JP2024005096A - Propylene-based polymer obtained from olefin containing chemical recycle-derived propylene, and production method of the propylene-based polymer - Google Patents

Abstract

To reduce the environmental burden (greenhouse gas emissions) during the life cycle from production to use and disposal of propylene-based polymers, and to provide propylene-based polymers with the same performance as propylene-based polymers obtained from raw materials containing only fossil fuel-derived propylene as propylene, using raw materials containing propylene derived from chemical recycling; to provide a production method of the polymer; and to provide propylene-based polymers with the same performance as propylene-based polymers obtained from raw materials containing only fossil fuel-derived propylene as propylene, using raw materials containing propylene derived from chemical recycling at a reduced cost, taking into account market needs and other factors.SOLUTION: There is provided a propylene-based polymer which is a propylene homopolymer or a copolymer of propylene and a specific olefin, in which the propylene-based polymers have the same performance as propylene-based polymers obtained from raw materials containing only fossil fuel-derived propylene as propylene, using raw materials containing propylene derived from chemical recycling.SELECTED DRAWING: None

Description

The present invention relates to a propylene polymer and a method for producing the polymer. More specifically, the present invention relates to a propylene polymer obtained by polymerizing propylene including propylene obtained by chemical recycling, and a method for producing the polymer.

In recent years, there has been a demand for a change to a sustainable society, and from the perspective of reducing the environmental impact of plastic products, instead of landfilling or incinerating used or discarded polyester, we can use the monomers or low-carbon materials obtained after depolymerization. It has been considered to produce recycled polyester by polymerizing the polymer again (Patent Document 1, Patent Document 2). Similarly, with polyamide, it is being considered to produce recycled polyamide by repolymerizing the obtained monomer after depolymerization, without burying or incinerating used or discarded polyamide (Patent Document 3). ). Compared to fossil fuel polyester film, chemically recycled polyester film has a smaller area ratio of the region with a molecular weight of 1,000 or less in the molecular weight distribution curve obtained from GPC measurements, and has excellent hygiene (there is no change in taste due to the film). (Patent Document 4).

Regarding polyolefins such as polyethylene and polypropylene, hydrocarbon oil is produced by thermal decomposition of waste polyolefin, and the obtained hydrocarbon oil is said to be suitable for fuel (Patent Document 5). In addition, the production of olefins with 2 to 4 carbon atoms by thermal decomposition of waste polyolefins is being considered, and olefin gas with 2 to 4 carbon atoms can be reused as a raw material for plastics, and hydrogen can be used as fuel for fuel cells and hydrogenated. - It is disclosed that it can be reused as a raw material for desulfurization, and that the liquid phase can be separated into benzene, toluene, and xylene using a distillation column and reused as a raw material for chemicals/medicines (Patent Document 6).

Japanese Patent Application Publication No. 2003-119316 Japanese Patent Application Publication No. 2009-173732 Japanese Patent Application Publication No. 7-310204 JP2022-002890A Japanese Patent Application Publication No. 10-330764 Japanese Patent Application Publication No. 2002-121318

However, Patent Document 6 does not clarify how the structure and performance of polyolefin obtained when polyolefin is produced by reusing olefin as a raw material through thermal decomposition of waste polyolefin.

The purpose of the present invention is to reduce the environmental burden (greenhouse gas generation) in the life cycle of propylene polymers, from production to utilization and disposal, and to use raw materials containing propylene derived from chemical recycling to produce propylene that is derived from fossil fuels. It is an object of the present invention to provide a propylene polymer having performance equivalent to that of a propylene polymer obtained from a raw material containing only propylene, and to provide a method for producing the polymer. In addition, another object of the present invention is to reduce the cost by taking into account market needs, etc., and using a raw material containing propylene derived from chemical recycling to produce a propylene-based heavy compound obtained from a raw material containing only propylene derived from fossil fuels as propylene. It is an object of the present invention to provide a propylene-based polymer having performance equivalent to that of a polymer.

As a result of intensive studies to solve the above-mentioned problems, the present inventors found that the propylene used as the raw material for the propylene polymer is a raw material containing propylene derived from specific chemical recycling, so that the resulting propylene polymer can The present inventors have discovered that the above-mentioned problems can be solved by having the same performance as a propylene-based polymer obtained from a raw material containing only fossil fuel-derived propylene as propylene, and have completed the present invention.

The present invention relates to the following [1] to [16].
[1] A propylene-based polymer which is a propylene homopolymer or a copolymer of propylene and at least one olefin selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms, A propylene-based polymer in which the propylene contained in the raw material of the polymer contains 0.1% by weight or more of propylene derived from chemical recycling.

[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 is 0.01 g/10 minutes or more and 2,000 g/10 minutes or less (ii) Isotactic pentad fraction is 90.0% or more 99.9% or less

[3] 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% to 99.9% by weight of structural units derived from propylene and 0.1% to 10.0% by weight of structural units derived from olefin (b). including,
The propylene polymer according to [1], which satisfies (iii) to (iv) below.
(iii) Melt flow rate (MFR) at 230℃ and 2.16kg load is 0.01g/10 minutes or more and 2,000g/10minutes or less (iv) Melting point is 100℃ or more and 160℃ or less

[4] The propylene-based polymer is a propylene/ethylene block copolymer,
The propylene/ethylene block copolymer is
Consisting of 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, and the following (v)
(v) a crystalline propylene polymer component having an intrinsic viscosity [η] of 0.8 (dl/g) or more and 3.0 (dl/g) or less (c) 55% by weight or more and 95% by weight or less;
Contains 20% to 80% by weight of structural units derived from propylene and 20% to 80% by weight of structural units derived from ethylene, and the following (vi)
(vi) A propylene/ethylene random copolymer component (d) with an intrinsic viscosity [η] of 1.0 (dl/g) or more and 10.0 (dl/g) or less (d) 5% by weight or more and 45% by weight or less The propylene polymer according to [1].

[5] A method for producing a propylene 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 α-olefins having 4 to 8 carbon atoms. and
Including the 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 polymer, wherein the propylene contained in the raw material contains 0.1% by weight or more of propylene derived from chemical recycling.
[6] The propylene-based polymer is a propylene homopolymer that satisfies the following (i) to (ii);
(i) Melt flow rate (MFR) at 230°C and 2.16 kg load is 0.01 g/10 minutes or more and 2,000 g/10 minutes or less (ii) Isotactic pentad fraction is 90.0% or more 99.9% or less The method for producing a propylene polymer according to [5], which includes a step of supplying propylene as a raw material to a polymerization vessel and polymerizing it with a polymerization catalyst.

[7] The propylene polymer is a combination of propylene and at least one olefin (b) selected from the group consisting of ethylene and α-olefin having 4 to 8 carbon atoms, which satisfies the following (iii) to (iv). It is a random copolymer,
(iii) The melt flow rate (MFR) at 230°C and a load of 2.16 kg is 0.01 g/10 minutes or more and 2,000 g/10 minutes or less (iv) The melting point is 100°C or more and 160°C or less. The method for producing a propylene polymer according to [5], wherein the raw material contains propylene, at least one olefin (b) selected from the group consisting of ethylene and α-olefins having 4 to 8 carbon atoms.
[8] The random copolymer contains 90.0% to 99.9% by weight of structural units derived from propylene and 0.1% to 10% by weight of structural units derived from at least one type of olefin (b). .0% by weight or less, the method for producing a propylene polymer according to [7].

[9] The propylene-based polymer is a propylene/ethylene block copolymer,
The propylene/ethylene block copolymer is
Consisting of 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, and the following (v)
(v) a crystalline propylene polymer component having an intrinsic viscosity [η] of 0.8 (dl/g) or more and 3.0 (dl/g) or less (c) 55% by weight or more and 95% by weight or less;
Contains 20% to 80% by weight of structural units derived from propylene and 20% to 80% by weight of structural units derived from ethylene, and the following (vi)
(vi) Propylene/ethylene random copolymer component (d) having an intrinsic viscosity [η] of 1.0 (dl/g) or more and 10.0 (dl/g) or less (d) 5% by weight or more and 45% by weight or less; Contains
Supplying propylene or a raw material (1) containing propylene and ethylene to a polymerization vessel and polymerizing it with a polymerization catalyst,
A crystalline propylene-based polymer consisting of 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 polymer according to [5], comprising the step (β).

[10] A resin composition containing the propylene homopolymer according to [2].
[11] A resin composition comprising a random copolymer of the propylene described in [3] and at least one olefin (b) selected from the group consisting of ethylene and α-olefins having 4 to 8 carbon atoms.
[12] A resin composition comprising the propylene/ethylene block copolymer according to [4].
[13] A molded article made of the propylene homopolymer according to [2].
[14] A molded article made of a random copolymer of the propylene described in [3] and at least one olefin (b) selected from the group consisting of ethylene and α-olefins having 4 to 8 carbon atoms.
[15] A molded article comprising the propylene/ethylene block copolymer according to [4].
[16] A molded article made of the resin composition according to any one of [10] to [12].

According to the propylene-based polymer and the method for producing the polymer of the present invention, the environmental load (greenhouse gas generation) during the life cycle can be reduced. Further, according to the propylene polymer and the method for producing the polymer of the present invention, using a raw material containing propylene derived from chemical recycling, the propylene is equivalent to a propylene polymer obtained from a raw material containing only propylene derived from fossil fuels. It becomes possible to produce a propylene-based polymer having the following performance, and it is possible to promote the spread of such a propylene-based polymer at a reduced cost, taking market needs into consideration.

The present invention will be explained in more detail below.
[Olefin derived from chemical recycling]
In the present invention, olefins such as ethylene and propylene obtained by thermal decomposition are converted into olefins derived from chemical recycling using waste plastics containing waste polyolefin resins (which may also include unused polyolefin resins) and waste oils derived from fossil fuels. (ethylene derived from chemical recycling, propylene derived from chemical recycling).
Further, the waste polyolefin resin (which may include unused polyolefin resin) may be a waste polyolefin resin containing biomass-derived carbon (biomass-derived olefin). The biomass-derived carbon concentration can be determined from the ¹⁴ C abundance ratio in carbon in accordance with ASTM D6866-21.

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

[Propylene polymer (A)]
The propylene 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). (exceeding and including) polymers. Such a propylene-based polymer (A) is typically a propylene homopolymer (A1) or at least one olefin selected from the group consisting of propylene, ethylene, and an α-olefin having 4 to 8 carbon atoms (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)) (hereinafter, copolymer (A2) with propylene-based copolymer) (also referred to as polymer (A2)).

As the propylene-based copolymer (A2), a random copolymer (A2-1) of propylene and olefin (b) (for example, propylene/ethylene random copolymer, propylene/α-olefin (carbon number 4 to 8 ) random copolymer, propylene/ethylene/α-olefin (carbon number 4 to 8) random copolymer, etc.) (hereinafter, random copolymer of propylene and olefin (b) (A2-1) (also simply referred to as propylene random copolymer (A2-1)), a propylene homopolymer or 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 crystalline propylene polymer component (c) consisting of a crystalline propylene/ethylene random copolymer, a structural unit derived from propylene of 20% to 80% by weight, and a structural unit derived from ethylene of 20% to 80% by weight A propylene/ethylene block copolymer (A2-2) containing a propylene/ethylene random copolymer component (d) containing % and the like can be mentioned.

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

(Raw material propylene for propylene polymer (A))
In the propylene polymer (A) of the present invention, propylene (a) contained in the raw material thereof (hereinafter, propylene (a) contained in the raw material of the propylene polymer (A) is also simply referred to as raw material propylene (a). ) contains 0.1% by weight or more of propylene derived from chemical recycling. The raw material propylene (a) may contain only propylene derived from chemical recycling (a1), but in addition to propylene derived from chemical recycling, propylene derived from fossil fuel (a2), propylene derived from biomass (a3), or propylene derived from fossil fuel Propylene (a2) and biomass-derived propylene (a3) may be included. Biomass refers to all renewable natural raw materials and their residues derived from plants or animals, including fungi, yeast, algae, and bacteria, and biomass-derived olefins (ethylene, α-olefins, etc.) , refers to the olefins obtained from this biomass. Biomass-derived carbon contains a certain amount of ¹⁴ C isotope as carbon (at a ratio of about 10 ^-12 ).
For example, it is preferable that the raw material propylene (a) contains propylene derived from chemical recycling (a1) and fossil fuel propylene (a2) as necessary. In this case, typically, the propylene derived from chemical recycling Contains propylene (a1) from 0.1% by weight to 100% by weight, and fossil fuel-derived propylene (a2) from 0% by weight to 99.9% by weight. In other words, when containing propylene derived from chemical recycling (a1) and fossil fuel propylene (a2) if necessary, as long as the raw material propylene (a) satisfies the above conditions, the form in which the raw material propylene (a) is entirely derived from chemical recycling, and the chemical A preferred form is a mixture of propylene derived from recycling and propylene derived from fossil fuels.
When the raw material propylene (a) is a mixture of chemical recycling-derived propylene (a1) and fossil fuel propylene (a2), the raw material propylene (a) preferably contains 1% by weight of chemical recycling-derived propylene (a1). 95% by weight or less and fossil fuel-derived propylene (a2) 5% to 99% by weight, more preferably 5% to 90% by weight of chemical recycling-derived propylene (a1) and fossil fuel-derived propylene (a2). ) 10% to 95% by weight, more preferably 10% to 69% by weight of chemical recycling-derived propylene (a1) and 31% to 90% by weight of fossil fuel-derived propylene (a2) . Here, the total of propylene derived from chemical recycling (a1) and propylene derived from fossil fuel (a2) is 100% by weight. In addition, chemical recycling-derived propylene (a1) means the chemical recycling-derived propylene contained in the raw material propylene (a), and fossil fuel-derived propylene (a2) means the fossil fuel-derived propylene contained in the raw material propylene (a). However, the biomass-derived propylene (a3) means the biomass-derived propylene contained in the raw material propylene (a).
In order to achieve a desired ratio (wt%) of propylene derived from chemical recycling (a1) and propylene derived from fossil fuels (a2) contained in the raw material propylene (a), for example, propylene derived from chemical recycling obtained separately (a1) and fossil fuel-derived propylene (a2) may be mixed in a desired ratio (wt%). Furthermore, even when biomass-derived propylene is included in the raw material propylene (a), it may be mixed in a desired ratio using the same method.

In addition, the raw material propylene (a) means that, for example, when the propylene polymer (A) is a propylene homopolymer (A1), the raw material propylene (a) satisfies the above requirements. However, when the propylene polymer (A) is a propylene copolymer (A2), it is confirmed that the propylene (a) contained as a raw material for the propylene copolymer (A2) satisfies the above requirements. means.

Since the production cost of propylene derived from chemical recycling is higher than that of propylene derived from fossil fuels, it is necessary to use raw materials in which the ratio of propylene derived from chemical recycling (a1) to propylene derived from fossil fuels (a2) satisfies the above requirements. The produced propylene-based polymer can promote the spread of cost-reduced propylene-based polymers while contributing to reducing the environmental load during its life cycle.
When the propylene polymer (A) is a propylene copolymer (A2), the olefin species other than propylene contained in the raw material may be only olefins derived from chemical recycling or only olefins derived from biomass. , may be only fossil fuel-derived olefins, or may be a mixture of these olefins. For example, if reducing environmental impact is important, it is desirable that the olefin species other than propylene include olefins derived from chemical recycling. Further, for example, if cost reduction is important, it is desirable that the olefin species other than propylene be only fossil fuel-derived olefins. Furthermore, for example, when it is desired to place importance on improving the biomass degree of the propylene-based polymer (A), it is desirable that the olefin species other than propylene be only biomass-derived olefins. Moreover, the olefin corresponding to olefin (a) can also be selected in consideration of ease of production of the olefin used as a raw material for propylene polymer (A).
According to the studies conducted by the present inventors, biomass-derived olefins and fossil fuel-derived olefins of the same olefin species have different polymerization performance (activity, copolymerizability, stereoregularity, etc.) under the same polymerization conditions (polymerization catalyst, polymerization temperature, etc.). There is no significant difference in the properties, stereoregularity distribution, molecular weight, molecular weight distribution, etc.).

