipment and conditions, Mw (weight average molecular weight) value in terms of polystyrene, Mn (number average molecular weight) value and Mw/Mn values were calculated.
(GPC measuring device)
Liquid chromatograph: manufactured by Tosoh Corporation, HLC-8321GPC/HT detector: RI
Column: Tosoh Corporation TOSOH GMHHR-H (S) HT × 2 connected in series <Measurement conditions>
Mobile phase medium: 1,2,4-trichlorobenzene Flow rate: 1.0 ml/min Measurement temperature: 145°C
Method of preparing standard curve: A standard curve was prepared using standard polystyrene samples.
Molecular weight conversion: conversion from PS (polystyrene) to PP (polypropylene) conversion molecular weight by universal calibration method Sample concentration: 5mg/10ml
Sample solution volume: 300 μl

(9) 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 maximum endothermic peak apex was defined as the melting point (Tm (°C)).
<Measurement conditions>
・Measurement environment: nitrogen gas atmosphere ・Sample amount: 5 mg
・Sample shape: Press film (molded at 230°C, thickness 200-400 μm)
・Sample set: sealed in an aluminum pan ・First step: The temperature was raised from 30°C to 240°C at a rate of 10°C/min and held for 10 minutes.
- 2nd step: The temperature is lowered to 30°C at a rate of 10°C/min.
- 3rd step: Heat up to 240°C at 10°C/min.

(10) Decane soluble portion (% by weight) and decane insoluble portion (% by weight) in propylene/ethylene block copolymer
5±0.05 g of the propylene/ethylene block copolymer was accurately weighed and placed in a 1,000-ml eggplant-shaped flask, and 1±0.05 g of BHT (dibutylhydroxytoluene (phenolic antioxidant)) was added. , rotor and 700±10 ml of n-decane were charged. Next, a condenser was attached to the eggplant-shaped flask, and the flask was heated in an oil bath at 135±5° C. for 120±30 minutes while the rotor was operating to dissolve the sample in n-decane. Next, after pouring the contents of the flask into a 1000 ml beaker, the solution in the beaker was allowed to cool (8 hours or more) to room temperature (25°C) while stirring with a stirrer. I filtered it out. The filtrate was further filtered with filter paper, poured into 2,000±100 ml of methanol contained in a 3,000 ml beaker, and stirred with a stirrer at room temperature (25° C.). It was left for 2 hours or more. Next, the resulting precipitate was collected by filtration through a wire mesh, air-dried for 5 hours or more, and dried in a vacuum dryer at 100±5°C for 240 to 270 minutes to recover the n-decane soluble portion at 25°C.
The content (x) of the n-decane soluble part at 25 ° C. is calculated by dividing the sample weight into Ag and the recovered n-decane soluble part into the propylene/ethylene random copolymer (propylene/ethylene random copolymer component (d) ) is Cg, x (% by weight)=100×C/A.
The decane-insoluble portion amount (y) is represented by y (% by weight)=100-x (% by weight).

(11) Intrinsic viscosity ([η] (dl/g))
About 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. 5 ml of the decalin solvent was added to the decalin solution to dilute it, and then the specific viscosity η _sp was measured in the same manner. This dilution operation was repeated twice, 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) Biaxially Stretched Film Lateral Stretching Load Shown as the yield load when laterally stretching with a table tenter during biaxially stretched film molding.

(13) Total film haze Measured according to JIS K-7105.

(14) Film Tensile Elastic Modulus Film tensile elastic modulus (MPa) was measured under the following conditions in accordance with JIS K7127.
<Measurement conditions>
- The film for evaluation was cut into strips with a width of 10 mm and a length of 150 mm. - Tensile tests were performed at a crosshead speed of 500 mm/min. - The machine direction was set to MD, and the direction perpendicular to MD was set to TD.

(15) Film heat-sealing temperature Film heat-sealing temperature (°C) was measured according to JIS K-1707. The welding conditions are described below. The temperature of the heat seal bar is calibrated by a surface thermometer. After sealing, the film was left at room temperature for a whole day and night, and then the peel strength was measured by the T-peel method at a room temperature peel speed of 200 mm/min. The heat sealing temperature was obtained by calculating the temperature at which the peel strength becomes 300 g/15 mm from the seal strength-peel strength curve.
<Fusing conditions>
Sealing time: 1 sec
Seal area: 15x10mm
Sealing pressure: 2.0 kg/ ^cm2
Seal temperature: Several temperatures were chosen so that the heat seal temperature can be interpolated.

(16) Film Impact Strength 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.

(17) Tensile Elongation at Break and Tensile Strength at Break of Injection Molded Article The tensile elongation at break (%) and tensile strength at break (MPa) of an injection molded article were measured under the following conditions according to ASTM D638.
<Measurement conditions>
Test piece: ASTM-1 dumbbell (19 mm (width) x 3.2 mm (thickness) x 165 mm (length))
Tensile speed: 50 mm/min Distance between spans: 115 mm
A molded article obtained from a glass fiber-containing polypropylene resin composition (short-fiber glass-reinforced PP (GFPP)) was measured under the following conditions in accordance with JIS K7161.
<Measurement conditions>
Test piece: multi-purpose test piece (ISO-A type: thickness 4 mm)
Tensile speed: 5mm/min Temperature: 23°C

(18) Bending Elastic Modulus and Bending Strength of Injection-molded Article The bending elastic modulus (MPa) and bending strength (MPa) of the injection-molded article were measured under the following conditions in accordance with JIS K7171.
<Measurement conditions>
Test piece: 10 mm (width) x 80 mm (length) x 4 mm (thickness)
Bending speed: 2 mm/min Bending span: 64 mm

(19) Izod impact strength of injection molded article The Izod impact strength of the injection molded article was measured under the following conditions in accordance with ASTM D256.
<Measurement conditions>
Temperature: 23°C
Specimen: 12.7 mm (width) x 6.4 mm (thickness) x 64 mm (length) (notched; notch machined)

(20) Charpy Impact Test of Injection Molded Article The Charpy impact value (kJ/m ² ) of the injection molded article was measured according to JIS K7111 under the following conditions.
<Measurement conditions>
Temperature: -30°C
Specimen: 10 mm (width) x 80 mm (length) x 4 mm (thickness) (with notches; notches are machined)

(21) Rockwell Hardness of Injection Molded Article The Rockwell hardness (R scale) of the injection molded article was measured according to JIS K7202 under the following conditions.
<Measurement conditions>
Test piece: 30 mm (width) x 30 mm (length) x 2 mm (thickness)
Two test pieces were piled up and measured.

(22) Weld Strength of Injection-Molded Article The weld strength of the injection-molded article was measured according to JISK7171 under the following conditions.
<Measurement conditions>
Test piece: 10 mm (width) x 80 mm (length) x 4 mm (thickness)
Bending speed: 2 mm/min Bending span: 64 mm

Raw materials other than propylene-based polymer (A) <Ethylene/α-olefin copolymer (B)>
Ethylene/1-butene random copolymer (manufactured by Mitsui Chemicals, Inc., Tafmer (registered trademark) A1050S, MFR (230°C, 2.16 kg load) = 2 g/10 min, density = 0.862 g/cm ³ )

<Talc (C)>
“JM-209” (manufactured by Asada Flour Milling Co., Ltd.) Average particle size of about 4 μm determined by laser diffraction method

<Short glass fiber (D)>
Chopped strands with an average fiber diameter of 10 µm, an average length of 3 mm, and a surface treatment with an aminosilane coupling agent

<Short Carbon Fiber (E)>
Chopped fiber carbon fiber (epoxy resin sizing) (HTA-C6-SR (trademark), manufactured by Toho Tenax Co., Ltd.)

<Maleic anhydride-modified polypropylene (F)>
Youmex 1010 (trademark), manufactured by Sanyo Kasei Co., Ltd.)

[Reference Example 1] (Fossil fuel-derived propylene homopolymer: PP-1-0)
(1-1) Preparation of Magnesium Compound After sufficiently purging a 12-liter glass reactor equipped with a stirrer with nitrogen gas, about 4,860 g of ethanol, 32 g of iodine, and 320 g of metallic magnesium were charged and stirred. A solid reaction product was obtained by reacting under reflux conditions. The magnesium compound (solid product) was obtained by drying the reaction liquid containing this solid reaction product under reduced pressure.

(1-2) Preparation of solid catalyst component 160 g of the magnesium compound (not pulverized) obtained in (1-1) was placed in a three-necked glass flask having an internal volume of 5 liters that was sufficiently purged with nitrogen gas. , 800 ml of purified heptane, 24 ml of silicon tetrachloride and 23 ml of diethyl phthalate were added. The inside of the system was kept at 90°C, and 770 ml of titanium tetrachloride was added while stirring. After reacting at 110°C for 2 hours, the solid component was separated and washed with purified heptane at 80°C. Further, 1,220 ml of titanium tetrachloride was added, reacted at 110° C. for 2 hours, and thoroughly washed with purified heptane to obtain a solid catalyst component.