The method for producing the propylene polymer (A) of the present invention is not particularly limited as long as the raw material propylene (a) satisfies the above requirements. The propylene polymer (A) of the present invention can be produced, for example, by the method for producing a propylene 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 it is sufficient that the raw material propylene (a) satisfies the above requirements (for example, the raw material propylene (a) Contains 0.1% to 100% by weight of propylene derived from chemical recycling (a1) and 0% to 99.9% by weight of propylene derived from fossil fuels (a2) (The total amount of propylene (a2) is 100% by weight).The same applies to preferred embodiments of the weight% of each component described in the explanation regarding the propylene polymer (A) below.)

The propylene homopolymer (A1) of the present invention preferably satisfies any of the following (i) to (ii), more preferably both of the following (i) to (ii).
(i) The melt flow rate (MFR) at 230°C and a load of 2.16 kg is 0.01 g/10 minutes or more and 2,000 g/10 minutes or less, preferably 0.05 g/10 minutes or more and 1,000 g/10 minutes or less. It takes less than 10 minutes. When the melt flow rate (MFR) is within this range, moldability and performance of the molded product when processed into various molded products are excellent.
(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, various molded products will have excellent performance. The isotactic pentad fraction is determined from ¹³ C-NMR measurement of the polymer.

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 even if it has a specific amount of low crystalline components, it cannot be irradiated with an electron beam. It 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, WO 2005/097842, JP 2000-44630, JP 11-349635, JP 11-100412, JP 8-85711, JP 8-73529, JP 2014-231604, WO 2008/088022, JP 2006-328300, JP 2011-26620, JP 10-17610, The propylene homopolymer (A1) of the present invention is prepared from at least a part of the propylene homopolymer described in publications such as JP-A-6-236709 and WO 1997/045563 so as to have the properties described in the above-mentioned publications. After that, 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, and for example, it may be a propylene homopolymer with an isotactic pentad fraction of less than 90.0%, and a syndiotactic structure. It may be a propylene homopolymer having an atactic structure, or a propylene homopolymer having an atactic structure.

[Propylene-based 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 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. The content of 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.

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

In the propylene random copolymer (A2-1) as well, the raw material propylene (a) needs to satisfy the above requirements. Since the production cost of chemically recycled olefins is higher than that of fossil fuel-derived olefins, propylene random copolymer (A2-1) produced using raw materials that meet the above requirements has the potential to reduce environmental impact. It is possible to promote the widespread use of random copolymers of propylene and olefin (b), which contribute to the development of the present invention and reduce costs.

When the propylene-based random copolymer (A2-1) contains structural units derived from ethylene, the manufacturing cost of ethylene derived from chemical recycling is high compared to the manufacturing cost of ethylene derived from fossil fuels. In addition, from the perspective of further promoting the spread of propylene-based random copolymer (A2-1) that reduces costs while contributing to reducing environmental impact, the raw material ethylene is, for example, 0.1% by weight of ethylene derived from chemical recycling. % or more and 100% by weight or less and fossil fuel-derived ethylene from 0% to 99.9% by weight (the total of chemical recycling-derived ethylene and fossil fuel-derived ethylene is 100% by weight).

When the propylene-based random copolymer (A2-1) contains structural units derived from α-olefins having 4 to 8 carbon atoms, the propylene-based random copolymer (A2-1) can be used to reduce costs while contributing to reducing environmental impact. From the perspective of further promoting the spread of copolymer (A2-1), the raw material α-olefin with 4 to 8 carbon atoms must contain α-olefin with 4 to 8 carbon atoms derived from chemical recycling (chemical One preferable form is a recycled α-olefin (4 to 8 carbon atoms) and a fossil fuel-derived α-olefin (4 to 8 carbon atoms, the total of which is 100% by weight).

The propylene random copolymer (A2-1) of the present invention preferably satisfies any of the following (iii) to (iv), more preferably both of the following (iii) to (iv).
(iii) The melt flow rate (MFR) at 230°C and a load of 2.16 kg is 0.01 g/10 minutes or more and 2,000 g/10 minutes or less, preferably 0.05 g/10 minutes or more and 1,000 g/10 minutes or less. It takes less than 10 minutes. When the melt flow rate (MFR) is within this range, moldability and performance of the molded product when processed into various molded products are excellent. Note that the MFR is a value measured at a measurement temperature of 230° C. and a load of 2.16 kg in accordance with ASTM D1238E.
(iv) The melting point is 100°C or more and 160°C or less, preferably 115°C or more and 155°C or less. When the melting point is within this range, transparency, sealability, and flexibility are excellent. Note that the above melting point is a value measured using a differential scanning calorimeter in accordance with JIS-K7121.

The propylene-based random copolymer (A2-1) may have a specific molecular weight distribution, or may be subjected to electron beam irradiation even if the low crystal component is in a specific amount. 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, and 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, The propylene random copolymer (A2-1) of the present invention is prepared from at least a part of the propylene random copolymer described in publications such as JP-A-2006-57010 so as to have the properties described in the above publication. After that, it can be used in place of the propylene random copolymer (A2-1).

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

The crystalline propylene polymer component (c) contained in the propylene/ethylene block copolymer (A2-2) preferably satisfies the following (v).
(v) The crystalline propylene polymer component (c) has an intrinsic viscosity [η] of 0.8 (dl/g) or more and 3.0 (dl/g) or less.
The content of the crystalline propylene polymer component (c) in the propylene/ethylene block copolymer (A2-2) is preferably 55% by weight or more and 95% by weight or less, more preferably 65% by weight or more and 90% by weight. % or less.

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

Propylene/ethylene block copolymer (A2-2) will be used as a raw material in order to further promote the spread of propylene/ethylene block copolymer (A2-2), which contributes to reducing environmental impact and reduces costs. For example, the ethylene contained in the raw material includes 0.1% to 100% by weight of ethylene derived from chemical recycling and 0% to 99.9% by weight of ethylene derived from fossil fuels (ethylene derived from chemical recycling and fossil fuels). (The total amount of derived ethylene is 100% by weight.) is a preferred form.

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 crystal components. Often, the propylene/ethylene random copolymer may have a specific amount, a specific molecular weight (intrinsic viscosity), or a specific amount of ethylene, or may contain two or more types of propylene/ethylene random copolymers. Electron beam irradiation may also be performed. For example, JP 9-286881, 2001-19826, 2002-030127, 2002-30128, 2004-292683, 2005-298706, and 2006-28449. , JP 2006-124453, JP 2006-152111, JP 2006-8983, WO 2006/068308, WO 2007/116709, JP 2009-84305, WO 2010/032793, JP 2011-190408, JP 8-217823, JP 10-182764, JP 10-330430, WO 1999/065965, JP 2001-233923, JP 2005-120388, At least a part of the propylene/ethylene block copolymer described in publications such as JP-A No. 2015-178568 is mixed with the propylene/ethylene block copolymer (A2-2) of the present invention so as to have the properties described in the above publication. After preparation, it can be used in place of the propylene/ethylene block copolymer (A2-2).

[Method for producing propylene polymer (A)]
The propylene polymer (A) of the present invention is produced by polymerizing a raw material containing propylene (a) and an olefin (b), which is included as necessary, using a polymerization catalyst, and which satisfies the above-mentioned requirements. can.
The propylene polymer (A) of the present invention can be produced preferably by a production method including a step of supplying a raw material containing propylene to a polymerization vessel and polymerizing the raw material with a polymerization catalyst.

The olefin (propylene, ethylene, α-olefin having 4 to 8 carbon atoms), which is a raw material used in the production of the propylene polymer (A), can be produced, for example, by the following method.

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

Examples of methods for producing ethylene derived from chemical recycling and propylene derived from chemical recycling include the method described in JP-A-2002-121318, or the method described in JP-A-5-287281, JP-A-9-302358, JP-A-10-330764, and JP-A-10-330764. An example of this is the production method described in JP-A-51-095001 in which petroleum residue is replaced with hydrocarbons obtained from waste plastics by the method described in JP-A-2001-123007.

As a method for producing 1-butene derived from chemical recycling, for example, in the method described in JP-A-58-146518 and International Publication No. 1989/000553, 1-butene is produced using ethylene derived from chemical recycling as the raw material ethylene. Examples include methods of manufacturing.

As a method for producing 1-hexene derived from chemical recycling, for example, in the method described in JP-A-7-149672 and JP-A-8-183747, 1-hexene is produced using ethylene derived from chemical recycling as the raw material ethylene. Examples of methods for producing 1-octene derived from chemical recycling include methods described in JP-A-2009-072666 and International Publication No. 2008/088178, in which ethylene derived from chemical recycling is used as the raw material ethylene. Examples include methods for producing 1-octene.

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

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

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

Fossil fuel-derived α-olefins having 4 to 8 carbon atoms can be produced by known synthesis methods using, for example, fossil fuel-derived propylene or fossil fuel-derived ethylene as raw materials. Examples of methods for producing 1-butene derived from fossil fuels include the methods described in JP-A-58-146518 and International Publication No. 1989/000553, and methods for producing 1-hexene derived from fossil fuels include, for example, , JP-A No. 7-149672, and JP-A No. 8-183747. Methods for producing fossil fuel-derived 1-octene include, for example, JP-A No. 2009-072666 and International Publication No. 2008/088178. Examples include the method described in .
As a method for producing fossil fuel-derived 4-methyl-1-pentene, for example, the method described in JP-A-60-132924 and JP-A-61-083135 uses fossil fuel-derived ethylene and fossil fuel-derived propylene as raw materials. Examples include a method for producing 4-methyl-1pentene.

The polymerization percentage (ratio) of propylene (ethylene) derived from chemical recycling and propylene (ethylene) derived from fossil fuels is adjusted to a desired ratio (for example, 0.1% by weight or more of propylene (ethylene) derived from chemical recycling and 100% by weight or less of propylene (ethylene) derived from fossil fuels). In order to obtain propylene (ethylene) containing 0% by weight or more and 99.9% by weight or less), propylene (ethylene) derived from chemical recycling and propylene (ethylene) derived from fossil fuels must be mixed in a desired specific ratio. It can be prepared with

Alternatively, light naphtha derived from fossil fuels and naphtha obtained using waste plastic as raw material, for example, as described in JP-A-5-287281, are mixed at a desired specific ratio, and this mixture is charged into a pyrolysis furnace. It can be prepared by extracting ethylene and propylene from a cracked gas fractionator. Note that a naphtha cracker that includes a pyrolysis furnace and a cracked gas fractionator in series is a device called an "ethylene cracker" in the petrochemical industry.

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

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

In the method for producing a propylene 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 that is normally used for polymerizing olefins containing propylene can be used. Examples of such polymerization catalysts include Ziegler-Natta catalysts and metallocene catalysts comprising a titanium catalyst component and an organic aluminum compound.

The Ziegler-Natta catalyst is generally made of a solid titanium catalyst component containing an internal donor (internal electron donor), an organoaluminum compound, and an external donor for the purpose of producing a highly stereoregular polymer. (external electron donor) is used. As such a Ziegler-Natta catalyst, for example, an olefin polymerization catalyst consisting of a magnesium chloride-supported solid titanium catalyst containing a carboxylic acid ester as an internal donor, an organoaluminum compound, and an organosilicon compound as an external donor may be used. (For example, olefin polymerization catalysts described in JP-A-08-003215 and JP-A-08-143620). Further, 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 usually has about 1×10 ⁻⁵ to 1 titanium atoms per liter of polymerization volume. It is used in an amount of mmol, preferably about 1×10 ^-4 to 0.1 mmol.
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 mol of aluminum atom of the organoaluminum compound.
In the Ziegler-Natta catalyst, the organoaluminum compound is used in an amount that is usually about 1 to 2000 mol, preferably about 2 to 500 mol, per 1 mol of titanium atoms in the polymerization system in terms of aluminum atoms in the compound. used in

In addition, when polymerizing a raw material containing propylene using a Ziegler-Natta catalyst, if the above-mentioned prepolymerization catalyst is used, polymerization may be possible without adding an organosilicon compound and/or an organoaluminum compound. When the catalyst for olefin polymerization is formed from a prepolymerized catalyst, an organosilicon compound and an organoaluminum compound, these organosilicon compounds and organoaluminum compounds can be suitably used in the amounts mentioned above.

Furthermore, if hydrogen is used during the polymerization of raw materials containing propylene, the molecular weight of the resulting propylene polymer (A) can be adjusted, and a polymer with a higher MFR can be obtained compared to the case where hydrogen is not added. can get.

In the method for producing a propylene polymer (A) of the present invention, the polymerization of the raw material containing propylene is usually carried out at a temperature of about 20 to 150°C, preferably about 50 to 100°C, and at a pressure of from normal pressure to 100 kg/cm ² , preferably is carried out under a pressure of approximately 2 to 50 kg/cm ² .

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

By the method for producing the propylene polymer (A) of the present invention, the above-mentioned propylene homopolymer (A1), propylene random copolymer (A2-1) and propylene/ethylene block copolymer (A2-2) are produced. ) Various propylene-based polymers (A) such as propylene-based copolymers (A2) can be produced.

The polymerization catalyst (catalyst component, electron donor, etc.) used in the method for producing the propylene polymer (A) of the present invention is not limited to the above-mentioned polymerization catalyst. The olefin polymerization catalyst (catalyst component, electron donor, etc.) used can be used without any restriction.

Examples of the Ziegler-Natta catalyst used in the method for producing the propylene polymer (A) of the present invention include JP-A-8-034814, JP-A-8-034813, JP-A-9-048814, and JP-A-9-9. 048813, JP 9-104709, JP 8-231630, JP 9-328513, JP 9-278819, JP 9-208615, JP 9-031119, JP 10-007716 No., JP 10-007715, JP 9-165414, JP 10-030004, JP 10-147611, JP 10-147610, JP 10-158317, JP 10-265519 , JP 10-060041, JP 11-012322, JP 11-035620, JP 10-316713, JP 11-035618, JP 11-035622, JP 10-287710, JP 11-106421, JP 11-147907, JP 11-158210, JP 11-217407, JP 11-222504, JP 11-302314, JP 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 2003-192718, JP 2004-002742, JP 2005-112920, JP 2005-187550, JP 2005-213367, JP 2005-126703, JP 2006 -199975, 2014-051669, 2013-227582, 2012-233195, 2008-024751, 2010-111755, 2013-249445, 2010- Polymerization catalysts (catalyst components, electron donors, etc. ).

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

[Production method of propylene homopolymer (A1)]
Propylene homopolymer (A1) can be produced, for example, by supplying raw material propylene (a) to a polymerization vessel according to the above-mentioned method for producing propylene polymer (A) (polymerization conditions such as polymerization catalyst, etc.). It can be produced by polymerizing raw materials using a polymerization catalyst.
As mentioned above, for the propylene homopolymer (A1), the raw material propylene (a) only needs to satisfy the above requirements (for example, the raw material propylene (a) contains 0.1% by weight or more of propylene derived from chemical recycling and 100% by weight). % or less and fossil fuel-derived propylene from 0% to 99.9% by weight (the total of chemical recycling-derived propylene and fossil fuel-derived propylene is 100% by weight).Hereinafter, regarding the propylene polymer (A) The same applies to preferred embodiments of the weight percentages of each component described in the description.

It is desirable for the propylene homopolymer (A1) to satisfy the above-mentioned (i) that the MFR is within a specific range. In order to keep the MFR within this specific range, for example, the ratio of propylene and hydrogen supplied to the polymerization vessel may be appropriately adjusted (the higher the hydrogen concentration relative to propylene, the higher the melt flow rate (MFR) becomes larger).

It is desirable that the propylene homopolymer (A1) 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 propylene polymer (A) described above can be employed. Further, as the polymerization conditions, known or similar polymerization conditions for propylene polymers may be employed.
For example, the polymerization of propylene introduced into a 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 by a gas phase polymerization method. good. Moreover, such polymerization may be carried out by combining two or more of these polymerization methods.
In addition, such polymerization is a batch polymerization in which the concentration of propylene 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 connected in parallel via piping. The polymerization conditions of each polymerization vessel (temperature, pressure, propylene concentration, concentration of hydrogen added as necessary, catalyst used and amount of catalyst supplied, type and amount of external electron donor supplied, organoaluminum compound) Semi-batch polymerization in which the type and supply amount of polymer, the ratio between the volume of the polymerization vessel and the volume of the liquid substance, etc.) are set arbitrarily; or, two or more polymerization vessels are connected in series with piping, and the polymerization conditions of each polymerization vessel ( Temperature, pressure, propylene concentration, hydrogen concentration, type and supply amount of external electron donor, type and supply amount of organoaluminum compound, ratio of polymerization vessel volume to liquid substance volume, etc.) are arbitrarily set, and 1 Either the catalyst supplied to the second polymerization vessel or the continuous polymerization in which the amount of catalyst supplied per hour may be set arbitrarily may be selected.

In addition, in the method for producing propylene homopolymer (A1), for example, JP-A-63-069809, JP-A-11-12310, JP-A-11-12308, JP-A-2001-48913, JP-A-2004-175976; The polymerization methods described in JP-A No. 2004-175933 and JP-A No. 2020-090621 can be employed.

[Method for producing propylene random copolymer (A2-1)]
The propylene-based random copolymer (A2-1) contains propylene and an olefin (b), for example, according to the description of the above-mentioned method for producing the propylene-based polymer (A) (polymerization conditions such as polymerization catalyst, etc.). It can be produced by supplying a raw material (a raw material satisfying the above requirement (I)) to a polymerization vessel and subjecting this raw material to random copolymerization using a polymerization catalyst.

Descriptions regarding preferred embodiments of raw materials (preferred embodiments of olefin (b), preferred embodiments of propylene (a), etc.) are the same as those described in the section of propylene-based random copolymer (A2-1).

The propylene random copolymer (A2-1) desirably satisfies the above-mentioned (iii) that the MFR is within a specific range. In order to keep the MFR within this specific range, for example, the ratio of olefin (propylene, olefin (b)), which is the raw material supplied to the polymerization vessel, and hydrogen may be appropriately adjusted (if the hydrogen concentration is high relative to propylene), (The melt flow rate (MFR) generally increases as the temperature decreases.)

The propylene random copolymer (A2-1) desirably satisfies the above-mentioned (iv) that the melting point is within a specific range. In order to keep the melting point within a specific range, for example, the ratio of propylene and olefin (b) contained in the raw material may be adjusted appropriately (the higher the ratio of olefin (b) to propylene, the lower the melting point will generally be). ), 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 random copolymer (A2-1), the same conditions as those for the propylene polymer (A) described above can be employed. Further, as the polymerization conditions, known or similar polymerization conditions for propylene polymers 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, or a suspension (slurry) polymerization method, or by a gas phase polymerization method. You may. Moreover, such polymerization may be carried out by combining two or more of these polymerization methods.
In addition, such polymerization includes 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 changed discontinuously in one polymerization vessel; The polymerization vessels are connected in parallel with piping, and the polymerization conditions of each polymerization vessel (temperature, pressure, concentration of propylene and olefin (b), concentration of hydrogen added as necessary, catalyst used/catalyst supply amount, external Semi-batch polymerization in which the type and supply amount of electron donor, type and supply amount of organoaluminum compound, ratio of polymerization vessel volume to liquid substance volume, etc.) are arbitrarily set; or, two or more polymerization vessels are connected by piping. Connected in series, the polymerization conditions of each polymerization vessel (temperature, pressure, concentration of propylene and olefin (b), hydrogen concentration, type and amount of external electron donor, type and amount of supply of organoaluminum compound, volume of polymerization vessel) and the volume of the liquid material, etc.), and the catalyst supplied to the first polymerization vessel and the amount of catalyst supplied per hour may be arbitrarily set. Either of these methods may be selected.

In addition, in the method for producing the propylene random copolymer (A2-1), for example, JP-A-63-069809, JP-A-11-12310, JP-A-11-12308, JP-A-2001-48915; The polymerization methods described in JP-A No. 2004-175976, JP-A No. 2004-175933, and JP-A No. 2020-090621 can be adopted.

[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 polymer (A) described above (polymerization conditions such as polymerization catalyst, etc.).
Supplying propylene or a raw material (1) containing propylene and ethylene to a polymerization vessel and polymerizing it with a polymerization catalyst,
A crystalline propylene-based polymer consisting of 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). It can be manufactured by a manufacturing method including the step (β).
In addition, in the method for producing the propylene/ethylene block copolymer (A2-2), the propylene (a) contained in the raw materials (1) and (2) meets the above requirements (chemical recycling-derived olefin and fossil fuel-derived olefin). (a specific quantity ratio) must be met.

The explanation regarding preferred embodiments (preferred embodiments of propylene, etc.) regarding the raw materials (raw materials (1) and (2)) is the same as that described in the section of the propylene/ethylene block copolymer (A2-2).

In the method for producing the propylene/ethylene block copolymer (A2-2), the first polymerization step is usually a step (α) of producing a crystalline propylene polymer component (c), and the second step is As a polymerization step, a step (β) of producing a propylene/ethylene random copolymer component (d) is performed.

In step (α), the crystalline propylene polymer component (c) contained in the propylene/ethylene block copolymer (A2-2) is produced. It is desirable that the crystalline propylene polymer component (c) satisfies the above-mentioned condition (v), that is, the intrinsic viscosity is within a specific range. When the crystalline propylene polymer component (c) is a propylene homopolymer, propylene is supplied to the polymerization vessel as a raw 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 reactor may be appropriately adjusted (the ratio of hydrogen to propylene is In general, the higher the intrinsic viscosity [η], the smaller the intrinsic viscosity [η]. When the crystalline propylene polymer component (c) is a propylene/ethylene random copolymer, propylene and ethylene are supplied to the polymerization vessel as raw materials for the polymer. At that time, in order to make the intrinsic viscosity [η] satisfy (v), as in the case of producing propylene homopolymer, for example, the ratio of hydrogen and propylene supplied to the polymerization vessel must be adjusted appropriately. Just adjust it. In addition, when the crystalline propylene polymer component (c) is a propylene/ethylene random copolymer, the polymerization vessel should be heated so that the desired value of structural units derived from propylene is 95% by weight or more and less than 100% by weight. The ratio of propylene and ethylene to be supplied may be adjusted appropriately.
Further, the step (α) of producing the crystalline propylene polymer component (c) may be carried out by one-stage polymerization carried out in one polymerization vessel, but it may also be carried out in two stages carried out in two or more polymerization vessels. The above polymerization may be performed, and when the polymerization is performed in two or more stages, the polymerization conditions in each stage may be the same or different.

In step (β), 20% to 80% by weight of structural units derived from propylene contained in the propylene-ethylene block copolymer (A2-2) and 20% to 80% by weight of structural units derived from ethylene. In order to produce a propylene/ethylene random copolymer component (d) containing propylene and ethylene, propylene and ethylene are supplied to a polymerization vessel. In order to set the proportion of structural units derived from propylene and the proportion of structural units derived from ethylene to desired values within the above-mentioned ranges, the ratio of propylene and ethylene supplied to the polymerization vessel may be appropriately adjusted. In addition, 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 vessel may be appropriately adjusted.
Further, 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 it may be carried out by two-stage polymerization carried out in two or more polymerization vessels. The polymerization may be carried out in stages or more, and when it is carried out in two or more stages, the polymerization conditions in each stage may be the same or different.

In order to make the quantitative ratio of the crystalline propylene polymer component (c) and the propylene/ethylene random copolymer component (d) within a desired range, for example, the crystalline propylene polymer component (c) is polymerized. The polymerization activity in step (α), the residence time of the polymer 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), the polymerization vessel of the polymer particles. The residence time and other factors may be adjusted appropriately.

As the polymerization conditions for the propylene/ethylene block copolymer (A2-2), the same conditions as those for the above-mentioned propylene-based polymer (A) can be adopted. Further, as the polymerization conditions, known or similar polymerization conditions for propylene polymers may be adopted.
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, or a suspension (slurry) polymerization method, or by a gas phase polymerization method. You may. Moreover, such polymerization may be carried out by combining two or more of these polymerization methods.
In addition, such polymerization can be carried out by batch polymerization, in which the concentrations of propylene and ethylene supplied to the polymerization vessel, and if necessary, the concentration of hydrogen added, are changed discontinuously in one polymerization vessel; or in which two or more polymerization vessels are used. They are connected in parallel with piping, and the polymerization conditions of each polymerization vessel (temperature, pressure, concentration of propylene and ethylene, concentration of hydrogen added as necessary, catalyst used and amount of catalyst supplied, type and type of external electron donor) Semi-batch polymerization in which the supply amount, type and amount of organoaluminium compound, ratio of polymerization vessel volume to liquid substance volume, etc.) are arbitrarily set; Alternatively, two or more polymerization vessels are connected in series with piping, and each Polymerization conditions in the polymerization vessel (temperature, pressure, concentration of propylene and ethylene, hydrogen concentration, type and supply amount of external electron donor, type and supply amount of organoaluminum compound, ratio of polymerization vessel volume to liquid substance volume, etc.), and continuous polymerization in which the catalyst supplied to the first polymerization vessel and the amount of catalyst supplied per hour are arbitrarily set.

In addition, in the method for producing a 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 8-231662, JP 11-12310, JP 2004-175976, JP 2004-175933, JP 2014-214202, JP 2016-84387, JP 2020-090621 The polymerization methods described can be employed.

[Resin composition]
The propylene polymer (A) obtained as described above in the present invention replaces part or all of the fossil fuel-derived propylene polymer obtained using only fossil fuel-derived olefins as a raw material, and It can be used as a resin composition containing. Note that, depending on the purpose, such a resin composition may further contain, as a propylene polymer, a biomass-derived propylene polymer obtained using only a biomass-derived olefin as a raw material. Moreover, the resin composition may contain only the propylene polymer (A) as the propylene polymer, or the propylene polymer (A) and the fossil fuel A mixture with a derived propylene polymer may also be included. Examples of the resin composition of the present invention include the following resin compositions.

[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 resin composition contains the propylene homopolymer (A1). This resin composition can be used as a resin composition.
When replacing the conventionally known propylene homopolymer with propylene homopolymer (A1), even if the properties of these polymers such as stereoregularity, average molecular weight, molecular weight distribution, catalyst residue, molecular structure and contained components are the same, For example, even after replacement, the performance of the resin composition can be made the same. This replacement makes it possible to reduce the environmental burden (reduce greenhouse gas emissions) in the life cycle of polymers, from production, processing, use, and disposal.

The resin composition containing the propylene homopolymer (A1) includes a resin composition containing two or more propylene homopolymers (A1) having different MFR or intrinsic viscosity, and a resin composition containing different average stereoregularity (pentad fraction). Resin composition containing two or more types of propylene homopolymer (A1), resin composition containing propylene homopolymer (A1) and propylene random copolymer, propylene homopolymer (A1) and propylene/ethylene block copolymer A resin composition containing a propylene homopolymer (A1) and an ethylene polymer, a resin composition containing a propylene homopolymer (A1) and a nucleating agent, a propylene homopolymer (A1) and a nucleating agent, a propylene homopolymer (A1) and a nucleating agent, Examples include resin compositions containing A1) and fillers.

Examples of the resin composition containing the propylene homopolymer (A1) include WO 2002/074855, WO 2019/00418, JP 2002-20560, JP 11-255987, and JP 2019-137847. No. 2019-137848, 2020-158787, 2020/091051, 2019-172730, 2017/195787, 2017-218509, 2016/159069 , JP 2000-319463, JP 2000-302925, JP 2004-315582, JP 2004-2655, JP 1-156353, and JP 2003-41072, Examples of the propylene homopolymer include resin compositions 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 also be a mixture of the propylene homopolymer (A1) and a fossil fuel-derived propylene homopolymer, or propylene homopolymer (A1). It may be a mixture of the homopolymer (A1) and the biomass-derived propylene homopolymer. In addition, when the above-mentioned resin composition contains an ethylene polymer, the raw material of the ethylene polymer is chemically recycled ethylene, and the ethylene polymer may contain an ethylene polymer derived from chemical recycling as the ethylene polymer. .

[Resin composition containing propylene random copolymer (A2-1)]
In a resin composition containing a propylene-based random copolymer which is a conventionally known random copolymer of propylene and olefin (b), part or all of the conventionally known propylene-based random copolymer is replaced by the present invention. It is possible to replace the propylene-based random copolymer (A2-1) with a resin composition containing the propylene-based random copolymer (A2-1), and use this resin composition.
When replacing the conventionally known propylene-based random copolymer with the propylene-based random copolymer (A2-1), the molecular structure and content of these polymers, such as stereoregularity, average molecular weight, molecular weight distribution, catalyst residue, etc. If the properties of the resin compositions are the same, the performance of the resin composition can be made the same even after replacement. This replacement makes it possible to reduce the environmental burden (reduce greenhouse gas emissions) in the life cycle of polymers, from production, processing, use, and disposal.

Examples of the resin composition containing the propylene random copolymer (A2-1) include 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 random copolymer (A2-1) and another body resin such as an ethylene 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. Examples include resin compositions containing the following.

Examples of the resin composition containing the propylene 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 In the resin composition containing the propylene random copolymer described in No. 2001-31804, International Publication No. 2015/137262, and JP2019-049001, the propylene random copolymer of the present invention is used as the propylene random copolymer. Examples include resin compositions using polymer (A2-1). The propylene random copolymer contained in these resin compositions may be only the propylene random copolymer (A2-1), but the propylene random copolymer (A2-1) and fossil fuel It may be a mixture of a propylene-based random copolymer derived from biomass, or a mixture of a propylene-based random copolymer (A2-1) and a biomass-derived propylene random copolymer. In addition, when the above-mentioned resin composition contains an ethylene polymer, this ethylene polymer contains, as an ethylene polymer, an ethylene polymer derived from chemical recycling whose raw material is ethylene derived from chemical recycling. Good too.

[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 the conventionally known propylene/ethylene block copolymer is replaced with the propylene/ethylene block copolymer of the present invention (A2- 2), a resin composition containing the propylene/ethylene block copolymer (A2-2) can be used, and this resin composition can be used.
When replacing the conventionally known propylene/ethylene block copolymer with a propylene/ethylene block copolymer (A2-2), the stereoregularity, average molecular weight, molecular weight distribution, comonomer species, comonomer amount, and composition of the propylene polymer are Even if the properties of these polymers such as distribution, ethylene content, molecular weight (intrinsic viscosity) of the propylene/ethylene random copolymer, and the content of each of these components in the entire block copolymer are the same, such as molecular structure and contained components are the same. For example, even after replacement, the performance of the resin composition can be made the same. This replacement makes it possible to reduce the environmental burden (reduce greenhouse gas emissions) in the life cycle of polymers, from production, processing, use, and disposal.

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 a polymer (A2-2) and a propylene random copolymer, a block copolymer containing two or more propylene and ethylene random copolymers with different ethylene contents, molecular weights (intrinsic viscosity), etc. Resin composition containing ethylene block copolymer (A2-2), resin composition containing propylene/ethylene block copolymer (A2-2) and other resin such as ethylene 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 Examples include 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, International Propylene-ethylene block copolymer described in Publication No. 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 Among the resin compositions, examples include resin compositions in which the propylene/ethylene block copolymer (A2-2) of the present invention is used as at least a part or all of the propylene/ethylene block copolymer. Note that 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 fossil fuel-derived propylene/ethylene block copolymer, or a mixture of a propylene/ethylene block copolymer (A2-2) and a biomass-derived propylene/ethylene block copolymer. In addition, when the above-mentioned resin composition contains an ethylene polymer, this ethylene polymer contains, as an ethylene polymer, an ethylene polymer derived from chemical recycling whose raw material is ethylene derived from chemical recycling. Good too.

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

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

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

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

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

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

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

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

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

[Denaturation]
The propylene polymer (A) or the resin composition containing the propylene polymer (A) of the present invention is modified by a known method with a modification compound such as an α,β-unsaturated carboxylic acid or an acid anhydride thereof. You can. Such modification can be carried out, for example, by dissolving the propylene polymer (A) or the propylene polymer (A) and the α,β-unsaturated carboxylic acid and/or its acid anhydride in a solvent, or by This can be carried out by reacting the resin composition in the presence of a radical generator in a melt-kneaded state.
As α,β-unsaturated carboxylic acids and their acid anhydrides, those having 20 or less carbon atoms, particularly those having 4 to 16 carbon atoms, are preferable, and specifically, acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, etc. The acids include fumaric acid, itaconic acid, citraconic acid, 3,6-endomethylene-2,3,4,6-tetrahydrosis-phthalic acid and acid anhydrides thereof.

[Molded object]
Conventionally known propylene polymers (propylene homopolymers, propylene 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/ethylene block copolymer (A2-2), etc.) The molded article of the present invention can be obtained by replacing the polymer with the polymer (A2)) and molding this replaced polymer. Furthermore, the molded article of the present invention can be obtained by molding a resin composition containing a propylene polymer in which part or all of a conventionally known propylene polymer is replaced with a propylene polymer (A).