(1-3) Polymerization Pretreatment Into a reactor with a stirring blade having an internal volume of 500 liters, 230 liters of n-heptane was added, and 25 kg of the solid catalyst component obtained in (1-2) was added, followed by After adding 0.6 mol of triethylaluminum and 0.4 mol of cyclohexylmethyldimethoxysilane per 1 g of Ti atoms in this solid catalyst component, fossil fuel-derived propylene was added at a propylene partial pressure of 0.3 kg/cm ^{2 .} It was introduced until reaching G and reacted at 20° C. for 4 hours.
After completion of the reaction, the solid catalyst component was washed several times with n-heptane, supplied with carbon dioxide, and stirred for 24 hours.

(1-4) Main Polymerization In a polymerization vessel with a stirring blade having an internal volume of 200 liters, the solid catalyst component treated in (1-3) above was added at a rate of 3 mmol/hr in terms of titanium atoms, and 0.37 mmol of triethylaluminum. /hr and 95 mmol/hr of cyclohexylmethyldimethoxysilane were supplied, respectively, and the reaction was carried out at a polymerization temperature of 80°C and a propylene pressure of 28 kg/cm ² G. As the propylene, fossil fuel-derived propylene was used. At this time, hydrogen gas was supplied so as to obtain a predetermined molecular weight. Table 1 shows the resin physical properties of the propylene homopolymer (PP-1-0) thus obtained. The MFR was measured using the granulated product obtained in (1-5) below.

(1-5) Additive formulation and granulation The polypropylene homopolymer (PP-1-0) powder thus obtained in (1-4) was added with 100 ppm of Irganox 1010 manufactured by Ciba-Geigy as an antioxidant and Ciba-Geigy. 1000 ppm of Irgafos 168, 1000 ppm of calcium stearate as a neutralizing agent, 2300 ppm of silica-based anti-blocking agent, and 500 ppm of erucamide as a slip agent. A polypropylene resin composition (granulated product) was prepared.
<Melt-kneading conditions>
Extruder: Product number: Twin-screw extruder “TEM-35” manufactured by Toshiba Machine Co., Ltd.
Nitrogen-sealed hopper Cylinder temperature: 210°C
Screw rotation speed: 150 rpm
Extrusion: 15 kg/h

(1-6) Preparation of biaxially stretched film Next, using a 35 mmφ sheet molding machine manufactured by Shinko Kikai Seisakusho, the resin composition obtained in (1-5) was molded under the conditions of a resin temperature of 260 ° C. and a chill roll temperature of 30 ° C. After forming the sheet, the sheet is longitudinally stretched with a roll stretching machine manufactured by Iwamoto Seisakusho under the conditions of a stretching temperature of 145°C and a stretching ratio of 5 times. , and transverse stretching under the conditions of a stretching rate of 90%/sec and a stretching ratio of 10 times to prepare a biaxially stretched film having a thickness of 25 μm. Subsequently, this biaxially stretched film was surface-treated by a roll electrode type corona discharge treatment machine manufactured by Kasuga Denki Co., Ltd. The wettability of the treated surface was 42 dyne/cm. Table 1 shows the evaluation results of this biaxially stretched film.

[Example 1] (propylene homopolymer (A1): PP-1-1)
(1-4) Same as (1-1) to (1-4) in Reference Example 1, except that biomass-derived propylene was used instead of fossil fuel-derived propylene as propylene in the main polymerization of Reference Example 1. A propylene homopolymer (PP-1-1), which is a propylene homopolymer (A1), was thus obtained. Table 1 shows the resin physical properties of the obtained propylene homopolymer (PP-1-1).
Using propylene homopolymer (PP-1-1) obtained instead of fossil fuel-derived propylene homopolymer (PP-1-0), (1-5) additive formulation and granulation of Reference Example 1 A polypropylene resin composition (granulated product) was prepared according to the above, and a biaxially stretched film was produced according to (1-6) Production of biaxially stretched film. Table 1 shows the physical properties of the obtained biaxially stretched film.

[Reference Example 2] (fossil fuel-derived propylene-based random copolymer: PP-2-0)
(2-1) Preparation of Magnesium Compound A reactor with a stirrer (inner volume: 500 liters) was sufficiently purged with nitrogen gas, and 97.2 kg of ethanol, 640 g of iodine, and 6.4 kg of metallic magnesium were charged and stirred. The reaction was continued under reflux conditions until hydrogen gas was no longer generated from the system to obtain a solid reaction product. The target magnesium compound (solid catalyst carrier) was obtained by drying the reaction solution containing the solid reaction product under reduced pressure.

(2-2) Preparation of solid catalyst component 30 kg of the magnesium compound (not pulverized) obtained in (2-1) was placed in a reactor with a stirrer (inner volume: 500 liters) sufficiently purged with nitrogen gas. , 150 liters of purified heptane (n-heptane), 4.5 liters of silicon tetrachloride, and 5.4 liters of di-n-butyl phthalate were added. The inside of the system was kept at 90°C, and 144 liters of titanium tetrachloride was added while stirring. After reacting at 110°C for 2 hours, the solid component was separated and washed with purified heptane at 80°C. Further, 228 liters of titanium tetrachloride was added, reacted at 110° C. for 2 hours, and thoroughly washed with purified heptane to obtain a solid catalyst component.

(2-3) Pretreatment for polymerization 230 liters of purified heptane was charged into a reaction tank with a stirrer having an internal volume of 500 liters, 25 kg of the solid catalyst component obtained in (2-2) was added, and titanium atoms in the solid catalyst component were , 1.0 mol/mol of triethylaluminum and 1.8 mol/mol of dicyclopentyldimethoxysilane were supplied. Thereafter, propylene was introduced until the propylene partial pressure reached 0.3 kg/cm ² G, and the mixture was reacted at 25°C for 4 hours. After completion of the stirring reaction, the solid catalyst component was washed several times with purified heptane, carbon dioxide was further supplied, and the mixture was stirred for 24 hours. As the propylene, fossil fuel-derived propylene was used.

(2-4) Main polymerization To a polymerization apparatus with an internal volume of 200 liters and equipped with a stirrer, the solid catalyst component treated in (2-3) above is supplied at a rate of 3 mmol/hr in terms of titanium atoms, and triethylaluminum is supplied at a rate of 120 mmol/hr. Then, propylene and ethylene were reacted at a polymerization temperature of 80° C. and a polymerization pressure (total pressure) of 28 kg/cm ² G. At this time, the amount of ethylene supplied and the amount of hydrogen supplied were adjusted so as to obtain the desired ethylene content and molecular weight, and propylene, ethylene and hydrogen were continuously supplied to the polymerization apparatus. The composition analysis value (gas chromatography analysis) of the gas portion in the polymerization apparatus showed an ethylene concentration of 3.4 mol % and a hydrogen concentration of 2.4 mol %. In addition, propylene derived from fossil fuel was used as propylene, and ethylene derived from fossil fuel was used as ethylene. Table 2 shows the physical properties of the propylene/ethylene random copolymer (PP-2-0) thus obtained. The MFR was measured using the granulated product obtained in (2-5) below.

(2-5) Additive formulation and granulation The propylene/ethylene random copolymer (PP-2-0) powder thus obtained in (2-4) was added with 1000 ppm of Irganox 1010 manufactured by Ciba-Geigy as an antioxidant. and 1000 ppm of Irgafos 168 manufactured by Ciba-Geigy, 1000 ppm of calcium stearate as a neutralizing agent, 2300 ppm of silica-based anti-blocking agent, and 500 ppm of erucamide as a slip agent. Granulated to prepare a resin composition (granulated product) containing a propylene-based random superpolymer.
<Melt-kneading conditions>
Extruder: Product number: Twin-screw extruder “TEM-35” manufactured by Toshiba Machine Co., Ltd.
Nitrogen-sealed hopper Cylinder temperature: 210°C
Screw rotation speed: 150 rpm
Extrusion: 15 kg/h

(2-6) Production of Film Next, using a 75 mmφ molding machine manufactured by Mitsubishi Heavy Industries, a film having a thickness of 30 μm was produced from the resin composition obtained in (2-5) under the following molding conditions.
<Molding conditions>
Processing temperature: 243°C
Chill roll temperature: 25°C
Take-up speed: 125m/min
The obtained film was conditioned at a temperature of 23±2° C. and a humidity of 50±10% for 16 hours or more, after which the physical properties of the film were measured under the same temperature and humidity conditions. Table 2 shows the physical properties of the obtained film.

[Example 2] (Propylene random copolymer (A2-1): PP-2-1)
(2-4) Same as (2-1) to (2-4) in Reference Example 2, except that biomass-derived propylene was used instead of fossil fuel-derived propylene as propylene in the main polymerization of Reference Example 2. Then, a propylene/ethylene random copolymer (PP-2-1), which is a propylene random copolymer (A2-1), was obtained. Table 2 shows the physical properties of the obtained propylene/ethylene random copolymer (PP-2-1).
(2-5) of Reference Example 2 was added using a propylene/ethylene random copolymer (PP-2-1) obtained in place of the fossil fuel-derived propylene-based random copolymer (PP-2-0). A polypropylene resin composition (granulated product) was prepared according to the agent formulation and granulation, and a film having a thickness of 30 μm was produced according to (2-6) Preparation of film. Table 2 shows the physical properties of the obtained film.