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

The propylene polymer (A) contains 0.1% by weight or more of propylene (a1) derived from chemical recycling as the propylene (a) contained in its raw material from the viewpoint of cost reduction and promotion of widespread use, and the propylene (a) ) in which the proportion of propylene derived from chemical recycling (a1) can be adjusted to a desired range, and the proportion of structural units derived from propylene derived from chemical recycling (a1) (propylene content derived from chemical recycling) can be adjusted to a desired proportion. Can be combined. Therefore, when a mixture of propylene (a1) derived from chemical recycling and propylene (a2) derived from fossil fuels in a desired ratio is used as the propylene (a) contained in the raw material, it is possible to The ratio of the structural units derived from chemical recycling-derived propylene (a1) (chemical recycling-derived propylene content) can be set to a desired value at the time of producing the polymer itself. Therefore, a chemically derived propylene polymer obtained using a raw material containing only propylene derived from chemical recycling (a1) is first produced as propylene (a), and then fossil fuel derived propylene (a2) is used as propylene (a). Proportion of structural units derived from chemically recycled propylene (a1) in a material containing a propylene polymer that is mixed with a fossil fuel-derived propylene polymer to form a molded product using a raw material containing only Compared to the case where the recycled propylene content is adjusted, additional dilution with a fossil fuel-derived propylene polymer is not necessary. Therefore, in the molded article of the present invention, the equipment and process for its production can be simplified, and the environmental load can be reduced.

The propylene polymer (A) of the present invention (propylene copolymers such as propylene homopolymer (A1), propylene random copolymer (A2-1), propylene/ethylene block copolymer (A2-2)) A2)) and the resin composition containing the propylene polymer (A) can be processed by injection molding, extrusion molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, injection stretch blow molding, press molding (compression molding) It can be molded into various molded products by known molding methods such as vacuum molding, calendar molding, foam molding, injection foam molding, foam blow molding, and blow molding.

<Injection molding>
The propylene polymer (A) of the present invention and the resin composition containing the propylene polymer (A) can be molded into molded articles for various uses by injection molding.
Examples of injection molding methods include JP-A-9-3296, JP-A-9-71712, JP-A-9-165477, JP-A-2004-83608, JP-A-2004-256606, and 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, The propylene polymer or propylene described in 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, and JP 2021-025015 A method for injection molding a resin composition containing a polymer based on the above method may be mentioned.

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

<Hollow molding>
The propylene polymer (A) of the present invention and the resin composition containing the propylene polymer (A) can be made into molded articles for various uses by blow molding.
As a blow molding method, for example, propylene polymers described in International Publication No. 2011/090101, International Publication WO2015/137268, Japanese Patent Application Publication No. 2015-168788, International Publication No. 2015/137262, and Japanese Patent Application Publication No. 2020-090616 Another example is a method of blow molding a resin composition containing a propylene polymer.

<Foam blow molding>
The propylene polymer (A) of the present invention and the resin composition containing the propylene polymer (A) can be made into molded articles for various uses by foam blow molding.
Examples of the method of foam blow molding include the method of foam blow molding of a propylene polymer or a resin composition containing a propylene polymer described in International Publication No. 2011/118281.

<Injection stretch blow molding>
The propylene polymer (A) of the present invention and the resin composition containing the propylene 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, propylene polymers or propylene polymers described in International Publication No. 2015/137268, International Publication No. 2019/139125, International Publication No. 2019/139125, and International Publication No. 2020/175138. Examples include a method of injection stretch blow molding of a resin composition containing the following.

<Compression molding>
The propylene-based polymer (A) of the present invention and the resin composition containing the propylene-based polymer (A) can be made into molded products for various uses by compression molding.
Examples of the compression molding method include the method of compression molding a propylene polymer or a resin composition containing a propylene polymer described in JP-A No. 2009-84393.

Examples of molded products produced by the above molding method include the following.
<Tube, tube>
Tubes and pipes for various uses can be molded from the propylene polymer (A) of the present invention and the resin composition containing the propylene polymer (A) by a molding method such as extrusion molding. The tube or pipe can be produced, for example, by the method of molding 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 used for various purposes can be formed by biaxially stretching the propylene polymer (A) of the present invention and a resin composition containing the propylene polymer (A). Biaxially stretched films are, 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, Propylene-based polymers or propylene-based polymers described in JP 2006-282761, JP 2016-187933, JP 2016-187934, JP 2017-177699, JP 2017-177726, and JP 2017-177727 It can be produced by a method of forming a biaxially stretched film from a resin composition containing a polymer. In addition, such a biaxially stretched film may be a single layer or a laminate.

<Unstretched film>
By forming a non-stretched film from the propylene polymer (A) of the present invention and a resin composition containing the propylene polymer (A), a non-stretched film for use in various applications can be formed. Examples of non-stretched films include, 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, 2002-317012, 2021/025142, 2006-52314, 2000-119480, 2001-261921, 2019/189486, 2009-161590, 2009-161590 A method of forming an unstretched film from a propylene polymer or a resin composition containing a propylene polymer described in 2014/030594, International Publication 2016/158982, JP 2015-193181, and JP 2020-114908 It can be made by In addition, such an unstretched film may be a single layer or a laminate.

<Sheet/vacuum formed body>
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 uses can be formed. Moreover, such a sheet can be further vacuum-formed to form a vacuum-formed product for use in various applications. The sheet and the vacuum-formed body are, for example, JP-A-2005-97548, JP-A 2002-284942, JP-A-7-33920, JP-A 2001-2859, JP-A 2015-124362, and International Publication 2016/114393. , WO 2016/114393, JP 2010-168052, JP 2014-169446, a method for molding a sheet from a propylene polymer or a resin composition containing a propylene polymer, and the obtained sheet It can be produced by a method of producing a vacuum-formed body from. Note that such sheets and vacuum-formed bodies may be a single layer or a laminate.

<Foam sheet>
By molding the propylene polymer (A) of the present invention and a resin composition containing the propylene polymer (A) into foam sheets, foam sheets for use in various purposes can be molded. The foamed sheet can be produced using a method of molding a foamed sheet from a propylene polymer or a resin composition containing a propylene polymer described in, for example, JP 2018-109104, WO 2006/054715, and JP 2009-221473. It can be made by In addition, such a foamed sheet may be a single layer or a laminate.

<Extrusion laminate products>
Extrusion laminate products used for various purposes can be produced from the propylene polymer (A) of the present invention and a resin composition containing the propylene polymer (A) by extrusion lamination molding. Extrusion laminate products can be produced, for example, by a method of producing an extrusion laminate product from a propylene polymer or a resin composition containing a propylene polymer described in JP-A-2-281055 and JP-A-2017-132134. Note that the laminate layer of such an extrusion laminate product may be a single layer or a laminate.

<Fiber/nonwoven fabric>
From the propylene polymer (A) of the present invention and the resin composition containing the propylene polymer (A), fibers used for various purposes can be obtained by, for example, filament molding using a winder. By molding or spunbond molding, nonwoven fabrics for various uses can be obtained. The fiber or nonwoven fabric is, for example, a propylene-based polymer or a resin composition containing 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 of producing fibers or nonwoven fabrics from materials.

<Shrink film>
Shrink films for various uses can be produced from the propylene polymer (A) of the present invention and a resin composition containing the propylene polymer (A), for example, by stretched 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 of producing a shrink film from a propylene polymer or a resin composition containing a propylene polymer. In addition, such a shrink film may be a single layer or a laminate.

<Separator>
From the propylene polymer (A) of the present invention and a resin composition containing the propylene polymer (A), separators for various uses can be produced by, for example, stretched film molding. The separator can be produced by a method of producing a separator from a propylene polymer or a resin composition containing a propylene polymer described in, for example, JP 2020-114909, WO 2014/065331, and WO 2010/079784. It can be made. Note that the resin layer constituting the separator may be a single layer or a multilayer.

<Application>
The molded articles obtained from the propylene polymer (A) of the present invention and the resin composition containing the propylene polymer (A) by the method described above can be used as automotive parts, containers for food and medical uses, and food uses. It can be applied to a variety of well-known uses, such as packaging materials for electronic materials.

Automotive parts include, for example, automotive exterior parts such as bumpers, side moldings, and aerodynamic undercovers; automotive interior parts such as instrument panels and interior trims; exterior parts such as fenders, door panels, and steps; engine covers, fans, and fans. Engine peripheral parts such as sherouds; etc.
Examples of containers for food and medical use include tableware, retort containers, frozen storage containers, retort pouches, microwave heat-resistant containers, frozen food containers, frozen dessert cups, cups, beverage bottles, and other food containers, retort containers, and bottles. Containers, blood transfusion sets, medical bottles, medical containers, medical hollow bottles, medical bags, infusion bags, blood storage bags, infusion bottles, drug containers, detergent containers, cosmetic containers, perfume containers, toner containers, etc. .
Examples of packaging materials include food packaging, meat packaging, processed fish packaging, vegetable packaging, fruit packaging, fermented food packaging, confectionery packaging, oxygen absorber packaging, retort food packaging, and freshness packaging. Retention films, pharmaceutical packaging materials, cell culture bags, cell inspection films, bulb packaging materials, seed packaging materials, films for vegetable and mushroom cultivation, heat-resistant vacuum-formed containers, side dish containers, lids for side dishes, wrap films for commercial use, household use Examples include cling film and baking cartons.

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

Other uses of the molded product of the present invention include, for example, housings for home appliances, hoses, tubes, wire covering materials, insulators for high-voltage wires, tubes for cosmetics and perfume sprays, medical tubes, infusion tubes, pipes, and wires. Harnesses, interior materials for motorcycles, railway vehicles, aircraft, ships, etc., instrument panel skins, door trim skins, rear package trim skins, ceiling skins, rear pillar skins, seat back garnishes, console boxes, armrests, airbag case lids, shift knobs , assist grips, side step mats, reclining covers, seats in the trunk, seatbelt buckles, inner/outer moldings, roof moldings, belt moldings and other molding materials, door seals, body seals and other automotive sealing materials, glass run channels, mudguards, etc. Automotive interior and exterior materials such as kicking plates, step mats, license plate housings, automotive hose parts, air duct hoses, air duct covers, air intake pipes, air dam skirts, timing belt cover seals, bonnet cushions, door cushions, and vibration damping tires. , static tires, car racing tires, special tires such as radio-controlled tires, packing, automobile dust covers, lamp seals, automobile boot materials, rack and pinion boots, timing belts, wire harnesses, grommets, emblems, air filter packing, furniture.・Surface materials for footwear, clothing, bags, building materials, etc., sealing materials for construction, waterproof sheets, construction material sheets, construction material gaskets, window films for construction materials, iron core protection members, gaskets, doors, door frames, window frames, surrounding edges, Baseboards, opening frames, etc., flooring materials, ceiling materials, wallpaper, health products (e.g., non-slip mats/sheets, anti-fall films/mats/sheets, etc.), health equipment components, shock-absorbing pads, protectors/protective equipment (e.g.) : helmets, guards), sports equipment (e.g. sports grips, protectors), sports protective equipment, rackets, mouthguards, balls, golf balls, transportation equipment (e.g. shock-absorbing grips for transportation, shock-absorbing sheets), vibration control Shock absorbing materials such as pallets, shock absorbing dampers, insulators, shock absorbing materials for footwear, shock absorbing foams, and 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, power tool parts, agricultural equipment parts, heat dissipation materials, transparent substrates, soundproofing materials, cushioning materials, electric wire cables, shape memory materials, medical gaskets, medical caps, medicines Stoppers, gaskets, packing materials for applications that require high-temperature processing such as boiling or high-pressure steam sterilization after filling bottles with baby food, dairy products, pharmaceuticals, sterilized water, etc., industrial sealing materials, industrial sewing machine tables, license plate housings. , cap liners such as PET bottle cap liners, stationery, office supplies, OA printer legs, fax legs, sewing machine legs, motor support mats, precision equipment and OA equipment support members such as audio vibration isolation materials, heat-resistant packing for OA, animal cages. , beakers, graduated cylinders and other physical and chemical experiment equipment, optical measurement cells, clothing cases, clear cases, clear files, clear sheets, desk mats, textiles, such as nonwoven fabrics, stretchable nonwoven fabrics, fibers, waterproof fabrics, Examples include breathable fabrics and cloth, disposable diapers, sanitary products, sanitary products, filters, bag filters, dust collection filters, air cleaners, hollow fiber filters, water purification filters, gas separation membranes, etc.

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

The propylene polymer (A) contains 0.1% by weight or more of propylene (a1) derived from chemical recycling as the propylene (a) contained in its raw material from the viewpoint of cost reduction and promotion of widespread use, and the propylene (a) ) in which the proportion of propylene derived from chemical recycling (a1) can be adjusted to a desired range, and the proportion of structural units derived from propylene derived from chemical recycling (a1) (propylene content derived from chemical recycling) can be adjusted to a desired proportion. Can be combined. Therefore, when a mixture of propylene (a1) derived from chemical recycling and propylene (a2) derived from fossil fuels in a desired ratio is used as the propylene (a) contained in the raw material, it is possible to The ratio of the structural units derived from chemical recycling-derived propylene (a1) (chemical recycling-derived propylene content) can be set to a desired value at the time of producing the polymer itself. Therefore, a chemically derived propylene polymer obtained using a raw material containing only propylene derived from chemical recycling (a1) is first produced as propylene (a), and then fossil fuel derived propylene (a2) is used as propylene (a). Proportion of structural units derived from chemically recycled propylene (a1) in a material containing a propylene polymer that is mixed with a fossil fuel-derived propylene polymer to form a molded product using a raw material containing only Compared to the case where the content of recycled propylene is adjusted, it is not necessary to additionally mix a fossil fuel-derived propylene polymer. For this reason, in order to obtain materials for producing molded bodies, equipment and processes for blending in-line and equipment and processes for melt-kneading are not required. In other words, the equipment for obtaining a molding material for producing a molded body can be simplified, and post-processes for producing a molding material after producing a propylene-based polymer derived from chemical recycling are not necessary. For these reasons, it is thought that reducing power consumption will contribute to reducing environmental impact.

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

<Various physical property measurement conditions>
The physical properties of the polymer and the physical properties of the molded article described in Reference Examples, Examples, etc. were measured according to the following conditions.

(1) Olefins derived from chemical recycling in raw material monomers (wt%)
Prepare a raw material source (1) containing only an olefin derived from chemical recycling of one type of olefin (for example, propylene) and a raw material source (2) containing only an olefin derived from fossil fuels of the same olefin as the one type of olefin, By adjusting the mixing ratio of the raw material source (1) and the raw material source (2), the weight percent of chemical recycling-derived olefin and the weight percent of fossil fuel-derived olefin in the raw material monomer were made to be the desired values. . In addition, when two or more types of olefins are a mixture of chemical recycling-derived olefins and fossil fuel-derived olefins, a raw material source (1') containing only two or more types of chemical recycling-derived olefins and two or more types of fossil fuel-derived olefins. If necessary (for example, if you want to change the weight percent of chemically recycled olefins for each olefin type), you can separately mix the raw material source (2') containing only one or more types of chemically recycled olefins. The raw material source (1'a) consisting of the raw material source (1'a) or the raw material source (2'a) consisting only of one or more types of fossil fuel-derived olefins is mixed, and the weight percent of the chemical recycling-derived olefin in the raw material monomer and the weight of the fossil fuel-derived olefin are mixed. % may be adjusted to a desired value.

(2) Melt flow rate (MFR: [g/10 minutes])
Measurement was performed with a load of 2.16 kg in accordance with ASTM D1238E. The measurement temperature was 230°C. In addition, when measuring the MFR of the polymer (for example, propylene homopolymer) that becomes the crystalline propylene polymer component (c) of the propylene/ethylene block copolymer, use Irganox manufactured by Ciba Geigy as an antioxidant. The measurement was carried out by adding 1000 ppm of 1010 and 1000 ppm of Irgafos 168 manufactured by Ciba Geigy.

(3) 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 polymer was determined by carbon nuclear magnetic resonance analysis ( ^13C -NMR) and assigned based on Macromolecules ⁸ , 687 (1975). Calculated from the peak intensity ratio of the NMR spectrum.