[Reference Example 3] (Fossil fuel-derived propylene/ethylene block copolymer: (PP-3-0))
(3-1) Preparation of Solid Titanium Catalyst Component 952 g of anhydrous magnesium chloride, 4420 ml of decane and 3906 g of 2-ethylhexyl alcohol were heated at 130° C. for 2 hours to form a homogeneous solution. 213 g of phthalic anhydride was added to this solution, and the mixture was further stirred and mixed at 130° C. for 1 hour to dissolve the phthalic anhydride.
After cooling the homogeneous solution thus obtained to 23° C., 750 ml of this homogeneous solution was dropped into 2000 ml of titanium tetrachloride kept at −20° C. over 1 hour. After the dropwise addition, the temperature of the resulting mixture was raised to 110°C over 4 hours, and when the temperature reached 110°C, 52.2 g of diisobutyl phthalate (DIBP) was added, followed by stirring at the same temperature for 2 hours. held to. Next, the solid portion was collected by hot filtration, resuspended in 2750 ml of titanium tetrachloride, and heated again at 110° C. for 2 hours.
After completion of heating, the solid portion was collected again by hot filtration and washed with 110° C. decane and hexane until no titanium compound was detected in the washing solution.
The solid titanium catalyst component prepared as described above was stored as a hexane slurry. The solid titanium catalyst component contained 2% by weight titanium, 57% by weight chlorine, 21% by weight magnesium and 20% by weight DIBP.

(3-2) Prepolymerization treatment 70 g of the solid titanium catalyst component obtained in (3-1), 44.0 mL of triethylaluminum, 15.0 mL of 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 80 L of heptane was inserted into an autoclave with an internal volume of 200 L equipped with a stirrer, and while the internal temperature was maintained at 5° C., 700 g of propylene was added and reacted with stirring for 60 minutes. After the polymerization was completed, the solid components were allowed to settle, and the supernatant was removed and washed with heptane twice. The resulting prepolymerized catalyst was resuspended in purified heptane, and the concentration of the solid titanium catalyst component was adjusted to 1.0 g/L with heptane. This prepolymerized catalyst contained 10 grams of polypropylene per gram of solid titanium catalyst component. Fossil fuel-derived propylene was used as the propylene.

(3-3) Main Polymerization Transferred to a vessel polymerization vessel (1) having an internal volume of 1000 L and equipped with a stirrer, and 133 kg/hour of propylene and hydrogen were supplied so that the hydrogen concentration in the gas phase was 8.0 mol %. 0.8 g/hour of the prepolymerized catalyst obtained in (3-2) as a solid titanium catalyst component, 15.3 g/hour of triethylaluminum, and 1.5 mL/hour of dicyclopentyldimethoxysilane were continuously supplied to polymerize. Polymerization was carried out at a temperature of 70° C. and a pressure of 3.4 MPa/G. As the propylene, fossil fuel-derived propylene was used (the same applies to the following steps).
The slurry containing the polymer obtained in the polymerization vessel (1) was sent to another vessel polymerization vessel (2) having an internal volume of 500 L and equipped with a stirrer, and was further polymerized. To the polymerization vessel (2), 21 kg/hour of propylene and hydrogen were supplied so that the hydrogen concentration in the gas phase was 7.0 mol %. Polymerization was carried out at a polymerization temperature of 70°C and a pressure of 3.35 MPa/G.
The slurry containing the polymer obtained in the polymerization vessel (2) was sent to another vessel polymerization vessel (3) having an internal capacity of 500 L and equipped with a stirrer, and further polymerization was carried out. To the polymerization vessel (3), 17 kg/hour of propylene and hydrogen were supplied so that the hydrogen concentration in the gas phase was 6.0 mol %. Polymerization was carried out at a polymerization temperature of 70°C and a pressure of 3.3 MPa/G.
A portion of the slurry obtained in the polymerization vessel (3) is sampled, filtered, and air-dried for 5 hours or more before ethylene/propylene block copolymerization (the step of preparing the propylene/ethylene random copolymer component (d)). After drying in a vacuum dryer at 100±5° C. for 240 to 270 minutes, MFR, melting point, pentad fraction and Mw/Mn were measured. When measuring the MFR, 1000 ppm of Irganox 1010 manufactured by Ciba-Geigy and 1000 ppm of Irgafos 168 manufactured by Ciba-Geigy were added as antioxidants.
The slurry obtained in the polymerization vessel (3) is sent to another vessel polymerization vessel (4) having an internal capacity of 500 L and equipped with a stirrer, and copolymerization (preparation of the propylene/ethylene random copolymer component (d)) is carried out. rice field. To the polymerization vessel (4), 15 kg/hour of propylene, 17 kg/hour of ethylene, and hydrogen were supplied so that the hydrogen concentration in the gas phase was 5.0 mol %. Polymerization was carried out at a polymerization temperature of 60°C and a pressure of 3.2 MPa/G. As ethylene, ethylene derived from fossil fuel was used.
After vaporizing the slurry obtained in the polymerization vessel (4), gas-solid separation was performed to obtain a propylene/ethylene block copolymer (PP-3-0). The obtained propylene/ethylene block copolymer was vacuum dried at 80°C. Table 3 shows the physical properties of the propylene/ethylene block copolymer (PP-3-0) thus obtained. The MFR was measured using the granulated product obtained in (3-4) below.

(3-4) Additive formulation and granulation To the propylene/ethylene block copolymer (PP-3-0) powder thus obtained in (3-3), 1000 ppm of Irganox 1010 manufactured by Ciba-Geigy was added as an antioxidant. 1000 ppm of Irgafos 168 manufactured by Ciba-Geigy and 1000 ppm of calcium stearate as a neutralizing agent were mixed in a tumbler and granulated under the following conditions to prepare a polypropylene resin composition (granulated product).
<Melt-kneading conditions>
Co-directional twin-screw kneader: Product number NR2-36 (manufactured by Nakatani Machinery Co., Ltd.)
Kneading temperature: 230°C
Screw rotation speed: 200 rpm
Feeder rotation speed: 500 rpm

(3-5) Injection molding Using the granulated product obtained in (3-4), an ASTM test piece (injection molded body ) was molded. Table 3 shows the physical properties of the injection molded article made of the propylene/ethylene block copolymer (PP-3-0).
<Injection molding conditions>
Injection molding machine: Product number IS100 (manufactured by Toshiba Machine Co., Ltd.)
Cylinder temperature: 190°C
Mold temperature: 40°C
Injection time - holding pressure time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds

[Example 3] (Propylene/ethylene block copolymer (A2-2): PP-3-1)
In (3-3) the main polymerization of Reference Example 3, biomass-derived propylene was used as propylene instead of fossil fuel-derived propylene, and biomass-derived ethylene was used instead of fossil fuel-derived ethylene as ethylene. A propylene/ethylene block copolymer (PP-3-1), which is a propylene/ethylene block copolymer (A2-2), was obtained in the same manner as in (3-1) to (3-3) of Reference Example 3. rice field. Table 3 shows the physical properties of the obtained propylene/ethylene block copolymer (PP-3-1).
(3-4) of Reference Example 3 using a propylene/ethylene block copolymer (PP-3-1) obtained in place of the fossil fuel-derived propylene/ethylene block copolymer (PP-3-0) A polypropylene resin composition (granulated product) was prepared according to the additive formulation and granulation, and an injection-molded article was produced according to (3-5) injection molding. Table 3 shows the physical properties of the obtained injection molded product.

[Reference Example 4] (Fossil fuel-derived propylene homopolymer, resin composition containing the propylene homopolymer)
<Preparation of Fossil Fuel Derived Propylene Homopolymer (PP-4-0)>
(4-1) Preparation of Solid Titanium Catalyst Component 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol were heated at 130° C. for 2 hours to form a homogeneous solution. 21.3 g of phthalic anhydride was added to this solution, and the mixture was stirred and mixed at 130° C. for 1 hour to dissolve the phthalic anhydride.
After the homogeneous solution thus obtained was cooled to room temperature, 75 ml of this homogeneous solution was dropped into 200 ml of titanium tetrachloride kept at -20° C. over 1 hour. After completion of charging, the temperature of this mixed solution was raised to 110°C over 4 hours, and when the temperature reached 110°C, 5.22 g of diisobutyl phthalate (DIBP) was added, followed by stirring at the same temperature for 2 hours. held.
After completion of the reaction for 2 hours, the solid portion was collected by hot filtration, resuspended in 275 ml of titanium tetrachloride, and heated again at 110° C. for 2 hours. After completion of the reaction, the solid portion was collected again by hot filtration and thoroughly washed with 110° C. decane and hexane until no free titanium compound was detected in the solution.
Here, the detection of this free titanium compound was confirmed by the following method. 10 ml of the supernatant liquid of the solid catalyst component was collected with a syringe and charged into a 100 ml branched Schlenk tube previously purged with nitrogen. Next, the solvent hexane was dried with a stream of nitrogen, followed by vacuum drying for 30 minutes. 40 ml of ion-exchanged water and 10 ml of 50% by volume sulfuric acid were added thereto and stirred for 30 minutes. This aqueous solution was transferred through a filter paper to a 100 ml volumetric flask, then 1 ml of concentrated phosphoric acid solution as a masking agent for iron (II) ions and 5 ml of 3% hydrogen peroxide solution as a coloring reagent for titanium were added, and the volume was adjusted to 100 ml with deionized water. The volumetric flask was shaken, and after 20 minutes, the absorbance at 420 nm was observed using UV, and free titanium was removed by washing until no absorption was observed.
The solid titanium catalyst component prepared as described above was stored as a decane slurry, a portion of which was dried for the purpose of investigating the catalyst composition. The composition of the resulting solid titanium catalyst component was 2.3 wt% titanium, 61 wt% chlorine, 19 wt% magnesium, and 12.5 wt% DIBP.

(4-2) Prepolymerization treatment 100 g of the solid titanium catalyst component obtained in (4-1), 39.3 mL of triethylaluminum, and 100 L of heptane were placed in an autoclave with an internal volume of 200 L and equipped with a stirrer, and the internal temperature was 15 to 20. C., 600 g of propylene was added, and the mixture was reacted with stirring for 60 minutes to obtain a catalyst slurry. Fossil fuel-derived propylene was used as the propylene.

(4-3) Main polymerization Into a 58 L jacketed circulating tubular polymerization reactor, 43 kg/hour of propylene and 177 NL/hour of hydrogen were charged, and the catalyst slurry obtained in (4-2) was added to 0 as a solid titanium catalyst component. 0.58 g/hour, 3.1 ml/hour of triethylaluminum, and 3.3 ml/hour of dicyclopentyldimethoxysilane were continuously supplied, and polymerization was carried out in a liquid-filled state in which no gas phase existed. The temperature of the tubular polymerization vessel was 70°C and the pressure was 3.53 MPa/G. Fossil fuel-derived propylene was used as the propylene (the same applies to the following steps).
The slurry obtained in the tubular polymerization vessel was sent to a vessel polymerization vessel having an internal volume of 100 L and equipped with a stirrer, and was further polymerized. To the polymerization vessel, 45 kg/hour of propylene and hydrogen were supplied so that the hydrogen concentration in the gas phase was 3.2 mol %. Polymerization was carried out at a polymerization temperature of 70° C. and a pressure of 3.28 MPa/G to obtain a propylene homopolymer (PP-4-0). The obtained propylene homopolymer was vacuum-dried at 80°C. Table 4 shows the resin physical properties of the propylene homopolymer (PP-4-0) thus obtained. When measuring the MFR, 1000 ppm of Irganox 1010 manufactured by Ciba-Geigy and 1000 ppm of Irgafos 168 manufactured by Ciba-Geigy were added as antioxidants.

<Preparation of resin composition containing propylene homopolymer derived from fossil fuel>
(4-4) Additive formulation and granulation 75% by weight of the propylene homopolymer (PP-4-0) powder thus obtained in (4-3) and 25% by weight of the ethylene/α-olefin copolymer (B) In addition, 1000 ppm of Irganox 1010 manufactured by Ciba Geigy and Irgafos manufactured by Ciba Geigy are added as antioxidants to the total of propylene homopolymer (PP-4-0) and ethylene / α-olefin copolymer (B). 168 at 1000 ppm and calcium stearate at 1000 ppm as a neutralizing agent, mixed in a tumbler, melt-kneaded in a twin-screw extruder under the following conditions, and a resin composition containing a propylene homopolymer (4B-0). pellets were prepared.
<Melt-kneading conditions>
Co-directional twin-screw kneader: Product number KZW-15 (manufactured by Technobell Co., Ltd.)
Kneading temperature: 190°C
Screw rotation speed: 500 rpm
Feeder rotation speed: 40 rpm

(4-5) Injection molding Using the pellets obtained in (4-4), an injection molding machine [product number EC40 (manufactured by Toshiba Machine Co., Ltd.)] is used to make a JIS test piece (injection molded body) under the following conditions. Molded. Table 4 shows the physical properties of the injection molded article made of the resin composition (4B-0).
<Injection molding conditions>
Injection molding machine: Product number EC40 (manufactured by Toshiba Machine Co., Ltd.)
Cylinder temperature: 190°C
Mold temperature: 40°C
Injection time - holding pressure time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds

[Example 4] (propylene homopolymer (A1): PP-4-1, resin composition containing the propylene homopolymer (A1))
(4-3) Same as (4-1) to (4-3) in Reference Example 4, except that biomass-derived propylene was used instead of fossil fuel-derived propylene as propylene in the main polymerization of Reference Example 4. Then, a propylene homopolymer (PP-4-1), which is the propylene homopolymer (A1), was obtained. Table 4 shows the resin physical properties of the obtained propylene homopolymer (PP-4-1).
Using propylene homopolymer (PP-4-1) obtained instead of fossil fuel-derived propylene homopolymer (PP-4-0), (4-4) additive formulation and granulation of Reference Example 4 Pellets of a resin composition (4B-1) containing a propylene homopolymer (PP-4-1) and an ethylene/α-olefin copolymer (B) are prepared according to (4-5) and injection molded. Therefore, an injection molded body was produced from pellets of the resin composition (4B-1). Table 4 shows the physical properties of the obtained injection molded product.

[Reference Example 5] (Fossil fuel-derived propylene homopolymer, resin composition containing the propylene homopolymer)
<Preparation of Fossil Fuel Derived Propylene Homopolymer (PP-5-0)>
(5-1) Preparation of solid titanium catalyst component 1.3% by weight of titanium and 20% by weight of magnesium in the same manner as in [Example 1] ([0157] to [0161]) of WO2019/004418 , 13.8% by weight of diisobutyl phthalate, and 0.8% by weight of diethyl phthalate, to obtain a solid titanium catalyst component (i-1). The present inventor believes that the diethyl phthalate detected in the solid titanium catalyst component (i-1) is probably used to produce diisobutyl phthalate and solid titanium during the production process of the solid titanium catalyst component. It is speculated that this is due to accompanying transesterification with the ethanol used.

(5-2) Prepolymerization Treatment 90.0 g of the solid titanium catalyst component (i-1) obtained in (5-1), 66.7 mL of triethylaluminum, 15.6 mL of isopropylpyrrolidinodimethoxysilane, and 10 L of heptane were The autoclave was placed in an autoclave with an internal volume of 20 L equipped with a stirrer, and 900 g of propylene was added while maintaining the internal temperature at 15 to 20° C., and the reaction was allowed to proceed for 100 minutes while stirring. After the polymerization was completed, the solid components were allowed to settle, and the supernatant was removed and washed with heptane twice. The resulting solid component was resuspended in purified heptane, and the concentration of the solid catalyst component was adjusted to 1.0 g/L with heptane to obtain a catalyst. As the propylene, fossil fuel-derived propylene was used.

(5-3) Main Polymerization 300 L of liquefied propylene was charged into a polymerization tank with an internal volume of 500 L and equipped with a stirrer. 0 g/h, 8.9 mL/h of triethylaluminum, and 2.8 mL/h of isopropylpyrrolidinodimethoxysilane were continuously fed and polymerized at a temperature of 70°C. Further, hydrogen was continuously supplied so that the hydrogen concentration in the gas phase portion in the polymerization tank was 6.9 mol %. Propylene derived from fossil fuel was used as the propylene. After the obtained slurry was deactivated, the propylene was evaporated to obtain a powdery propylene polymer (PP-5-0). The obtained propylene homopolymer was vacuum-dried at 80°C. Table 5 shows the resin physical properties of the propylene homopolymer (PP-5-0) thus obtained. When measuring the MFR, 1000 ppm of Irganox 1010 manufactured by Ciba-Geigy and 1000 ppm of Irgafos 168 manufactured by Ciba-Geigy were added as antioxidants.

<Preparation of resin composition containing propylene homopolymer derived from fossil fuel>
(5-4) Additive formulation and granulation 80% by weight of the propylene homopolymer powder thus obtained in (5-3), 20% by weight of talc (C), and the propylene homopolymer as an antioxidant 1000 ppm of Irganox 1010 manufactured by Ciba Geigy, 1000 ppm of Irgafos 168 manufactured by Ciba Geigy, and 1000 ppm of calcium stearate as a neutralizing agent were mixed in a tumbler and then melt-kneaded by a twin-screw extruder under the following conditions. Pellets of a resin composition (5B-0) containing propylene homopolymer were prepared.
<Melt-kneading conditions>
Co-directional twin-screw kneader: Product number KZW-15 (manufactured by Technobell Co., Ltd.)
Kneading temperature: 190°C
Screw rotation speed: 500 rpm
Feeder rotation speed: 50 rpm

(5-5) Injection molding Using the pellets obtained in (5-4), an injection molding machine [product number EC40 (manufactured by Toshiba Machine Co., Ltd.)] is used to make a JIS test piece (injection molded body) under the following conditions. Molded. Table 5 shows the physical properties of the injection molded article made of the resin composition (5B-0).
<Injection molding conditions>
Injection molding machine: Product number EC40 (manufactured by Toshiba Machine Co., Ltd.)
Cylinder temperature: 190°C
Mold temperature: 40°C
Injection time - holding pressure time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds

[Example 5] (propylene homopolymer (A1): PP-5-1, resin composition containing the propylene homopolymer (A1))
(5-3) Same as (5-1) to (5-3) in Reference Example 5, except that biomass-derived propylene was used instead of fossil fuel-derived propylene as propylene in the main polymerization of Reference Example 5. Then, a propylene homopolymer (PP-5-1), which is the propylene homopolymer (A1), was obtained. Table 5 shows the resin physical properties of the obtained propylene homopolymer.
Using propylene homopolymer (PP-5-1) obtained in place of fossil fuel-derived propylene homopolymer (PP-5-0), (5-4) additive formulation and granulation of Reference Example 5 Prepare pellets of resin composition (5B-1) containing propylene homopolymer (PP-5-1) and talc (C) according to (5-5) injection molding according to resin composition (5B- An injection molded body was produced from the pellets of 1). Table 5 shows the physical properties of the obtained injection molded article.