< ^13C -NMR measurement device and measurement conditions>
Measurement equipment: AVANCE III 500 nuclear magnetic resonance apparatus (equipped with cryoprobe) (manufactured by Bruker Biospin)
Measurement nucleus: ^13C (125MHz)
Measurement mode: Single pulse proton broadband decoupling Pulse width: 45°
Number of points: 64k
Measurement range: 240ppm (-60 to 180ppm)
Repetition time: 5.5 seconds Number of integration: 256 Measurement solvent: Orthodichlorobenzene/benzene-d6 (4/1v/v)
Sample concentration: ca. 50mg/0.6mL
Measurement temperature: 120℃
Window function: exponential (BF: 0.5Hz)
Chemical shift standard: mmmm (21.59ppm)

(4) Content of structural units derived from ethylene in propylene polymer (weight (%))
The measurement conditions are the same as those for (3) isotactic pentad fraction measurement.
From the spectrum obtained in the measurement, the ratio of monomer chain distribution (triad distribution) was determined according to the following document (1), and the ratio of monomer chain distribution (triad distribution) was determined, and The mole fraction (mol%) of the structural unit derived from ethylene (hereinafter referred to as E (mol%)) and the mole fraction (mol%) of the constitutional unit derived from propylene (hereinafter referred to as P (mol%)) Calculated.

The obtained E (mol%) and P (mol%) are converted into weight% according to the following formula (1), and the content (weight%) of the structural unit derived from ethylene in the above-mentioned Dinsol and Dsol of the propylene-based polymer is calculated. ) (hereinafter referred to as E (wt%)) was calculated.
Literature (1): Kakugo, M. ; Naito, Y.; ; Mizunuma, K.; ; Miyatake, T. , Carbon-13 NMR determination of monomer sequence distribution in ethylene-propylene copolymers prepared with delta-titan ium trichloride-diethylaluminum chloride. Macromolecules 1982, 15, (4), 1150-1152
E (wt%) = E (mol%) x 28 x 100/[P (mol%) x 42 + E (mol%) x 28] (1)

(5) Content of structural units derived from α-olefin having 4 to 8 carbon atoms in propylene polymer (wt%)
The measurement conditions were the same as for the measurement of isotactic pentad fraction.
From the spectra obtained in the measurements, chemical shift standards were appropriately determined depending on the α-olefin species used as the propylene copolymerization component, and calculations were made based on these.

(6) Mw/Mn
The gel permeation chromatography (GPC) method was used to measure with the following equipment and conditions, and by analyzing the obtained chromatogram, the polystyrene-equivalent Mw (weight average molecular weight) value, Mn (number average molecular weight) value, and The Mw/Mn value was calculated.

(GPC measurement device)
Liquid chromatograph: manufactured by Tosoh Corporation, HLC-8321GPC/HT detector: RI
Column: 2 TOSOH GMHHR-H(S)HT manufactured by Tosoh Corporation connected in series

<Measurement conditions>
Mobile phase medium: 1,2,4-trichlorobenzene Flow rate: 1.0 ml/min Measurement temperature: 145°C
Method for creating a calibration curve: A calibration curve was created using standard polystyrene samples.
Molecular weight conversion: Converted from PS (polystyrene) to PP (polypropylene) equivalent molecular weight using the universal calibration method Sample concentration: 5mg/10ml
Sample solution volume: 300μl

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

<Measurement conditions>
・Measurement environment: Nitrogen gas atmosphere ・Sample amount: 5mg
・Sample shape: Press film (molded at 230℃, thickness 200-400μm)
- Sample set: sealed in an aluminum pan - 1st step: Raise the temperature from 30°C to 240°C at 10°C/min and hold for 10 minutes.
・Second step: Lower the temperature to 30°C at a rate of 10°C/min.
- Third step: Raise the temperature to 240°C at 10°C/min.

(8) Amount of decane soluble portion (wt%) and decane insoluble portion (wt%) in propylene/ethylene block copolymer
5±0.05g of propylene/ethylene block copolymer was accurately weighed into a 1,000ml eggplant-shaped flask, and 1±0.05g 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 operating the rotor 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 left to cool (over 8 hours) to room temperature (25°C) while stirring with a stirrer, and the precipitate was poured into a wire mesh. I picked it up. The filtrate was further filtered through filter paper, and then poured into 2,000±100 ml of methanol contained in a 3,000 ml beaker, and this liquid was stirred with a stirrer at room temperature (25°C). It was left for more than 2 hours. Next, the obtained precipitate was filtered through a wire mesh, air-dried for 5 hours or more, and then dried in a vacuum dryer at 100±5°C for 240 to 270 minutes to collect the n-decane soluble portion at 25°C.
The content (x) of the n-decane soluble portion at 25°C is determined by comparing the sample weight with Ag and the recovered n-decane soluble portion with propylene/ethylene random copolymer (propylene/ethylene random copolymer component (d)). ) is expressed as x (weight %) = 100 x C/A. The amount of decane insoluble portion (y) is expressed as y (wt%) = 100-x (wt%).

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

(10) Biaxially stretched film transverse stretching load It is shown as the descending load when transversely stretching with a table tenter during biaxially stretched film molding.

(11) Total film haze Measured in accordance with JIS K-7105.

(12) Film tensile modulus Film tensile 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. A tensile test was carried out by pulling at a crosshead speed of 500 mm/min. The machine direction was defined as MD, and the direction perpendicular to MD was defined as TD.

(13) Film heat-sealing temperature Film heat-sealing temperature (°C) was measured in accordance with JIS K-1707. The fusion conditions are described below. Note that the temperature of the heat seal bar is calibrated using a surface thermometer. After sealing, it was left at room temperature for a day and night, and then the peel strength was measured by the T-peel method at a peel rate of 200 mm/min at room temperature. The heat sealing temperature was determined by calculating the temperature at which the peel strength was 300 g/15 mm from the seal strength-peel strength curve.

<Fusing conditions>
Seal time: 1sec
Seal area: 15 x 10mm
Seal pressure: 2.0kg/cm ²
Seal temperature: Several temperatures were selected so that the heat seal temperature could be interpolated.

(14) 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.

(15) Injection molded product tensile elongation at break and tensile stress at break The tensile elongation at break (%) and tensile stress at break (MPa) of the injection molded product were measured under the following conditions in accordance with ASTM D638.

<Measurement conditions>
Test piece: ASTM-1 dumbbell (19mm (width) x 3.2mm (thickness) x 165mm (length))
Pulling speed: 50mm/min Distance between spans: 115mm
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: Multipurpose test piece (ISO-A type: thickness 4mm)
Tensile speed: 5mm/min Temperature: 23℃

(16) Bending elastic modulus and bending strength of injection molded product The bending elastic modulus (MPa) and bending strength (MPa) of the injection molded product were measured under the following conditions in accordance with JIS K7171.

<Measurement conditions>
Test piece: 10mm (width) x 80mm (length) x 4mm (thickness)
Bending speed: 2mm/min Bending span: 64mm

(17) Izod impact strength of injection molded product The Izod impact strength of the injection molded product was measured under the following conditions in accordance with ASTM D256.

<Measurement conditions>
Temperature: 23℃
Test piece: 12.7mm (width) x 6.4mm (thickness) x 64mm (length) (with notch; notch is machined)

(18) Charpy impact test of injection molded product The Charpy impact value (kJ/m ² ) of the injection molded product was measured under the following conditions in accordance with JIS K7111.
<Measurement conditions>
Temperature: -30℃
Test piece: 10 mm (width) x 80 mm (length) x 4 mm (thickness) (with a notch; the notch is machined.)

(19) Rockwell hardness of injection molded product The Rockwell hardness (R scale) of the injection molded product was measured under the following conditions in accordance with JIS K7202.

<Measurement conditions>
Test piece: 30mm (width) x 30mm (length) x 2mm (thickness)
Measurements were made by stacking two test pieces.

(20) Weld strength of injection molded product The weld strength of the injection molded product was measured under the following conditions in accordance with JIS K7171, and the highest load in a bending test with the weld portion as the center line was defined as the weld strength.

<Measurement conditions>
Test piece: 10mm (width) x 80mm (length) x 4mm (thickness)
Bending speed: 2mm/min Bending span: 64mm

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

<Talc (C)>
"JM-209" (manufactured by Asada Seifun Co., Ltd.) Average particle diameter approximately 4 μm determined by laser diffraction method

<Glass short fiber (D)>
Chopped strands with an average fiber diameter of 10 μm and an average length of 3 mm, surface treated 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)>
Umex 1010 (trademark), manufactured by Sanyo Chemical Co., Ltd.)

[Reference Example 1] (Fossil fuel-derived propylene homopolymer: PP-1-0)
(1-1) Preparation of magnesium compound After sufficiently purging a glass reactor with an internal volume of 12 liters with nitrogen gas, approximately 4,860 g of ethanol, 32 g of iodine, and 320 g of metallic magnesium were added and stirred. The mixture was reacted under reflux conditions to obtain a solid reaction product. A magnesium compound (solid product) was obtained by drying the reaction solution containing this solid reaction product under reduced pressure.

(1-2) Preparation of solid catalyst component 160 g of the magnesium compound obtained in (1-1) (unpulverized) was placed in a 5-liter glass three-necked flask 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 maintained at 90°C, and 770 ml of titanium tetrachloride was added while stirring and reacted at 110°C for 2 hours, after which the solid component was separated and washed with purified heptane at 80°C. Further, 1,220 ml of titanium tetrachloride was added, and the mixture was reacted at 110° C. for 2 hours, followed by thorough washing with purified heptane to obtain a solid catalyst component.

(1-3) Polymerization pretreatment 230 liters of n-heptane was put into a reaction tank with an internal volume of 500 liters equipped with stirring blades, and 25 kg of the solid catalyst component obtained in (1-2) was added, and then, After adding 0.6 mol of triethylaluminum and 0.4 mol of cyclohexylmethyldimethoxysilane to 1 g of Ti atom in this solid catalyst component, fossil fuel-derived propylene was added at a propylene partial pressure of 0.3 kg/cm ² G and reacted at 20° C. for 4 hours. After the reaction was completed, the solid catalyst component was washed several times with n-heptane, carbon dioxide was supplied, and the mixture was stirred for 24 hours.

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

(1-5) Additive formulation and granulation To the polypropylene homopolymer (PP-1-0) powder thus obtained in (1-4), 100 ppm of Irganox 1010 manufactured by Ciba Geigy as an antioxidant and Ciba Geigy 1000 ppm of Irgafos 168 manufactured by Manufacturer Co., Ltd., 1000 ppm of calcium stearate as a neutralizing agent, 2300 ppm of a silica-based anti-blocking agent, and 500 ppm of erucic acid amide as a slip agent were mixed in a tumbler and then granulated under the following conditions, A polypropylene resin composition (granulated product) was prepared.

<Melt-kneading conditions>
Extruder: Product number Toshiba Machine Co., Ltd. twin screw extruder “TEM-35”
Seal the hopper with nitrogen cylinder temperature: 210℃
Screw rotation speed: 150rpm
Extrusion amount: 15kg/h

(1-6) Preparation of biaxially stretched film Next, using a 35 mmφ sheet forming machine manufactured by Shinko Kikai Seisakusho, the resin composition obtained in (1-5) was heated at a resin temperature of 260°C and a chill roll temperature of 30°C. After forming the sheet, this sheet was longitudinally stretched using a roll stretching machine manufactured by Iwamoto Seisakusho at a stretching temperature of 145°C and a stretching ratio of 5 times, and then using a table tenter manufactured by Iwamoto Seisakusho at a stretching temperature of 164°C and a preheating time of 80 seconds. , a biaxially stretched film having a thickness of 25 μm was produced by transversely stretching at a stretching speed of 90%/sec and a stretching ratio of 10 times. Subsequently, this biaxially stretched film was surface-treated using a roll electrode type corona discharge treatment machine manufactured by Kasuga Electric 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)
In the main polymerization (1-4) of Reference Example 1, a propylene mixture containing 40% by weight of propylene derived from chemical recycling and 60% by weight of propylene derived from fossil fuels was used instead of propylene derived from fossil fuels as propylene. A propylene homopolymer (PP-1-1), which is a propylene homopolymer (A1), was obtained in the same manner as in Reference Example 1 (1-1) to (1-4). Table 1 shows the resin physical properties of the obtained propylene homopolymer (PP-1-1).
Using the propylene homopolymer (PP-1-1) obtained in place of the fossil fuel-derived propylene homopolymer (PP-1-0), (1-5) additive formulation and granulation in Reference Example 1 A polypropylene resin composition (granulated product) was prepared according to (1-6), and a biaxially stretched film was produced according to (1-6) Preparation of biaxially stretched film. Table 1 shows the physical properties of the obtained biaxially stretched film.

[Example 2] (Propylene homopolymer (A1): PP-1-2)
(1-4) of Reference Example 1 In the main polymerization, propylene derived from chemical recycling was used as the propylene instead of propylene derived from fossil fuels. In the same manner, a propylene homopolymer (PP-1-2), which is a propylene homopolymer (A1), was obtained. Table 1 shows the resin physical properties of the obtained propylene homopolymer (PP-1-2).
Using the propylene homopolymer (PP-1-2) obtained in place of the fossil fuel-derived propylene homopolymer (PP-1-0), (1-5) additive formulation and granulation in Reference Example 1 A polypropylene resin composition (granulated product) was prepared according to (1-6), and a biaxially stretched film was produced according to (1-6) Preparation of biaxially stretched film. Table 1 shows the physical properties of the obtained biaxially stretched film.

[Reference Example 2] (Fossil fuel-derived propylene random copolymer: PP-2-0)
(2-1) Preparation of magnesium compound A reaction tank equipped with a stirrer (inner volume 500 liters) was sufficiently replaced with nitrogen gas, and 97.2 kg of ethanol, 640 g of iodine, and 6.4 kg of metallic magnesium were added, and while stirring, The reaction was carried out under reflux conditions until no hydrogen gas was 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 this solid reaction product under reduced pressure.

(2-2) Preparation of solid catalyst component 30 kg of the magnesium compound obtained in (2-1) (unpulverized) was placed in a reaction tank (inner volume 500 liters) with a stirrer that was 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, and the mixture was reacted at 110°C for 2 hours.The solid component was then separated and washed with purified heptane at 80°C. Further, 228 liters of titanium tetrachloride was added, and the mixture was reacted at 110° C. for 2 hours, and then thoroughly washed with purified heptane to obtain a solid catalyst component.

(2-3) Polymerization pretreatment 230 liters of purified heptane was charged into a reaction tank with an internal volume of 500 liters equipped with a stirrer, and 25 kg of the solid catalyst component obtained in (2-2) was added to the titanium atoms in the solid catalyst component. To this, triethylaluminum was supplied at a rate of 1.0 mol/mol and dicyclopentyldimethoxysilane at a rate of 1.8 mol/mol. 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 the stirring reaction was completed, the solid catalyst component was washed several times with purified heptane, carbon dioxide was further supplied, and the mixture was stirred for 24 hours. Note that fossil fuel-derived propylene was used as the propylene.

(2-4) Main polymerization 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 into a polymerization apparatus with an internal volume of 200 liters and equipped with a stirrer. 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 respectively 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 compositional analysis values (gas chromatography analysis) of the gas section inside the polymerization apparatus showed that the ethylene concentration was 3.4 mol%, and the hydrogen concentration was 2.4 mol%. Note that fossil fuel-derived propylene was used as propylene, and fossil fuel-derived ethylene was used as ethylene. Table 2 shows the resin physical properties of the propylene/ethylene random copolymer (PP-2-0) thus obtained. Note that MFR was measured using the granulated product obtained in (2-5) below.

(2-5) Additive formulation and granulation To the propylene/ethylene random copolymer (PP-2-0) powder thus obtained in (2-4), 1000 ppm of Irganox 1010 manufactured by Ciba Geigy was added as an antioxidant. 1,000 ppm of Irgafos 168 manufactured by Ciba Geigy, 1,000 ppm of calcium stearate as a neutralizing agent, 2,300 ppm of a silica-based anti-blocking agent, and 500 ppm of erucic acid amide as a slip agent were mixed in a tumbler, and then manufactured under the following conditions. The mixture was granulated to prepare a resin composition (granulated product) containing a propylene random superpolymer.