[Reference Example 6] (Fossil fuel-derived propylene homopolymer, resin composition containing the propylene homopolymer)
<Preparation of Fossil Fuel-Derived Propylene Homopolymer (PP-6-0)>
(6-1) Preparation of Solid Titanium Catalyst Component 952 g of anhydrous magnesium chloride, 4420 ml of decane and 3906 g of 2-ethylhexyl alcohol were heated at 130° C. for 2 hours to form a homogeneous solution. 213 g of phthalic anhydride was added to this solution, and the mixture was further stirred and mixed at 130° C. for 1 hour to dissolve the phthalic anhydride.
After cooling the homogeneous solution thus obtained to 23° C., 750 ml of this homogeneous solution was dropped into 2000 ml of titanium tetrachloride kept at −20° C. over 1 hour. After the dropwise addition, the temperature of the resulting mixture was raised to 110°C over 4 hours, and when the temperature reached 110°C, 52.2 g of diisobutyl phthalate (DIBP) was added, followed by stirring at the same temperature for 2 hours. held to. Next, the solid portion was collected by hot filtration, resuspended in 2750 ml of titanium tetrachloride, and heated again at 110° C. for 2 hours.
After completion of heating, the solid portion was collected again by hot filtration and washed with 110° C. decane and hexane until no titanium compound was detected in the washing solution.
The solid titanium catalyst component prepared as described above was stored as a hexane slurry. The solid titanium catalyst component contained 2 wt% titanium, 57 wt% chlorine, 21 wt% magnesium and 20 wt% DIBP.

(6-2) Prepolymerization treatment 56 g of the solid titanium catalyst component prepared in (6-1) above, 20.7 ml of triethylaluminum, and 80 L of heptane were placed in an autoclave with an internal volume of 200 L and equipped with a stirrer, and the internal temperature was raised to 5°C. While holding, 560 g of propylene was added and reacted with stirring for 60 minutes. After the polymerization was completed, the solid components were allowed to settle, and the supernatant was removed and washed with heptane twice. The obtained prepolymerized catalyst was resuspended in purified heptane, and adjusted with heptane so that the titanium catalyst component concentration was 0.7 g/L. The prepolymerization catalyst contained 10 grams of polypropylene per gram of solid titanium catalyst component. As the propylene, fossil fuel-derived propylene was used.

(6-3) Main Polymerization Into a jacketed circulating tubular polymerization reactor having an internal capacity of 58 L, 30 kg/hour of propylene, 33 NL/hour of hydrogen, 0.6 g/hour of catalyst slurry as a titanium catalyst component, and 1.9 ml/hour of triethylaluminum were injected. 1.1 ml/hour of cyclohexylmethyldimethoxysilane was continuously supplied, and polymerization was carried out in a liquid-filled state in which no gas phase existed. The temperature of the tubular reactor was 70° C. and the pressure was 3.6 MPa/G.
The resulting slurry was sent to a 100-L vessel polymerization vessel equipped with a stirrer and polymerized. To the polymerization reactor, 15 kg/hour of propylene and hydrogen were supplied so that the hydrogen concentration in the gas phase was 2.2 mol %. Polymerization was carried out at a polymerization temperature of 70°C and a pressure of 3.1 MPa/G. As the propylene, fossil fuel-derived propylene was used.
After vaporizing the resulting slurry, gas-solid separation was performed to obtain a powdery propylene homopolymer (PP-6-0). The propylene homopolymer was vacuum dried at 80°C. Table 6 shows the resin physical properties of the propylene homopolymer (PP-6-0) thus obtained. When measuring the MFR, 1000 ppm of Irganox 1010 manufactured by Ciba-Geigy and 1000 ppm of Irgafos 168 manufactured by Ciba-Geigy were added as antioxidants.

<Preparation of resin composition containing propylene homopolymer derived from fossil fuel>
(6-4) Additive formulation and kneading/granulation 79% by weight of propylene homopolymer (PP-6-0) powder thus obtained in (6-3) and 1% by weight of maleic anhydride-modified polypropylene (F) , with respect to the total of propylene homopolymer (PP-6-0) and maleic anhydride-modified polypropylene (F), 1000 ppm of Irganox 1010 manufactured by Ciba-Geigy and 1000 ppm of Irgafos 168 manufactured by Ciba-Geigy as antioxidants, Prescribe 1000 ppm of calcium stearate as a neutralizing agent, mix them with a tumbler, feed them into a hopper part with a metering feeder, melt and knead them with a twin screw extruder under the following conditions, and further on the side of the twin screw extruder. 20% by weight of the short glass fiber (D) is meteredly supplied from the feed port to the melt-kneaded components by a metering feeder, and further melt-kneaded to obtain pellets of the resin composition (6B-0) containing the propylene homopolymer. was prepared.
<Melt-kneading conditions>
Co-directional twin-screw kneader: Product number TEX-30α (manufactured by Nippon Steel Corporation)
Kneading temperature: 210°C

(6-5) Injection Molding Using the pellets obtained in (6-4), a test piece (injection molding) was molded using an injection molding machine under the following conditions. Table 6 shows the physical properties of the injection molded article made of the resin composition (6B-0).
<Injection molding conditions>
Injection molding machine: Product number ROBOSHOT α-100B (manufactured by FANUC Co., Ltd.)
Cylinder temperature: 230°C
Mold temperature: 40°C

[Example 6] (propylene homopolymer (A1): PP-6-1, resin composition containing the propylene homopolymer (A1))
(6-3) Same as (6-1) to (6-3) in Reference Example 6, except that biomass-derived propylene was used instead of fossil fuel-derived propylene as propylene in the main polymerization of Reference Example 6. Then, a propylene homopolymer (PP-6-1), which is the propylene homopolymer (A1), was obtained. Table 6 shows the resin physical properties of the obtained propylene homopolymer (PP-6-1).
Using propylene homopolymer (PP-6-1) obtained in place of fossil fuel-derived propylene homopolymer (PP-6-0), (6-4) additive formulation and kneading / Pellets of resin composition (6B-1) containing propylene homopolymer (PP-6-1), maleic anhydride-modified polypropylene (F), and short glass fiber (D) were prepared according to granulation, and the same ( 6-5) An injection molded article was produced from pellets of the resin composition (6B-1) according to injection molding. Table 6 shows the physical properties of the obtained injection molded product.

[Reference Example 7] (Fossil fuel-derived propylene homopolymer, resin composition containing the propylene homopolymer)
<Preparation of Fossil Fuel Derived Propylene Homopolymer (PP-7-0)>
(7-1) Preparation of solid titanium catalyst component In the same manner as in Reference Example (6-1) Preparation of solid titanium catalyst component, 2% by weight of titanium, 57% by weight of chlorine, 21% by weight of magnesium and DIBP were added. A solid titanium catalyst component containing 20% by weight of was prepared.

(7-2) Prepolymerization treatment 180 g of a solid titanium catalyst component, 30.9 mL of triethylaluminum, and 120 L of heptane are charged into an autoclave with an internal capacity of 200 L and equipped with a stirrer. The reaction was allowed to proceed with stirring for 60 minutes. After the polymerization was completed, the solid components were allowed to settle, and the supernatant was removed and washed with heptane twice. The obtained prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the titanium catalyst component concentration was 1.5 g/L. The prepolymerization catalyst contained 6 grams of polypropylene per gram of solid titanium catalyst component. As the propylene, fossil fuel-derived propylene was used.