<Melt-kneading conditions>
Extruder: Product number Toshiba Machine Co., Ltd. twin screw extruder “TEM-35”
Seal the hopper with nitrogen cylinder temperature: 210℃
Screw rotation speed: 150rpm
Extrusion amount: 15kg/h

(2-6) Production of film Next, using a 75 mmφ molding machine manufactured by Mitsubishi Heavy Industries, a film with 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℃
Chill roll temperature: 25℃
Pick-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, and then 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 3] (Propylene-based random copolymer (A2-1): PP-2-1)
In (2-4) main polymerization of Reference Example 2, as propylene, a propylene mixture containing 40% by weight of chemical recycling-derived propylene and 60% by weight of fossil fuel-derived propylene was used instead of fossil fuel-derived propylene, and as ethylene, (2-1) to (2-4) of Reference Example 2 except that an ethylene mixture containing 40% by weight of ethylene derived from chemical recycling and 60% by weight of ethylene derived from fossil fuels was used instead of ethylene derived from fossil fuels. Similarly, a propylene-ethylene random copolymer (PP-2-1), which is a propylene-based random copolymer (A2-1), was obtained. Table 2 shows the resin physical properties of the obtained propylene/ethylene random copolymer (PP-2-1).
Addition of (2-5) in Reference Example 2 using the propylene/ethylene random copolymer (PP-2-1) obtained in place of the fossil fuel-derived propylene random copolymer (PP-2-0) A polypropylene resin composition (granulated product) was prepared according to the drug formulation and granulation, and a film with a thickness of 30 μm was prepared according to the same method (2-6) for film preparation. Table 2 shows the physical properties of the obtained film.

[Example 4] (Propylene-based random copolymer (A2-1): PP-2-2)
Reference Example 2 (2-4) In the main polymerization, as propylene, propylene derived from chemical recycling was used instead of propylene derived from fossil fuels, and as ethylene, ethylene derived from chemical recycling was used instead of ethylene derived from fossil fuels. In the same manner as (2-1) to (2-4) of Reference Example 2, a propylene-ethylene random copolymer (PP-2-2), which is a propylene-based random copolymer (A2-1), was prepared. Obtained. Table 2 shows the resin physical properties of the obtained propylene/ethylene random copolymer.
Addition of (2-5) in Reference Example 2 by using the propylene/ethylene random copolymer (PP-2-2) obtained in place of the fossil fuel-derived propylene random copolymer (PP-2-0). A polypropylene resin composition (granulated product) was prepared according to the drug formulation and granulation, and a film with a thickness of 30 μm was produced according to the same method (2-6) for film production. 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 the homogeneous solution thus obtained was cooled to 23°C, 750ml of this homogeneous solution was dropped over 1 hour into 2000ml of titanium tetrachloride maintained at -20°C. After the dropwise addition, the temperature of the resulting mixture was raised to 110°C over 4 hours, and when it reached 110°C, 52.2 g of diisobutyl phthalate (DIBP) was added, and the mixture was kept at the same temperature for 2 hours with stirring. was held at Next, a solid portion was collected by filtration while hot, and this solid portion was resuspended in 2750 ml of titanium tetrachloride, and then heated again at 110° C. for 2 hours.

After heating, the solid portion was collected again by hot filtration and washed with decane and hexane at 110° C. until no titanium compound was detected in the washing liquid.
The solid titanium catalyst component prepared as described above was stored as a hexane slurry, and a portion of it was dried to examine the catalyst composition. The solid titanium catalyst component contained 2% titanium, 57% chlorine, 21% magnesium, and 20% DIBP by weight.

(3-2) Polymerization pretreatment 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 a 200 L autoclave equipped with a stirrer, and 700 g of propylene was inserted while keeping the internal temperature at 5° C., 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 twice with heptane. The obtained 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. This prepolymerized catalyst contained 10 g of polypropylene per gram of solid titanium catalyst component. Note that fossil fuel-derived propylene was used as propylene.

(3-3) Main polymerization The polymerization vessel was sent to a vessel polymerization vessel (1) with an internal capacity of 1000 L and equipped with a stirrer, and propylene was supplied at 133 kg/hour and hydrogen was supplied so that the hydrogen concentration in the gas phase was 8.0 mol%. The prepolymerized catalyst obtained in (3-2) was continuously supplied as a solid titanium catalyst component at 0.8 g/hour, triethylaluminum 15.3 g/hour, and dicyclopentyldimethoxysilane 1.5 mL/hour, and polymerization was carried out. Polymerization was carried out at a temperature of 70° C. and a pressure of 3.4 MPa/G. Note that fossil fuel-derived propylene was used as the propylene (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) with an internal capacity of 500 L and equipped with a stirrer for further polymerization. To the polymerization vessel (2), propylene was supplied at 21 kg/hour and hydrogen was 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) with an internal capacity of 500 L equipped with a stirrer, and further polymerization was carried out. To the polymerization vessel (3), propylene was supplied at 17 kg/hour and hydrogen was 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 and filtered before ethylene/propylene block copolymerization (the step of producing the propylene/ethylene random copolymer component (d)), and air-dried for at least 5 hours. 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. During 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.

The slurry obtained in the polymerization vessel (3) was sent to another vessel polymerization vessel (4) with an internal capacity of 500 L and equipped with a stirrer, and copolymerization (preparation of propylene/ethylene random copolymer component (d)) was performed. Ta. Propylene was supplied to the polymerization reactor (4) at 15 kg/hour, ethylene at 17 kg/hour, and hydrogen 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. Note that fossil fuel-derived ethylene was used as ethylene.
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 resin physical properties of the propylene/ethylene block copolymer (PP-3-0) thus obtained. Note that 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℃
Screw rotation speed: 200rpm
Feeder rotation speed: 500rpm

(3-5) Injection molding Using the granulated product obtained in (3-4), the ASTM test piece (injection molded product ) was molded. Table 3 shows the physical properties of the injection molded article made of 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℃
Mold temperature: 40℃
Injection time-holding time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds

[Example 5] (Propylene/ethylene block copolymer (A2-2): PP-3-1)
In (3-3) main polymerization of Reference Example 3, as propylene, a propylene mixture containing 40% by weight of propylene derived from chemical recycling and 60% by weight of propylene derived from fossil fuel was used instead of propylene derived from fossil fuel, and as ethylene, (3-1) to (3-3) of Reference Example 3 except that an ethylene mixture containing 40% by weight of ethylene derived from chemical recycling and 60% by weight of ethylene derived from fossil fuels was used instead of ethylene derived from fossil fuels. Similarly, a propylene/ethylene block copolymer (PP-3-1), which is a propylene/ethylene block copolymer (A2-2), was obtained. Table 3 shows the resin physical properties of the obtained propylene/ethylene block copolymer (PP-3-1).
(3-4) of Reference Example 3 using the 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 injection molding (3-5). Table 3 shows the physical properties of the injection molded product obtained.

[Example 6] (Propylene/ethylene block copolymer (A2-2): PP-3-2)
In the main polymerization of (3-3) of Reference Example 3, as propylene, propylene derived from chemical recycling was used instead of propylene derived from fossil fuel, and as ethylene, ethylene derived from chemical recycling was used instead of ethylene derived from fossil fuel. Other than that, propylene/ethylene block copolymer (PP-3-2) which is propylene/ethylene block copolymer (A2-2) was prepared in the same manner as in Reference Example 3 (3-1) to (3-3). ) was obtained. Table 3 shows the resin physical properties of the obtained propylene/ethylene block copolymer (PP-3-2).
(3-4) of Reference Example 3 using the propylene/ethylene block copolymer (PP-3-2) 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 injection molding (3-5). Table 3 shows the physical properties of the injection molded product obtained.

[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 and reacted 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 added dropwise over 1 hour to 200 ml of titanium tetrachloride maintained at -20°C. After charging, the temperature of this mixed solution was raised to 110°C over 4 hours, and when it reached 110°C, 5.22 g of diisobutyl phthalate (DIBP) was added, and the mixture was stirred at the same temperature for 2 hours. held.
After the 2-hour reaction was completed, the solid portion was collected by hot filtration, and this solid portion was resuspended in 275 ml of titanium tetrachloride, and then heated again at 110° C. for 2 hours. After the reaction was completed, the solid portion was collected again by hot filtration and thoroughly washed with decane and hexane at 110° C. until no free titanium compound was detected in the solution.
Here, 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 which had been previously purged with nitrogen. Next, the hexane solvent was dried in a nitrogen stream, and the product was further vacuum dried for 30 minutes. 40 ml of ion-exchanged water and 10 ml of 50% by volume sulfuric acid were added to this and stirred for 30 minutes. Transfer this aqueous solution to a 100 ml volumetric flask through filter paper, then add 1 ml of concentrated phosphoric acid aqueous solution as a masking agent for iron (II) ions and 5 ml of 3% hydrogen peroxide solution as a coloring reagent for titanium, and further increase the volume to 100 ml with ion-exchanged water. The volumetric flask was shaken and the absorbance at 420 nm was observed after 20 minutes using UV light, and free titanium was washed and removed until this absorption was no longer observed.
The solid titanium catalyst component prepared as described above was stored as a decane slurry, and a portion of it was dried for the purpose of investigating the catalyst composition. The composition of the obtained solid titanium catalyst component was 2.3% by weight of titanium, 61% by weight of chlorine, 19% by weight of magnesium, and 12.5% by weight of DIBP.

(4-2) Polymerization pretreatment 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 a 200 L autoclave equipped with a stirrer, and the internal temperature was 15 to 20. The mixture was maintained at ℃ and 600 g of propylene was added thereto, and the mixture was reacted with stirring for 60 minutes to obtain a catalyst slurry. Note that fossil fuel-derived propylene was used as propylene.

(4-3) Main polymerization 43 kg/hour of propylene and 177 NL/hour of hydrogen were placed in a jacketed circulating tubular polymerization vessel with an internal capacity of 58 L, and the catalyst slurry obtained in (4-2) was used as a solid titanium catalyst component. .58 g/hour, triethylaluminum 3.1 ml/hour, and dicyclopentyldimethoxysilane 3.3 ml/hour were continuously fed, and polymerization was carried out in a full liquid state without the presence of a gas phase. The temperature of the tubular polymerization vessel was 70°C, and the pressure was 3.53 MPa/G. Note that 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 with an internal capacity of 100 L equipped with a stirrer for further polymerization. Propylene was supplied to the polymerization vessel at a rate of 45 kg/hour, and hydrogen was supplied such 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. 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.

<Preparation of resin composition containing fossil fuel-derived propylene homopolymer>
(4-4) Additive formulation and granulation 75% by weight of propylene homopolymer (PP-4-0) powder and 25% by weight of ethylene/α-olefin copolymer (B) thus obtained in (4-3) To the total of propylene homopolymer (PP-4-0) and ethylene/α-olefin copolymer (B), 1000 ppm of Irganox 1010 (manufactured by Ciba Geigy) and Irgafos (manufactured by Ciba Geigy) were added as antioxidants. 1000 ppm of 168 and 1000 ppm of calcium stearate as a neutralizing agent were mixed in a tumbler, and then melt-kneaded in a twin-screw extruder under the following conditions to obtain a resin composition (4B-0) containing a propylene homopolymer. pellets were prepared.

<Melt-kneading conditions>
Co-directional twin-screw kneader: Product number KZW-15 (manufactured by Technovel Co., Ltd.)
Kneading temperature: 190℃
Screw rotation speed: 500rpm
Feeder rotation speed: 40rpm

(4-5) Injection molding Using the pellets obtained in (4-4), JIS test pieces (injection molded products) were made using an injection molding machine [product number EC40 (manufactured by Toshiba Machinery Co., Ltd.)] 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℃
Mold temperature: 40℃
Injection time-holding time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds

[Example 7] (Propylene homopolymer (A1): PP-4-1, resin composition containing the propylene homopolymer (A1))
In the main polymerization (4-3) of Reference Example 4, a propylene mixture containing 40% by weight of propylene derived from chemical recycling and 60% by weight of propylene derived from fossil fuels was used instead of propylene derived from fossil fuels as propylene. In the same manner as in Reference Example 4 (4-1) to (4-3), a propylene homopolymer (PP-4-1), which is a propylene homopolymer (A1), was obtained. Table 4 shows the resin properties of the obtained propylene homopolymer (PP-4-1).
Using the propylene homopolymer (PP-4-1) obtained in place of the fossil fuel-derived propylene homopolymer (PP-4-0), (4-4) additive formulation and granulation in Reference Example 4 Pellets of a resin composition (4B-1) containing a propylene homopolymer (PP-4-1) and an ethylene/α-olefin copolymer (B) were prepared according to (4-5) and injection molded. Therefore, an injection molded article was produced from pellets of the resin composition (4B-1). Table 4 shows the physical properties of the injection molded product obtained.

[Example 8] (Propylene homopolymer (A1): PP-4-2, resin composition containing the propylene homopolymer (A1))
(4-3) of Reference Example 4 In the main polymerization, propylene derived from chemical recycling was used as the propylene instead of propylene derived from fossil fuels. Similarly, a propylene homopolymer (PP-4-2), which is a propylene homopolymer (A1), was obtained. Table 4 shows the resin properties of the obtained propylene homopolymer (PP-4-2).
Using the propylene homopolymer (PP-4-2) obtained in place of the fossil fuel-derived propylene homopolymer (PP-4-0), (4-4) additive formulation and granulation in Reference Example 4 Pellets of a resin composition (4B-2) containing a propylene homopolymer (PP-4-2) and an ethylene/α-olefin copolymer (B) were prepared according to (4-5) and injection molded. Therefore, an injection molded article was produced from pellets of the resin composition (4B-2). Table 4 shows the physical properties of the injection molded product obtained.

[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 Titanium: 1.3 wt%, magnesium: 20 wt% A solid titanium catalyst component (i-1) containing 13.8% by weight of diisobutyl phthalate and 0.8% by weight of diethyl phthalate was obtained. The present inventors believe that the diethyl phthalate detected in the solid titanium catalyst component (i-1) is probably a combination of diisobutyl phthalate and solid titanium during the manufacturing process of the solid titanium catalyst component. We speculate that this may be due to accompanying transesterification with the ethanol used.

(5-2) Polymerization pretreatment 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. The mixture was placed in a 20 L autoclave equipped with a stirrer, and 900 g of propylene was added while keeping the internal temperature at 15 to 20° C., followed by reaction with stirring for 100 minutes. After the polymerization was completed, the solid components were precipitated, and the supernatant was removed and washed twice with heptane. The obtained solid component was resuspended in purified heptane, and the solid catalyst component concentration was adjusted with heptane to be 1.0 g/L to obtain a catalyst. Note that fossil fuel-derived propylene was used as the propylene.

(5-3) Main polymerization 300 L of liquefied propylene was charged into a polymerization tank with an internal volume of 500 L equipped with a stirrer, and while maintaining this liquid level, 100 kg/h of liquefied propylene was added to the catalyst 1 obtained in (5-2). 0 g/h, triethylaluminum 8.9 mL/h, and isopropylpyrrolidinodimethoxysilane 2.8 mL/h were continuously supplied, and polymerization was carried out at a temperature of 70°C. Further, hydrogen was continuously supplied so that the hydrogen concentration in the gas phase within the polymerization tank was 6.9 mol%. Note that fossil fuel-derived propylene was used as the propylene. After the obtained slurry was deactivated, propylene was evaporated to obtain a powdery propylene homopolymer (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. 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.

<Preparation of resin composition containing fossil fuel-derived propylene homopolymer>
(5-4) Additive formulation and granulation In this way, 80% by weight of the propylene homopolymer powder obtained in (5-3) and 20% by weight of talc (C) were added to 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 melted and kneaded in a twin screw extruder under the following conditions. Pellets of a resin composition (5B-0) containing a propylene homopolymer were prepared.

<Melt-kneading conditions>
Co-directional twin-screw kneader: Product number KZW-15 (manufactured by Technovel Co., Ltd.)
Kneading temperature: 190℃
Screw rotation speed: 500rpm
Feeder rotation speed: 50rpm

(5-5) Injection molding Using the pellets obtained in (5-4), JIS test pieces (injection molded products) were made using an injection molding machine [product number EC40 (manufactured by Toshiba Machinery Co., Ltd.)] 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℃
Mold temperature: 40℃
Injection time-holding time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds

[Example 9] (Propylene homopolymer (A1): PP-5-1, resin composition containing the propylene homopolymer (A1))
In the main polymerization (5-3) of Reference Example 5, a propylene mixture containing 40% by weight of propylene derived from chemical recycling and 60% by weight of propylene derived from fossil fuels was used as propylene instead of propylene derived from fossil fuels. In the same manner as in Reference Example 5 (5-1) to (5-3), a propylene homopolymer (PP-5-1), which is a propylene homopolymer (A1), was obtained. Table 5 shows the resin physical properties of the obtained propylene homopolymer.
Using the propylene homopolymer (PP-5-1) obtained in place of the fossil fuel-derived propylene homopolymer (PP-5-0), (5-4) additive formulation and granulation in Reference Example 5 Pellets of the resin composition (5B-1) containing a propylene homopolymer (PP-5-1) and talc (C) were prepared according to (5-5) injection molding. An injection molded article was produced from the pellets of 1). Table 5 shows the physical properties of the injection molded product obtained.

[Example 10] (Propylene homopolymer (A1): PP-5-2, resin composition containing the propylene homopolymer (A1))
(5-3) of Reference Example 5 In the main polymerization, propylene derived from chemical recycling was used as the propylene instead of propylene derived from fossil fuels. Similarly, a propylene homopolymer (PP-5-2), which is a propylene homopolymer (A1), was obtained. Table 5 shows the resin physical properties of the obtained propylene homopolymer (PP-5-2).
Using the propylene homopolymer (PP-5-2) obtained in place of the fossil fuel-derived propylene homopolymer (PP-5-0), (5-4) additive formulation and granulation in Reference Example 5 Pellets of a resin composition (5B-2) containing a propylene homopolymer (PP-5-2) and talc (C) were prepared according to (5-5) injection molding. An injection molded article was produced from the pellets of 2). Table 5 shows the physical properties of the injection molded product obtained.

[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, 750ml of this homogeneous solution was dropped over 1 hour into 2000ml of titanium tetrachloride maintained at -20°C. After the dropwise addition, the temperature of the resulting mixed solution was raised to 110°C over 4 hours, and when it reached 110°C, 52.2 g of diisobutyl phthalate (DIBP) was added, and from this point on, the temperature was raised with stirring for 2 hours. was held at Next, a solid portion was collected by filtration while hot, and this solid portion was resuspended in 2750 ml of titanium tetrachloride, and then heated again at 110° C. for 2 hours.
After heating, the solid portion was collected again by hot filtration and washed with decane and hexane at 110° C. until no titanium compound was detected in the washing liquid.
The solid titanium catalyst component prepared as described above was stored as a hexane slurry, and a portion of it was dried to examine the catalyst composition. The solid titanium catalyst component contained 2% titanium, 57% chlorine, 21% magnesium, and 20% DIBP by weight.

(6-2) Polymerization pretreatment 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 a 200 L autoclave equipped with a stirrer, and the internal temperature was brought to 5°C. 560g of propylene was then added and reacted for 60 minutes with stirring. After the polymerization was completed, the solid components were allowed to settle, and the supernatant was removed and washed twice with heptane. The obtained prepolymerization catalyst was resuspended in purified heptane, and the titanium catalyst component concentration was adjusted to 0.7 g/L using heptane. The prepolymerization catalyst contained 10 grams of polypropylene per gram of solid titanium catalyst component. Note that fossil fuel-derived propylene was used as the propylene.

(6-3) Main polymerization In a jacketed circulating tubular polymerization vessel with an internal capacity of 58 L, propylene was fed at 30 kg/hour, hydrogen was fed at 33 NL/hour, catalyst slurry was used as a titanium catalyst component at 0.6 g/hour, and triethylaluminum 1.9 ml/hour. 1.1 ml/hour of cyclohexylmethyldimethoxysilane was continuously supplied for 1 hour, and polymerization was carried out in a full liquid state without the presence of a gas phase. The temperature of the tubular reactor was 70°C and the pressure was 3.6 MPa/G.
The obtained slurry was sent to a vessel polymerization vessel with an internal capacity of 100 L equipped with a stirrer for further polymerization. Propylene was supplied at 15 kg/hour and hydrogen was supplied to the polymerization reactor 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. Note that fossil fuel-derived propylene was used as the propylene.
After vaporizing the obtained 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. 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.

<Preparation of resin composition containing fossil fuel-derived propylene homopolymer>
(6-4) Additive formulation and kneading/granulation In this way, 79% by weight of the propylene homopolymer (PP-6-0) powder obtained in (6-3) and 1% by weight of maleic anhydride-modified polypropylene (F) were added. , 1000 ppm of Irganox 1010 manufactured by Ciba Geigy and 1000 ppm of Irgafos 168 manufactured by Ciba Geigy as antioxidants, based on the total of propylene homopolymer (PP-6-0) and maleic anhydride modified polypropylene (F), 1000 ppm of calcium stearate was formulated as a neutralizing agent, mixed in a tumbler, fed quantitatively to the hopper section with a quantitative feeder, melted and kneaded in a twin-screw extruder under the following conditions, and then mixed on the side of the twin-screw extruder. 20% by weight of short glass fibers (D) is quantitatively fed from the feed port to the melt-kneaded components using a quantitative feeder, and further melt-kneaded to form pellets of a resin composition (6B-0) containing a propylene homopolymer. was prepared.

<Melt-kneading conditions>
Co-directional twin-screw kneader: Product number TEX-30α (manufactured by Nippon Steel Corporation)
Kneading temperature: 210℃

(6-5) Injection molding Using the pellets obtained in (6-4), test pieces (injection molded products) were 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℃
Mold temperature: 40℃

[Example 11] (Propylene homopolymer (A1): PP-6-1, resin composition containing the propylene homopolymer (A1))
In the main polymerization (6-3) of Reference Example 6, a propylene mixture containing 40% by weight of propylene derived from chemical recycling and 60% by weight of propylene derived from fossil fuels was used instead of propylene derived from fossil fuels as propylene. In the same manner as in Reference Example 6 (6-1) to (6-3), a propylene homopolymer (PP-6-1), which is a propylene homopolymer (A1), was obtained. Table 6 shows the resin physical properties of the obtained propylene homopolymer (PP-6-1).
Using the propylene homopolymer (PP-6-1) obtained in place of the fossil fuel-derived propylene homopolymer (PP-6-0), additive formulation and kneading/kneading in (6-4) of Reference Example 6 were carried out. According to granulation, pellets of a resin composition (6B-1) containing a propylene homopolymer (PP-6-1), a maleic anhydride-modified polypropylene (F), and short glass fibers (D) were prepared, and the same (6B-1) was prepared. 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 injection molded product obtained.

[Example 12] (Propylene homopolymer (A1): PP-6-2, resin composition containing the propylene homopolymer (A1))
(6-3) of Reference Example 6 In the main polymerization, propylene derived from chemical recycling was used as the propylene instead of propylene derived from fossil fuels. Similarly, a propylene homopolymer (PP-6-2), which is a propylene homopolymer (A1), was obtained. Table 6 shows the resin physical properties of the obtained propylene homopolymer (PP-6-2).
Using the propylene homopolymer (PP-6-2) obtained in place of the fossil fuel-derived propylene homopolymer (PP-6-0), additive formulation and kneading/kneading in (6-4) of Reference Example 6 were carried out. According to granulation, pellets of a resin composition (6B-2) containing a propylene homopolymer (PP-6-2), a maleic anhydride-modified polypropylene (F), and short glass fibers (D) were prepared, and the same (6B-2) was prepared. 6-5) An injection molded article was produced from pellets of the resin composition (6B-2) according to injection molding. Table 6 shows the physical properties of the injection molded product obtained.

[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 used. A solid titanium catalyst component was prepared containing 20% by weight of .

(7-2) Polymerization pretreatment 180 g of solid titanium catalyst component, 30.9 mL of triethylaluminum, and 120 L of heptane were charged into a 200 L autoclave equipped with a stirrer, and the internal temperature was kept at 5°C, and 1080 g of propylene was charged. The reaction was allowed to proceed for 60 minutes with stirring. After the polymerization was completed, the solid components were allowed to settle, and the supernatant was removed and washed twice with heptane. The obtained prepolymerization catalyst was resuspended in purified heptane, and the titanium catalyst component concentration was adjusted to 1.5 g/L using heptane. The prepolymerized catalyst contained 6 grams of polypropylene per gram of solid titanium catalyst component. Note that fossil fuel-derived propylene was used as the propylene.

(7-3) Main polymerization Propylene was supplied at 110 kg/h and hydrogen was supplied to a vessel polymerization vessel (1) with an internal capacity 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 produced in (7-2) as a solid titanium catalyst component, 5.8 ml/h of triethylaluminum, and 2.7 ml/h of dicyclopentyldimethoxysilane were continuously fed. The polymerization temperature was 73° C. and the pressure was 3.2 MPa/G. Note that fossil fuel-derived propylene was used as the propylene. (The same applies to the following steps.)
The slurry obtained in the vessel polymerization vessel (1) was sent to another vessel polymerization vessel (2) with an internal capacity of 1000 L and equipped with a stirrer for further polymerization. To the vessel polymerization vessel (2), propylene was supplied at 30 kg/h and hydrogen was 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) with an internal capacity of 500 L and equipped with a stirrer for further polymerization. Propylene was supplied at 45 kg/h and hydrogen was supplied to the vessel polymerization reactor (3) 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 obtained slurry, gas-solid separation was performed to obtain a powdered 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. 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.

<Preparation of resin composition containing fossil fuel-derived propylene homopolymer>
(7-4) Additive formulation and kneading/granulation 85% by weight of the propylene homopolymer (PP-7-0) powder thus obtained in (7-3), 5% by weight of maleic anhydride-modified polypropylene (F), 10% by weight of carbon single fiber (E), 1000 ppm of Irganox 1010 manufactured by Ciba Geigy as an antioxidant, based on the total of propylene homopolymer (PP-7-0) and maleic anhydride-modified polypropylene (F). and Ciba Geigy's Irgafos 168 at 1000 ppm and calcium stearate as a neutralizing agent at 1000 ppm, 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. (7B-0) pellets were prepared.

<Melt-kneading conditions>
Single-shaft kneading machine: Product number Labo Plastomill 10M100 (manufactured by Toyo Seiki Co., Ltd.)
Kneading temperature: 220℃
Screw rotation speed: 60rpm
Pellet length: about 5mm

(7-5) Injection molding Using the pellets obtained in (7-4), test pieces (injection molded products) were 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℃
Mold temperature: 40℃
Injection time-holding time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds

[Example 13] (Propylene homopolymer (A1): PP-7-1, resin composition containing the propylene homopolymer (A1))
In the main polymerization (7-3) of Reference Example 7, a propylene mixture containing 40% by weight of propylene derived from chemical recycling and 60% by weight of propylene derived from fossil fuels was used instead of propylene derived from fossil fuels as propylene. In the same manner as in Reference Example 7 (7-1) to (7-3), a propylene homopolymer (PP-7-1), which is a propylene homopolymer (A1), was obtained. Table 7 shows the resin physical properties of the obtained propylene homopolymer (PP-7-1).
Using the propylene homopolymer (PP-7-1) obtained in place of the fossil fuel-derived propylene homopolymer (PP-7-0), additive formulation and kneading/kneading in (7-4) of Reference Example 7 were carried out. According to granulation, pellets of a resin composition (7B-1) containing a propylene homopolymer (PP-7-1), a maleic anhydride-modified polypropylene (F), and a carbon single fiber (E) were prepared, and the same (PP-7-1) was prepared. 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 injection molded product obtained.

[Example 14] (Propylene homopolymer (A1): PP-7-2, resin composition containing the propylene homopolymer (A1))
(7-1) to (7-3) of Reference Example 7, except that in the main polymerization of (7-3) of Reference Example 7, propylene derived from chemical recycling was used instead of propylene derived from fossil fuels. In the same manner as above, a propylene homopolymer (PP-7-2), which is a propylene homopolymer (A1), was obtained. Table 7 shows the resin physical properties of the obtained propylene homopolymer (PP-7-2).
Using the propylene homopolymer (PP-7-2) obtained in place of the fossil fuel-derived propylene homopolymer (PP-7-0), additive formulation and kneading/kneading in (7-4) of Reference Example 7 were carried out. According to granulation, pellets of a resin composition (7B-2) containing a propylene homopolymer (PP-7-2), a maleic anhydride-modified polypropylene (F), and a carbon single fiber (E) were prepared, and the same (PP-7-2) was prepared. 7-5) An injection molded article was produced from pellets of the resin composition (7B-2) according to injection molding. Table 7 shows the physical properties of the injection molded product obtained.

[Reference Example 8] (Fossil fuel-derived propylene random copolymer, resin composition containing the propylene random copolymer)
<Preparation of fossil fuel-derived propylene 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 (2-1) of Reference Example 2.

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

(8-3) Polymerization pretreatment 230 liters of purified heptane was charged into a reaction tank with an internal volume of 500 liters equipped with a stirrer, 25 kg of the solid catalyst component was added, and 1 portion of triethylaluminum was added to each titanium atom in the solid catalyst component. .0 mol/mol and dicyclopentyldimethoxysilane were supplied at a rate of 1.8 mol/mol. Thereafter, propylene was introduced until the propylene partial pressure reached 0.03 MPa-G, and the mixture was reacted at 25° C. for 4 hours. After the reaction was completed, the solid catalyst component was washed several times with purified heptane, carbon dioxide was further supplied, and the mixture was stirred for 24 hours. Note that fossil fuel-derived propylene was used as the propylene.

(8-4) Main polymerization In a polymerization apparatus with an internal capacity of 200 liters and equipped with a stirrer, the treated solid catalyst component of (8-3) was added at 3 mmol/hr in terms of titanium atoms in the component, and triethylaluminum was added at 2.5 mmol/hr. kg-PP, and dicyclopentyldimethoxysilane was supplied at 0.25 mmol/kg-PP, respectively. Then, propylene, ethylene, and 1-butene were continuously supplied at a rate of 46.0 kg/hr, 2.0 kg/hr, and 2.4 kg/hr, respectively, at a polymerization temperature of 82°C and a polymerization pressure of 2.8 MPa-G to cause the reaction. Ta. 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%. Note that fossil fuel-derived propylene was used as propylene, fossil fuel-derived ethylene was used as ethylene, and fossil fuel-derived 1-butene was used as 1-butene.
Table 8 shows the resin physical properties of the propylene/ethylene/1-butene random copolymer (PP-8-0) 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.

<Preparation of resin composition containing fossil fuel-derived propylene random copolymer>
(8-5) Additive formulation and kneading/granulation Propylene/ethylene/1-butene random copolymer powder 75% by weight thus obtained in (8-4), ethylene/α-olefin copolymer (B) 25 In terms of weight percent, 1000 ppm of Irganox 1010 manufactured by Ciba Geigy and 1000 ppm of Irganox 1010 manufactured by Ciba Geigy as an antioxidant were added to the total of propylene/ethylene/1-butene random copolymer and ethylene/α-olefin copolymer (B). 1,000 ppm of Irgafos 168 and 1,000 ppm of calcium stearate as a neutralizing agent were mixed in a tumbler, and then melt-kneaded in a twin-screw extruder under the following conditions to obtain a resin composition (8B) containing a propylene-based random copolymer. -0) pellets were prepared.

<Melt-kneading conditions>
Co-directional twin-screw kneader: Product number KZW-15 (manufactured by Technovel Co., Ltd.)
Kneading temperature: 190℃
Screw rotation speed: 500rpm
Feeder rotation speed: 40rpm

(8-6) Injection molding Using the pellets obtained in (8-5), JIS test pieces (injection molded products) 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℃
Mold temperature: 40℃
Injection time-holding time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds

[Example 15] (Propylene-based random copolymer (A2-1): PP-8-1, resin composition containing the propylene-based random copolymer (A2-1))
In the main polymerization (8-4) of Reference Example 8, a propylene mixture containing 40% by weight of propylene derived from chemical recycling and 60% by weight of propylene derived from fossil fuels was used as propylene instead of propylene derived from fossil fuels, and as ethylene, (8-1) to (8-4) of Reference Example 8 except that an ethylene mixture containing 40% by weight of chemically recycled ethylene and 60% by weight of fossil fuel-derived ethylene was used instead of fossil fuel-derived ethylene. Similarly, a propylene-ethylene-1-butene random copolymer (PP-8-1), which is a propylene-based random copolymer (A2-1), was obtained. Table 8 shows the resin physical properties of the obtained propylene/ethylene/1-butene random copolymer (PP-8-1).
Additive (8-5) of Reference Example 8 was obtained by using the propylene random copolymer (PP-8-1) obtained in place of the fossil fuel-derived propylene random copolymer (PP-8-0). Prepare pellets of a resin composition (8B-1) containing a propylene random copolymer (PP-8-1) and an ethylene/α-olefin copolymer (B) according to the prescription, kneading and granulation, An injection molded article was produced from pellets of the resin composition (8B-1) according to the injection molding procedure (8-6). Table 8 shows the physical properties of the injection molded product obtained.