(7-3) Main Polymerization 110 kg/h of propylene and hydrogen were supplied to a vessel polymerization vessel (1) having an internal volume of 100 L and equipped with a stirrer so that the hydrogen concentration in the gas phase was 0.8 mol %. 1.4 g/h of the slurry of the prepolymerization catalyst prepared in (7-2) as a solid titanium catalyst component, 5.8 ml/h of triethylaluminum and 2.7 ml/h of dicyclopentyldimethoxysilane were continuously supplied. The polymerization temperature was 73°C and the pressure was 3.2 MPa/G. As the propylene, fossil fuel-derived propylene was used. (The same applies to the following steps.)
The slurry obtained in the vessel polymerization vessel (1) was sent to another vessel polymerization vessel (2) having an internal capacity of 1000 L and equipped with a stirrer, and was further polymerized. To the vessel polymerization vessel (2), 30 kg/h of propylene and hydrogen were supplied so that the hydrogen concentration in the gas phase was 1.1 mol %. Polymerization was carried out at a polymerization temperature of 71°C and a pressure of 3.1 MPa/G.
The slurry obtained in the vessel polymerization vessel (2) was sent to another vessel polymerization vessel (3) having an internal capacity of 500 L and equipped with a stirrer, and was further polymerized. To the vessel polymerization vessel (3), 45 kg/h of propylene and hydrogen were supplied so that the hydrogen concentration in the gas phase was 1.1 mol %. Polymerization was carried out at a polymerization temperature of 69°C and a pressure of 3.0 MPa/G.
After vaporizing the resulting slurry, gas-solid separation was performed to obtain a powdery propylene homopolymer (PP-7-0). The propylene homopolymer was vacuum dried at 80°C. Table 7 shows the resin physical properties of the propylene homopolymer (PP-7-0) thus obtained. When measuring the MFR, 1000 ppm of Irganox 1010 manufactured by Ciba-Geigy and 1000 ppm of Irgafos 168 manufactured by Ciba-Geigy were added as antioxidants.

<Preparation of resin composition containing propylene homopolymer derived from fossil fuel>
(7-4) Additive formulation and kneading/granulation 85% by weight of propylene homopolymer (PP-7-0) powder thus obtained in (7-3), 5% by weight of maleic anhydride-modified polypropylene (F), 1000 ppm of Irganox 1010 manufactured by Ciba-Geigy as an antioxidant with respect to the total of propylene homopolymer (PP-7-0) and maleic anhydride-modified polypropylene (F), to 10% by weight of carbon single fiber (E). 1000 ppm of Irgafos 168 manufactured by Ciba-Geigy and 1000 ppm of calcium stearate as a neutralizing agent are mixed in a tumbler and then melt-kneaded in a single-screw extruder under the following conditions to obtain a resin composition containing a propylene homopolymer. A pellet of (7B-0) was prepared.
<Melt-kneading conditions>
Single shaft kneader: Product number: Labo Plastomill 10M100 (manufactured by Toyo Seiki Co., Ltd.)
Kneading temperature: 220°C
Screw rotation speed: 60 rpm
Pellet length: about 5 mm

(7-5) Injection Molding Using the pellets obtained in (7-4), a test piece (injection molding) was molded using an injection molding machine under the following conditions. Table 7 shows the physical properties of the injection molded article made of the resin composition (7B-0).
<Injection molding conditions>
Injection molding machine: Product number EC40 (manufactured by Toshiba Machine Co., Ltd.)
Cylinder temperature: 210°C
Mold temperature: 40°C
Injection time - holding pressure time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds

[Example 7] (propylene homopolymer (A1): PP-7-1, resin composition containing the propylene homopolymer (A1))
(7-3) Same as (7-1) to (7-3) in Reference Example 7, except that biomass-derived propylene was used instead of fossil fuel-derived propylene as propylene in the main polymerization of Reference Example 7. Then, a propylene homopolymer (PP-7-1), which is the propylene homopolymer (A1), was obtained. Table 7 shows the resin physical properties of the obtained propylene homopolymer (PP-7-1).
Using propylene homopolymer (PP-7-1) obtained in place of fossil fuel-derived propylene homopolymer (PP-7-0), (7-4) additive formulation and kneading / Pellets of resin composition (7B-1) containing propylene homopolymer (PP-7-1), maleic anhydride-modified polypropylene (F), and carbon single fiber (E) were prepared according to granulation, and the same ( 7-5) An injection molded article was produced from pellets of the resin composition (7B-1) according to injection molding. Table 7 shows the physical properties of the obtained injection molded article.

[Reference Example 8] (Fossil fuel-derived propylene-based random copolymer, resin composition containing the propylene-based random copolymer)
<Preparation of Fossil Fuel-Derived Propylene-Based Random Copolymer (PP-8-0)>
(8-1) Preparation of magnesium compound A magnesium compound (solid catalyst carrier) was obtained in the same manner as in Reference Example 2 (2-1).

(8-2) Preparation of Solid Catalyst Component A solid catalyst component was obtained in the same manner as in Reference Example 2 (2-2).

(8-3) Prepolymerization treatment 230 liters of purified heptane was charged into a reactor with a stirrer and having an internal volume of 500 liters, and 25 kg of the solid catalyst component was added. .0 mol/mol, and dicyclopentyldimethoxysilane was supplied at a ratio of 1.8 mol/mol. Thereafter, propylene was introduced until the propylene partial pressure reached 0.03 MPa-G, and the reaction was carried out at 25°C for 4 hours. After completion of the reaction, the solid catalyst component was washed several times with purified heptane, carbon dioxide was supplied, and the mixture was stirred for 24 hours. As the propylene, fossil fuel-derived propylene was used.

(8-4) Main Polymerization Into a polymerization apparatus with a stirrer having an inner capacity of 200 liters, the solid catalyst component treated in (8-3) above was added at 3 mmol/hr in terms of titanium atoms in the component, and 2.5 mmol/hr of triethylaluminum was added. kg-PP and dicyclopentyldimethoxysilane were fed at 0.25 mmol/kg-PP, respectively. Then, at a polymerization temperature of 82° C. and a polymerization pressure of 2.8 MPa-G, propylene, ethylene, and 1-butene were continuously supplied at 46.0 kg/hr, 2.0 kg/hr, and 2.4 kg/hr, respectively, and reacted. rice field. At this time, the ethylene concentration in the polymerization was 2.4 mol %, the 1-butene concentration was 1.8 mol %, and the hydrogen concentration was 8.2 mol %. In addition, propylene derived from fossil fuel was used as propylene, ethylene derived from fossil fuel was used as ethylene, and 1-butene derived from fossil fuel was used as 1-butene.
Table 8 shows the physical properties of the propylene/ethylene/1-butene random copolymer (PP-8-0) thus obtained. When measuring the MFR, 1000 ppm of Irganox 1010 manufactured by Ciba-Geigy and 1000 ppm of Irgafos 168 manufactured by Ciba-Geigy were added as antioxidants.

<Preparation of Resin Composition Containing Fossil Fuel-Derived Propylene-Based Random Copolymer>
(8-5) Additive formulation and kneading/granulation 75% by weight of the propylene/ethylene/1-butene random copolymer powder thus obtained in (8-4), ethylene/α-olefin copolymer (B) 25 1000 ppm of Ciba-Geigy Irganox 1010 as an antioxidant and Ciba-Geigy Co. 1000 ppm of Irgafos 168 and 1000 ppm of calcium stearate as a neutralizing agent are formulated, mixed with a tumbler, melt-kneaded with a twin-screw extruder under the following conditions, and a resin composition containing a propylene-based random copolymer (8B -0) pellets were prepared.
<Melt-kneading conditions>
Co-directional twin-screw kneader: Product number KZW-15 (manufactured by Technobell Co., Ltd.)
Kneading temperature: 190°C
Screw rotation speed: 500 rpm
Feeder rotation speed: 40 rpm

(8-6) Injection molding Using the pellets obtained in (8-5), JIS test pieces (injection moldings) were molded using an injection molding machine under the following conditions. Table 8 shows the physical properties of the injection molded article made of the resin composition (8B-0).
<Injection molding conditions>
Injection molding machine: Product number EC40 (manufactured by Toshiba Machine Co., Ltd.)
Cylinder temperature: 190°C
Mold temperature: 40°C
Injection time - holding pressure time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds

[Example 8] (Propylene-based random copolymer (A2-1): PP-8-1, resin composition containing the propylene-based random copolymer (A2-1))
(8-4) in Reference Example 8 (8-1) to (8-4) in Reference Example 8, except that biomass-derived propylene 1 was used as propylene instead of fossil fuel-derived propylene. Similarly, a propylene/ethylene/1-butene random copolymer (PP-8-1), which is a propylene random copolymer (A2-1), was obtained. Table 8 shows the physical properties of the obtained propylene/ethylene/1-butene random copolymer (PP-8-1).
Using a propylene-based random copolymer (PP-8-1) obtained in place of the fossil fuel-derived propylene-based random copolymer (PP-8-0), additive (8-5) of Reference Example 8 Pellets of a resin composition (8B-1) containing a propylene-based random copolymer (PP-8-1) and an ethylene/α-olefin copolymer (B) are prepared according to the formulation and kneading/granulation, An injection-molded article was produced from pellets of the resin composition (8B-1) in accordance with the same (8-6) injection molding. Table 8 shows the physical properties of the obtained injection molded product.

[Reference Example 9] (Fossil fuel-derived propylene/ethylene block copolymer, resin composition containing the propylene/ethylene block copolymer)
<Preparation of Fossil Fuel Derived Propylene/Ethylene Block Copolymer (PP-9-0)>
(9-1) Preparation of solid titanium catalyst component A solid titanium catalyst component was obtained in the same manner as in Reference Example 4 (4-1).

(9-2) Prepolymerization Treatment A catalyst slurry containing a prepolymerization catalyst component was obtained in the same manner as in Reference Example 4 (4-2).

(9-3) Main Polymerization Into a jacketed circulating tubular polymerization reactor having an internal capacity of 58 L, 43 kg/hour of propylene and 300 NL/hour of hydrogen were charged, and 0.5 kg of the catalyst slurry produced in (9-2) was added as a solid titanium catalyst component. 55 g/hour, 2.9 ml/hour of triethylaluminum, and 3.1 ml/hour of dicyclopentyldimethoxysilane were continuously supplied, and polymerization was carried out in a liquid-filled state in which no gas phase existed. The temperature of the tubular polymerization vessel was 70°C and the pressure was 3.74 MPa/G. As the propylene, fossil fuel-derived propylene was used. (The same applies to the following steps.)
The slurry obtained in the cyclic tubular polymerization vessel was sent to a vessel polymerization vessel having an internal volume of 100 L and equipped with a stirrer, and was further polymerized. To the polymerization reactor, 45 kg/hour of propylene and hydrogen were supplied so that the hydrogen concentration in the gas phase was 8.7 mol %. Polymerization was carried out at a polymerization temperature of 70°C and a pressure of 3.49 MPa/G.
The slurry obtained in the Vessel polymerization vessel was transferred to a liquid transfer tube with a content of 2.4 L, the slurry was gasified, and gas-solid separation was performed. It was sent to a phase polymerizer and ethylene/propylene block copolymerization (preparation of propylene/ethylene random copolymer component (d)) was carried out. At this time, the powder was sampled before copolymerization, and MFR, melting point, pentad fraction, and Mw/Mn were measured. When measuring the MFR, 1000 ppm of Irganox 1010 manufactured by Ciba-Geigy and 1000 ppm of Irgafos 168 manufactured by Ciba-Geigy were added as antioxidants.
Propylene, ethylene, and hydrogen were continuously added so that the gas composition in the gas phase polymerization vessel was 0.23 (molar ratio) as ethylene/(ethylene + propylene) and 0.031 (molar ratio) as hydrogen/ethylene. supplied. Polymerization was carried out at a polymerization temperature of 70°C and a pressure of 1.0 MPa/G. As ethylene, ethylene derived from fossil fuel was used.
After vaporizing the slurry obtained in the gas phase polymerization reactor, gas-solid separation was performed to obtain a propylene/ethylene block copolymer (PP-9-0). The obtained propylene/ethylene block copolymer was vacuum dried at 80°C. Table 9 shows the resin physical properties of the propylene/ethylene block copolymer (PP-9-0) thus obtained. In the MFR measurement, 1000 ppm of Irganox 1010 manufactured by Ciba-Geigy and 1000 ppm of Irgafos 168 manufactured by Ciba-Geigy were added as antioxidants, and 1000 ppm of calcium stearate was added as a neutralizer, and pellets obtained by melt-kneading were obtained. Using.

<Preparation of Resin Composition Containing Fossil Fuel-Derived Propylene/Ethylene Block Copolymer>
(9-4) Additive formulation and kneading/granulation To 75% by weight of the propylene/ethylene block copolymer powder thus obtained in (9-3) and 25% by weight of the ethylene/α-olefin copolymer (B), 1000 ppm of Irganox 1010 manufactured by Ciba-Geigy and 1000 ppm of Irgafos 168 manufactured by Ciba-Geigy are neutralized with respect to the total of the propylene/ethylene block copolymer and the ethylene/α-olefin copolymer (B). 1000 ppm of calcium stearate was formulated as an agent, mixed in a tumbler, and then melt-kneaded in a twin-screw extruder under the following conditions to prepare pellets of a resin composition (9B-0) containing a propylene/ethylene block copolymer. bottom.
<Melt-kneading conditions>
Co-directional twin-screw kneader: Product number KZW-15 (manufactured by Technobell Co., Ltd.)
Kneading temperature: 190°C
Screw rotation speed: 500 rpm
Feeder rotation speed: 40 rpm

(9-5) Injection molding Using the pellets obtained in (9-4), a JIS test piece (injection molded body) is molded under the following conditions with an injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.]. bottom. Table 9 shows the physical properties of the injection molded article made of the resin composition (9B-0).
<Injection molding conditions>
Injection molding machine: Product number EC40 (manufactured by Toshiba Machine Co., Ltd.)
Cylinder temperature: 190°C
Mold temperature: 40°C
Injection time - holding pressure time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds

[Example 9]
(9-3) In the main polymerization of Reference Example 9, as propylene, biomass-derived propylene was used instead of fossil fuel-derived propylene, and biomass-derived ethylene was used instead of fossil fuel-derived ethylene. A propylene/ethylene block copolymer (PP-9-1), which is a propylene/ethylene block copolymer (A2-2), was obtained in the same manner as (9-1) to (9-3). Table 9 shows the physical properties of the obtained propylene/ethylene block copolymer (PP-9-1).
(9-4) of Reference Example 9 using a propylene/ethylene block copolymer (PP-9-1) obtained in place of the fossil fuel-derived propylene/ethylene block copolymer (PP-9-0) Pellets of a resin composition (9B-1) containing a propylene/ethylene block copolymer (PP-9-1) and an ethylene/α-olefin copolymer (B) are produced according to the additive formulation and kneading/granulation. An injection molded product was produced from pellets of the resin composition (9B-1) according to the same (9-5) injection molding. Table 9 shows the physical properties of the obtained injection molded product.

[Reference Example 10] (Fossil fuel-derived propylene/ethylene block copolymer, resin composition containing the propylene/ethylene block copolymer)
<Preparation of Fossil Fuel-Derived Propylene/Ethylene Block Copolymer (PP-10-0)>
(10-1) Preparation of solid titanium catalyst component A solid titanium catalyst component was obtained in the same manner as in Reference Example 4 (4-1).

(10-2) Prepolymerization treatment 100 g of the solid titanium catalyst component obtained in (10-1), 131 mL of triethylaluminum, 37.3 mL of diethylaminotriethoxysilane, and 14.3 L of heptane are placed in an autoclave with an internal capacity of 20 L and equipped with a stirrer. Then, 1000 g of propylene was added while the internal temperature was kept at 15 to 20° C., and the reaction was allowed to proceed for 120 minutes while stirring. After the polymerization was completed, the solid components were allowed to settle, and the supernatant was removed and washed with heptane twice. The resulting prepolymerized catalyst was resuspended in purified heptane, and adjusted with heptane so that the concentration of the solid titanium catalyst component was 1.0 g/L, to obtain a catalyst slurry.

(10-3) Main Polymerization Into a jacketed circulating tubular polymerization reactor having an internal capacity of 58 L, 43 kg/hour of propylene and 256 NL/hour of hydrogen were charged, and 0.05% of the catalyst slurry produced in (10-2) was added as a solid titanium catalyst component. 49 g/hour, 4.5 ml/hour of triethylaluminum, and 1.8 ml/hour of diethylaminotriethoxysilane were continuously supplied, and polymerization was carried out in a liquid-filled state in which no gas phase existed. The temperature of the tubular polymerization vessel was 70°C and the pressure was 3.57 MPa/G. As the propylene, fossil fuel-derived propylene was used (the same applies to the following steps).
The slurry obtained in the tubular polymerization vessel was sent to a vessel polymerization vessel having an internal capacity of 100 L and equipped with a stirrer, and was further polymerized. To the polymerization vessel, 45 kg/hour of propylene and hydrogen were supplied so that the hydrogen concentration in the gas phase was 8.8 mol %. Polymerization was carried out at a polymerization temperature of 68°C and a pressure of 3.36 MPa/G.
The slurry obtained in the Vessel polymerization vessel was transferred to a liquid transfer tube with a content of 2.4 L, the slurry was gasified, and gas-solid separation was performed. The mixture was sent to a gas-phase polymerization vessel and subjected to ethylene/propylene block copolymerization (preparation of propylene/ethylene random copolymer component (d)). At this time, the powder was sampled before copolymerization, and MFR, melting point, pentad fraction, and Mw/Mn were measured. When measuring the MFR, 1000 ppm of Irganox 1010 manufactured by Ciba-Geigy and 1000 ppm of Irgafos 168 manufactured by Ciba-Geigy were added as antioxidants.
Propylene, ethylene, and hydrogen were continuously added so that the gas composition in the gas phase polymerization reactor was 0.20 (molar ratio) as ethylene/(ethylene + propylene) and 0.0063 (molar ratio) as hydrogen/ethylene. supplied. Polymerization was carried out at a polymerization temperature of 70°C and a pressure of 1.40 MPa/G. As ethylene, ethylene derived from fossil fuel was used.
After vaporizing the slurry obtained in the gas phase polymerization reactor, gas-solid separation was performed to obtain a propylene/ethylene block copolymer (PP-10-0). The obtained propylene/ethylene block copolymer was vacuum-dried at 80°C. Table 10 shows the resin physical properties of the propylene/ethylene block copolymer (PP-10-0) thus obtained. In the MFR measurement, 1000 ppm of Irganox 1010 manufactured by Ciba-Geigy and 1000 ppm of Irgafos 168 manufactured by Ciba-Geigy were added as antioxidants, and 1000 ppm of calcium stearate was added as a neutralizer, and pellets obtained by melt-kneading were obtained. Using.