[Example 16] (Propylene-based random copolymer (A2-1): PP-8-2, resin composition containing the propylene-based random copolymer (A2-1))
Reference Example 8 (8-4) In the main polymerization, as propylene, propylene derived from chemical recycling was used instead of propylene derived from fossil fuels, and as ethylene, ethylene derived from chemical recycling was used instead of ethylene derived from fossil fuels. A propylene-based random copolymer (A2-1), a propylene-ethylene-1-butene random copolymer (PP-8), was prepared in the same manner as in Reference Example 8 (8-1) to (8-4). -2) was obtained. Table 8 shows the resin physical properties of the obtained propylene/ethylene/1-butene random copolymer (PP-8-2).
Using the propylene random copolymer (PP-8-2) obtained in place of the fossil fuel-derived propylene random copolymer (PP-8-0), the (8-5) additive of Reference Example 8 was added. Prepare pellets of a resin composition (8B-2) containing a propylene random copolymer (PP-8-2) and an ethylene/α-olefin copolymer (B) according to the prescription and kneading/granulation, An injection molded article was produced from pellets of the resin composition (8B-2) according to the injection molding procedure (8-6). Table 8 shows the physical properties of the injection molded product obtained.

[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 (4-1) of Reference Example 4.

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

(9-3) Main polymerization In a jacketed circulating tubular polymerization vessel with an internal capacity of 58 L, 43 kg/hour of propylene and 300 NL/hour of hydrogen were used, and the catalyst slurry produced in (9-2) was used as a solid titanium catalyst component at 0.0. 55 g/hour, triethylaluminum 2.9 ml/hour, and dicyclopentyldimethoxysilane 3.1 ml/hour were continuously fed, and polymerization was carried out in a full liquid state without the presence of a gas phase. The temperature of the tubular polymerization vessel was 70°C, and the pressure was 3.74 MPa/G. Note that fossil fuel-derived propylene was used as the propylene. (The same applies to the following steps.)
The slurry obtained in the cyclic tubular polymerization vessel was sent to a vessel polymerization vessel with an internal capacity of 100 L equipped with a stirrer for further polymerization. Propylene was supplied at 45 kg/hour and hydrogen was supplied to the polymerization reactor 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 an internal capacity of 2.4 L, the slurry was gasified, and gas-solid separation was performed. The mixture was sent to a phase polymerization vessel, and ethylene/propylene block copolymerization (preparation of propylene/ethylene random copolymer component (d)) was performed. At this time, the powder before copolymerization was sampled and the MFR, melting point, pentad fraction, and Mw/Mn were measured. During 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.

Propylene, ethylene, and hydrogen were continuously added so that the gas composition in the gas phase polymerization vessel was 0.23 (mole ratio) as ethylene/(ethylene + propylene) and 0.031 (mole ratio) as hydrogen/ethylene. supplied. Polymerization was carried out at a polymerization temperature of 70° C. and a pressure of 1.0 MPa/G. Note that fossil fuel-derived ethylene was used as ethylene.
After vaporizing the slurry obtained in a gas phase polymerizer, 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. For 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 were added as a neutralizing agent, and pellets obtained by melt-kneading were used. Using.

<Preparation of resin composition containing fossil fuel-derived propylene/ethylene block copolymer>
(9-4) Additive formulation and kneading/granulation In this way, 75% by weight of the propylene/ethylene block copolymer powder obtained in (9-3) and 25% by weight of the ethylene/α-olefin copolymer (B), Neutralize the total amount of propylene/ethylene block copolymer and ethylene/α-olefin copolymer (B) with 1000 ppm of Irganox 1010 manufactured by Ciba Geigy and 1000 ppm of Irgafos 168 manufactured by Ciba Geigy as antioxidants. 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. did.

<Melt-kneading conditions>
Co-directional twin-screw kneader: Product number KZW-15 (manufactured by Technovel Co., Ltd.)
Kneading temperature: 190℃
Screw rotation speed: 500rpm
Feeder rotation speed: 40rpm

(9-5) Injection molding Using the pellets obtained in (9-4), mold JIS test pieces (injection molded products) using an injection molding machine [product number EC40, manufactured by Toshiba Machinery Co., Ltd.] under the following conditions. did. 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℃
Mold temperature: 40℃
Injection time-holding time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds

[Example 17]
In (9-3) main polymerization of Reference Example 9, a propylene mixture containing 40% by weight of propylene derived from chemical recycling and 60% by weight of propylene derived from fossil fuels was used as propylene instead of propylene derived from fossil fuels, and as ethylene, (9-1) to (9-3) of Reference Example 9 except that an ethylene mixture containing 40% by weight of ethylene derived from chemical recycling and 60% by weight of ethylene derived from fossil fuels was used instead of ethylene derived from fossil fuels. Similarly, a propylene/ethylene block copolymer (PP-9-1), which is a propylene/ethylene block copolymer (A2-2), was obtained. Table 9 shows the resin physical properties of the obtained propylene/ethylene block copolymer (PP-9-1).

(9-4) of Reference Example 9 using the 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 prepared according to the additive formulation and kneading/granulation. An injection molded article was produced from the pellets of the resin composition (9B-1) according to the same procedure (9-5) injection molding. Table 9 shows the physical properties of the injection molded product obtained.

[Example 18]
Reference Example 9 (9-3) In the main polymerization, as propylene, propylene derived from chemical recycling was used instead of propylene derived from fossil fuels, and as ethylene, ethylene derived from chemical recycling was used instead of ethylene derived from fossil fuels. is a propylene/ethylene block copolymer (PP-9-2) which is a propylene/ethylene block copolymer (A2-2) in the same manner as (9-1) to (9-3) of Reference Example 9. I got it. Table 9 shows the resin physical properties of the obtained propylene/ethylene block copolymer (PP-9-2).

(9-4) of Reference Example 9 using the propylene/ethylene block copolymer (PP-9-2) obtained in place of the fossil fuel-derived propylene/ethylene block copolymer (PP-9-0) Pellets of a resin composition (9B-2) containing a propylene/ethylene block copolymer (PP-9-2) and an ethylene/α-olefin copolymer (B) are prepared according to the additive formulation and kneading/granulation. An injection molded article was produced from the pellets of the resin composition (9B-2) according to the same procedure (9-5) injection molding. Table 9 shows the physical properties of the injection molded product obtained.

[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 (4-1) of Reference Example 4.

(10-2) Polymerization pretreatment 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 inserted into a 20 L autoclave equipped with a stirrer. Then, while maintaining the internal temperature at 15 to 20°C, 1,000 g of propylene was added, and the mixture was reacted for 120 minutes with stirring. After the polymerization was completed, the solid components were allowed to settle, and the supernatant was removed and washed twice with heptane. The obtained prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid titanium catalyst component concentration was 1.0 g/L to obtain a catalyst slurry.

(10-3) Main polymerization 43 kg/hour of propylene and 256 NL/hour of hydrogen were placed in a jacketed circulating tubular polymerization vessel with an internal capacity of 58 L. The catalyst slurry produced in (10-2) was used as a solid titanium catalyst component at 0.00%. 49 g/hour, triethylaluminum at 4.5 ml/hour, and diethylaminotriethoxysilane at 1.8 ml/hour were continuously fed, and polymerization was carried out in a full liquid state without the presence of a gas phase. The temperature of the tubular polymerization vessel was 70°C, and the pressure was 3.57 MPa/G. Note that 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 with an internal capacity of 100 L equipped with a stirrer for further polymerization. Propylene was supplied at 45 kg/hour and hydrogen was supplied to the polymerization reactor 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 transfer tube with an internal capacity 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 ethylene/propylene block copolymerization (preparation of propylene/ethylene random copolymer component (d)) was performed. At this time, the powder before copolymerization was sampled and the MFR, melting point, pentad fraction, and Mw/Mn were measured. During 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.

Propylene, ethylene, and hydrogen were continuously added so that the gas composition in the gas phase polymerization vessel was 0.20 (mole ratio) as ethylene/(ethylene + propylene) and 0.0063 (mole ratio) as hydrogen/ethylene. supplied. Polymerization was carried out at a polymerization temperature of 70° C. and a pressure of 1.40 MPa/G. Note that fossil fuel-derived ethylene was used as ethylene.
After vaporizing the slurry obtained in a gas phase polymerizer, 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. For 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 were added as a neutralizing agent, and pellets obtained by melt-kneading were used. Using.

<Preparation of resin composition containing fossil fuel-derived propylene/ethylene block copolymer>
(10-4) Additive formulation and kneading/granulation 60% by weight of the propylene/ethylene block copolymer powder obtained in (10-3), 20% by weight of ethylene/α-olefin copolymer (B), talc (C) 20% by weight, 1000 ppm of Irganox 1010 manufactured by Ciba Geigy as an antioxidant, and 1000 ppm of Irganox 1010 manufactured by Ciba Geigy, based on the total of propylene/ethylene block copolymer and ethylene/α-olefin copolymer (B) A resin composition containing a propylene/ethylene block copolymer ( 10B-0) was prepared.

<Melt-kneading conditions>
Co-directional twin-screw kneader: Product number KZW-15 (manufactured by Technovel Co., Ltd.)
Kneading temperature: 190℃
Screw rotation speed: 500rpm
Feeder rotation speed: 40rpm

(10-5) Injection molding Using the pellets obtained in (10-4), JIS test pieces (injection molded products) 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℃
Mold temperature: 40℃
Injection time-holding time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds

[Example 19]
In the main polymerization (10-3) of Reference Example 10, as propylene, a propylene mixture containing 40% by weight of propylene derived from chemical recycling and 60% by weight of propylene derived from fossil fuel was used instead of propylene derived from fossil fuel, and as ethylene, (10-1) to (10-3) of Reference Example 10 except that an ethylene mixture containing 40% by weight of chemically recycled ethylene and 60% by weight of fossil fuel-derived ethylene was used instead of fossil fuel-derived ethylene. Similarly, a propylene/ethylene block copolymer (PP-10-1), which is a propylene/ethylene block copolymer (A2-2), was obtained. Table 10 shows the resin physical properties of the obtained propylene/ethylene block copolymer (PP-10-1).

(10-4) of Reference Example 10 using the 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- Pellets of 1) were prepared, and an injection molded article was produced from the pellets of the resin composition (10B-1) according to injection molding (10-5). Table 10 shows the physical properties of the injection molded product obtained.

[Example 20]
Reference Example 10 (10-3) In the main polymerization, as propylene, propylene derived from chemical recycling was used instead of propylene derived from fossil fuels, and as ethylene, ethylene derived from chemical recycling was used instead of ethylene derived from fossil fuels. is a propylene/ethylene block copolymer (PP-10-2) which is a propylene/ethylene block copolymer (A2-2) in the same manner as (10-1) to (10-3) of Reference Example 10. I got it. Table 10 shows the resin physical properties of the obtained propylene/ethylene block copolymer (PP-10-2).

(10-4) of Reference Example 10 using the propylene/ethylene block copolymer (PP-10-2) obtained in place of the fossil fuel-derived propylene/ethylene block copolymer (PP-10-0) A resin composition (10B- Pellets of 2) were prepared, and an injection molded article was produced from the pellets of the resin composition (10B-2) according to injection molding (10-5). Table 10 shows the physical properties of the injection molded product obtained.

From the results in Tables 1 to 10, it can be seen that the propylene polymer (A) of the present invention and the resin composition containing the propylene polymer (A) have a large environmental load because the propylene raw material is only propylene derived from fossil fuels. It has performance equivalent to existing fossil fuel-derived propylene polymers and resin compositions containing the propylene polymers. According to the present invention, it is possible to reduce the environmental load, hold down costs, and promote the spread of propylene-based polymers that have the effect of reducing the environmental load.

Claims (16)

A propylene polymer which is a propylene homopolymer or a copolymer of propylene and at least one olefin selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms; A propylene-based polymer in which the propylene contained in the raw material contains 0.1% by weight or more of propylene derived from chemical recycling. 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 is 0.01 g/10 minutes or more and 2,000 g/10 minutes or less (ii) Isotactic pentad fraction is 90.0% or more 99.9% or less 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% to 99.9% by weight of structural units derived from propylene and 0.1% to 10.0% by weight of structural units derived from olefin (b). including,
The propylene polymer according to claim 1, which satisfies the following (iii) to (iv).
(iii) Melt flow rate (MFR) at 230℃ and 2.16kg load is 0.01g/10 minutes or more and 2,000g/10minutes or less (iv) Melting point is 100℃ or more and 160℃ or less The propylene-based polymer is a propylene/ethylene block copolymer,
The propylene/ethylene block copolymer is
Consisting of 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, and the following (v)
(v) a crystalline propylene polymer component having an intrinsic viscosity [η] of 0.8 (dl/g) or more and 3.0 (dl/g) or less (c) 55% by weight or more and 95% by weight or less;
Contains 20% to 80% by weight of structural units derived from propylene and 20% to 80% by weight of structural units derived from ethylene, and the following (vi)
(vi) A propylene/ethylene random copolymer component (d) with an intrinsic viscosity [η] of 1.0 (dl/g) or more and 10.0 (dl/g) or less (d) 5% by weight or more and 45% by weight or less The propylene polymer according to claim 1, which contains the propylene polymer according to claim 1. 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 the 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 polymer, wherein the propylene contained in the raw material contains 0.1% by weight or more of propylene derived from chemical recycling. The propylene-based polymer is a propylene homopolymer that satisfies the following (i) to (ii);
(i) Melt flow rate (MFR) at 230°C and 2.16 kg load is 0.01 g/10 minutes or more and 2,000 g/10 minutes or less (ii) Isotactic pentad fraction is 90.0% or more 99.9% or less The method for producing a propylene polymer according to claim 5, comprising the step of supplying propylene as a raw material to a polymerization vessel and polymerizing it with a polymerization catalyst. Random copolymerization of propylene with at least one olefin (b) selected from the group consisting of ethylene and α-olefins having 4 to 8 carbon atoms, wherein the propylene polymer satisfies the following (iii) to (iv): It is a combination,
(iii) The melt flow rate (MFR) at 230°C and a load of 2.16 kg is 0.01 g/10 minutes or more and 2,000 g/10 minutes or less (iv) The melting point is 100°C or more and 160°C or less. The method for producing a propylene polymer according to claim 5, wherein the raw material contains propylene, 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% to 99.9% by weight of structural units derived from propylene and 0.1% to 10.0% by weight of structural units derived from at least one type of olefin (b). % or less, the method for producing a propylene polymer according to claim 7. The propylene-based polymer is a propylene/ethylene block copolymer,
The propylene/ethylene block copolymer is
Consisting of 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, and the following (v)
(v) a crystalline propylene polymer component having an intrinsic viscosity [η] of 0.8 (dl/g) or more and 3.0 (dl/g) or less (c) 55% by weight or more and 95% by weight or less;
Contains 20% to 80% by weight of structural units derived from propylene and 20% to 80% by weight of structural units derived from ethylene, and the following (vi)
(vi) A propylene/ethylene random copolymer component (d) with an intrinsic viscosity [η] of 1.0 (dl/g) or more and 10.0 (dl/g) or less (d) 5% by weight or more and 45% by weight or less Contains
Supplying propylene or a raw material (1) containing propylene and ethylene to a polymerization vessel and polymerizing it with a polymerization catalyst,
A crystalline propylene-based polymer consisting of 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 polymer according to claim 5, comprising the step (β). A resin composition comprising the propylene homopolymer according to claim 2. A resin composition comprising a random copolymer of the propylene according to claim 3 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 4. A molded article comprising the propylene homopolymer according to claim 2. A molded article made of a random copolymer of the propylene according to claim 3 and at least one olefin (b) selected from the group consisting of ethylene and α-olefin having 4 to 8 carbon atoms. A molded article comprising the propylene/ethylene block copolymer according to claim 4. A molded article made of the resin composition according to any one of claims 10 to 12.