<Preparation of Resin Composition Containing Fossil Fuel-Derived Propylene/Ethylene Block Copolymer>
(10-4) Additive formulation and kneading/granulation 60% by weight of propylene/ethylene block copolymer powder thus obtained in (10-3), 20% by weight of ethylene/α-olefin copolymer (B), talc (C) 20% by weight of propylene/ethylene block copolymer and ethylene/α-olefin copolymer (B) combined with 1000 ppm of Ciba-Geigy Irganox 1010 as an antioxidant and Ciba-Geigy 1000 ppm of Irgafos 168 and 1000 ppm of calcium stearate as a neutralizing agent are mixed in a tumbler and then melt-kneaded by a twin-screw extruder under the following conditions to obtain a resin composition containing a propylene/ethylene block copolymer ( 10B-0) were prepared.
<Melt-kneading conditions>
Co-directional twin-screw kneader: Product number KZW-15 (manufactured by Technobell Co., Ltd.)
Kneading temperature: 190°C
Screw rotation speed: 500 rpm
Feeder rotation speed: 40 rpm

(10-5) Injection Molding Using the pellets obtained in (10-4), JIS test pieces (injection molded articles) were molded using an injection molding machine under the following conditions. Table 10 shows the physical properties of the injection molded article made of the resin composition (10B-0).
<Injection molding conditions>
Injection molding machine: Product number EC40 (manufactured by Toshiba Machine Co., Ltd.)
Cylinder temperature: 190°C
Mold temperature: 40°C
Injection time - holding pressure time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds

[Example 10]
(10-3) of Reference Example 10, except that biomass-derived propylene was used instead of fossil fuel-derived propylene as propylene in the main polymerization, and biomass-derived ethylene was used as ethylene (10-1) of Reference Example 10. A propylene/ethylene block copolymer (PP-10-1), which is a propylene/ethylene block copolymer (A2-2), was obtained in the same manner as in (10-3). Table 10 shows the physical properties of the obtained propylene/ethylene block copolymer (PP-10-1).
(10-4) of Reference Example 10 using a propylene/ethylene block copolymer (PP-10-1) obtained in place of the fossil fuel-derived propylene/ethylene block copolymer (PP-10-0) A resin composition (10B- The pellets of 1) were prepared, and an injection-molded article was produced from the pellets of the resin composition (10B-1) according to the same (10-5) injection molding. Table 10 shows the physical properties of the obtained injection molded product.

From the results of Tables 1 to 10, the propylene-based polymer (A) of the present invention and the resin composition containing the propylene-based polymer (A) are made of fossil fuel-derived olefins as raw materials, existing fossil fuels with a large environmental load. It has the same performance as the derived propylene-based polymer and the resin composition containing the propylene-based polymer. The present invention can reduce the environmental load.

Claims (19)

A propylene homopolymer or a propylene-based polymer that is a copolymer of propylene and at least one olefin (b) selected from the group consisting of ethylene and α-olefins having 4 to 8 carbon atoms, A propylene-based polymer in which the propylene contained in the coalesced raw material is biomass-derived propylene. The propylene-based polymer is a propylene homopolymer,
The propylene-based polymer according to claim 1, wherein the propylene homopolymer satisfies the following (i) to (ii).
(i) Melt flow rate (MFR) at 230° C. and 2.16 kg load of 0.01 g/10 min or more and 2,000 g/10 min or less (ii) Isotactic pentad fraction of 90.0% or more 99.9% or less 3. The propylene-based polymer according to claim 2, which is a propylene homopolymer having a biomass content of 100% according to ASTM D 6866. The propylene-based polymer is a random copolymer of propylene and at least one olefin (b) selected from the group consisting of ethylene and α-olefins having 4 to 8 carbon atoms,
The random copolymer contains 90.0% by weight or more and 99.9% by weight or less of structural units derived from propylene and 0.1% by weight or more and 10.0% by weight or less of structural units derived from olefin (b). including
The propylene-based polymer according to claim 1, which satisfies the following (iii) to (iv).
(iii) Melt flow rate (MFR) at 230°C and 2.16 kg load of 0.01 g/10 min or more and 2,000 g/10 min or less (iv) Melting point of 100°C or more and 160°C or less A random copolymer of propylene having a biomass degree of 90% or more according to ASTM D 6866 and at least one olefin (b) selected from the group consisting of ethylene and α-olefins having 4 to 8 carbon atoms, The propylene-based polymer according to claim 4. The propylene-based polymer is a propylene/ethylene block copolymer,
The propylene/ethylene block copolymer is
A propylene homopolymer or a crystalline propylene/ethylene random copolymer containing 95% by weight or more and less than 100% by weight of structural units derived from propylene and 5% by weight or less of structural units derived from ethylene, the following (v)
(v) Intrinsic viscosity [η] of 0.8 (dl/g) or more and 3.0 (dl/g)
55% by weight or more and 95% by weight of the crystalline propylene-based polymer component (c) satisfying
Containing 20% by weight or more and 80% by weight or less of structural units derived from propylene and 20% by weight or more and 80% by weight of structural units derived from ethylene, the following (vi)
(vi) Intrinsic viscosity [η] of 1.0 (dl/g) or more and 10.0 (dl/g)
2. The propylene-based polymer according to claim 1, containing 5% by weight or more and 45% by weight or less of the propylene-ethylene random copolymer component (d) satisfying 7. The propylene-based polymer according to claim 6, which is a propylene/ethylene block copolymer having a biomass content of 61% or more and 100% or less according to ASTM D 6866. A method for producing a propylene-based polymer which is a propylene homopolymer or a copolymer of propylene and at least one olefin (b) selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms,
including a step of supplying a raw material containing propylene to a polymerization vessel and polymerizing it with a polymerization catalyst;
A method for producing a propylene-based polymer, wherein the propylene contained in the raw material is biomass-derived propylene. The method for producing a propylene-based polymer according to claim 8, wherein the propylene-based polymer is a propylene homopolymer satisfying the following (i) to (ii).
(i) Melt flow rate (MFR) at 230°C and 2.16 kg load of 0.
01 g/10 min or more and 2,000 g/10 min or less (ii) The isotactic pentad fraction is 90.0% or more and 99.9% or less The propylene-based polymer satisfies the following (iii) to (iv) by random copolymerization of propylene and at least one olefin (b) selected from the group consisting of ethylene and α-olefins having 4 to 8 carbon atoms. The method for producing a propylene-based polymer according to claim 8, wherein the propylene-based polymer is a coalescence.
(iii) Melt flow rate (MFR) at 230°C and 2.16 kg load of 0.01 g/10 min or more and 2,000 g/10 min or less (iv) Melting point of 100°C or more and 160°C or less The random copolymer contains 90.0% by weight or more and 99.9% by weight or less of structural units derived from propylene and 0.1% by weight or more and 10.0% by weight of structural units derived from at least one olefin (b). % or less. The propylene-based polymer is a propylene/ethylene block copolymer,
The propylene/ethylene block copolymer is
A propylene homopolymer or a crystalline propylene/ethylene random copolymer containing 95% by weight or more and less than 100% by weight of structural units derived from propylene and 5% by weight or less of structural units derived from ethylene, the following (v)
(v) Intrinsic viscosity [η] of 0.8 (dl/g) or more and 3.0 (dl/g)
55% by weight or more and 95% by weight of the crystalline propylene-based polymer component (c) satisfying
Containing 20% by weight or more and 80% by weight or less of structural units derived from propylene and 20% by weight or more and 80% by weight of structural units derived from ethylene, the following (vi)
(vi) Intrinsic viscosity [η] of 1.0 (dl/g) or more and 10.0 (dl/g)
5% by weight or more and 45% by weight or less of the propylene/ethylene random copolymer component (d) satisfying
A raw material (1) containing propylene or propylene and ethylene is supplied to a polymerization vessel and polymerized with a polymerization catalyst,
A crystalline propylene-based polymer comprising a propylene homopolymer or a crystalline propylene/ethylene random copolymer containing 95% by weight or more and less than 100% by weight of structural units derived from propylene and 5% by weight or less of structural units derived from ethylene. A step (α) of preparing component (c), and supplying raw material (2) containing propylene and ethylene to a polymerization vessel and polymerizing with a polymerization catalyst to prepare propylene/ethylene random copolymer component (d). The method for producing a propylene-based polymer according to claim 8, comprising the step (β) of A resin composition comprising the propylene homopolymer according to claim 2 or 3. 6. A resin composition comprising a random copolymer of propylene according to claim 4 or 5 and at least one olefin (b) selected from the group consisting of ethylene and α-olefins having 4 to 8 carbon atoms. A resin composition comprising the propylene/ethylene block copolymer according to claim 6 or 7. A molded article comprising the propylene homopolymer according to claim 2 or 3. A molded article comprising a random copolymer of the propylene according to claim 4 or 5 and at least one olefin (b) selected from the group consisting of ethylene and α-olefins having 4 to 8 carbon atoms. A molded article comprising the propylene/ethylene block copolymer according to claim 6 or 7. A molded article made of the resin composition according to any one of claims 13 to 15.