JP7004864B1 - A propylene-based polymer obtained from an olefin mixture containing a biomass-derived olefin and a fossil fuel-derived olefin, and a method for producing the propylene-based polymer. - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce an environmental load (greenhouse gas generation) in a life cycle from production to utilization and disposal of a propylene-based polymer, and to adjust the amount of biomass-derived olefin in the propylene-based polymer. To provide a propylene-based polymer having equivalent performance at an arbitrary biomass-derived carbon concentration without the need for additional equipment / steps for mixing the system polymer and the fossil fuel-derived propylene-based polymer. To provide a propylene-based polymer having a desired biomass-derived carbon concentration and equivalent performance in consideration of market needs and the like at a low cost. SOLUTION: The propylene homopolymer or the propylene-based polymer which is a copolymer of propylene and a specific olefin, and (I) at least one kind of olefin contained in the raw material of the propylene-based polymer is a specific A propylene-based polymer that satisfies the condition that it is an olefin mixture of a weight% biomass-derived olefin and a specific weight% fossil fuel-derived olefin, and (II) the biomass-derived carbon concentration of the propylene-based polymer satisfies the specific condition. [Selection diagram] None

Description

The present invention relates to a propylene-based polymer and a method for producing the polymer. More specifically, the present invention relates to a propylene-based polymer obtained by polymerizing propylene composed of propylene derived from biomass and propylene derived from fossil fuel, and a method for producing the polymer.

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

However, while the world's fossil fuel production is about 7.9 billion tons (oil equivalent) / year (Non-Patent Document 1), the world's biomass fuel production is about 595 million tons (oil equivalent) / year. The number of years (Non-Patent Document 2) is small, and the production cost of biomass-derived propylene is high. Therefore, in order to widely spread a material containing a polymer derived from biomass-derived propylene, which has a low environmental load, a material having an adjusted biomass degree is required in consideration of product price, market needs, and the like.

Examples of the material for which the biomass degree of the material is adjusted include a material obtained by mixing polypropylene derived from biomass with crushed and regenerated polypropylene (Patent Document 3), and the abundance ratio of carbon derived from biomass is 70% or more and less than 100%. In addition, a material (Patent Document 4) in which a polyolefin chip derived from biomass and a polyolefin chip composed only of a petroleum-based material are mixed has been studied.

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

International Publication No. 2007-055361 Japanese Patent Publication No. 2010-511634 Japanese Patent Publication No. 2014-508688 Japanese Unexamined Patent Publication No. 2013-0762192 Japanese Patent Application Laid-Open No. 2021-091881 Japanese Unexamined Patent Publication No. 10-237127 Japanese Unexamined Patent Publication No. 9-031265 Japanese Unexamined Patent Publication No. 2004-292683

Strategic Research Seminar Global Long-term Energy Supply and Demand Outlook and the Role of Nuclear Energy (November 24, 2005), Internet <URL: https://www.jaea.go.JP/03/senryaku/seminar/05-1.pdf> International Institute for Environmental Economics Current Status and Future of Biofuels (1) (October 27, 2020), Internet <URL: https://ieei.or.JP/2020/10/expl201027/>

However, as in Patent Documents 3 and 4, the material whose degree of biomass is adjusted by mixing the polyolefin derived from biomass and the polyolefin derived from fossil fuel is a propylene-based polymer derived from biomass and a conventional propylene-based material derived from fossil fuel. It is necessary to mix the polymer, a mixing step is required, equipment for that is required, energy is consumed in the mixing step, and as a result, there is a concern that the environmental load will increase.

Further, in the material obtained by mixing the biomass-derived propylene-based polymer with the conventional fossil fuel-derived propylene-based polymer and adjusting the degree of biomass, the steric regularity and steric regularity distribution of the fossil fuel-derived propylene-based polymer If the physical characteristics of the propylene-based polymer, such as molecular weight and molecular weight distribution, are not completely the same as those of the biomass-derived propylene-based polymer, the original physical properties of the biomass-derived propylene-based polymer will change. In some cases, there is concern that the desired physical properties may be impaired.

Further, when the degree of biomass is adjusted by the method of Patent Document 5, biomass polyethylene is indispensable for the polymer composition (10 to 49 parts by weight), so that the propylene-based polymer simple substance and polyethylene are not contained. Compared to the propylene-based polymer composition, there is a concern that the performance derived from the propylene-based polymer simple substance, such as low rigidity and low deflection temperature under load, will be difficult to develop.

Further, the propylene-based polymer is a copolymer, and among the plurality of olefins constituting the copolymer, one olefin (for example, ethylene) uses only a biomass-derived olefin as a raw material, and another olefin (for example, propylene) is used. A method of producing a copolymer using olefin consisting only of petroleum-based material as a raw material can be considered, but if the abundance ratio of biomass-derived carbon in the copolymer is adjusted to a desired value, the copolymer can be produced. There is concern that the molecular structure (for example, the ratio of propylene to ethylene) will be a constant value depending on the abundance ratio of biomass-derived carbon, and the value of physical properties based on the molecular structure cannot be set to a desired value. ..

Structural differences between biomass-derived olefins (ethylene, propylene, α-olefins with 4-8 carbon atoms) and fossil fuel-derived olefins (ethylene, propylene, α-olefins with 4-8 carbon atoms) include 14C isotopes. Only that ( ¹⁴ C is present in the biomass-derived olefin at a concentration of about ^10-12 with respect to the total carbon). The only difference in the molecular structure of propylene-based polymers made from these materials is whether they have ¹⁴ C or not, and other molecular weights, molecular weight distributions, stereoregularities, stereoregularity distributions, compositions, composition distributions, and decans. As long as the molecular structure such as the amount of soluble part is the same, it is said that there is no difference in performance between the propylene-based polymer made of biomass-derived olefin and the conventional propylene-based polymer made of fossil fuel-derived olefin. The performance of the propylene-based polymer (for example, mechanical properties such as rigidity and impact resistance) includes the stereoregularity, molecular weight distribution, composition distribution (propylene / α-olefin random copolymer), and rubber amount (for example) of the propylene-based polymer. It is considered that the dependence on the molecular structure other than the 14C concentration (Patent Documents 6 to 8) such as the propylene / ethylene block copolymer) also applies to the propylene-based polymer containing the structural unit derived from the biomass-derived olefin.

An object of the present invention is to reduce the environmental load (greenhouse gas generation) in the life cycle from the production to utilization and disposal of the propylene-based polymer, and to adjust the amount of biomass-derived olefin in the propylene-based polymer. To provide a propylene-based polymer having equivalent performance at an arbitrary biomass-derived carbon concentration without the need for additional equipment / steps for mixing the biomass-derived propylene-based polymer and the fossil fuel-derived propylene-based polymer. , And a method for producing the polymer. Another object of the present invention is to provide a propylene-based polymer having a desired biomass-derived carbon concentration and equivalent performance in consideration of market needs and the like at a low cost.

As a result of diligent studies to solve the above problems, the present inventors have selected at least one of the group consisting of propylene, ethylene, and α-olefin having 4 to 8 carbon atoms as the monomer as a raw material of the propylene-based polymer. By containing an olefin mixture of a specific weight% biomass-derived olefin and a specific weight% fossil fuel-derived olefin, the type of olefin becomes a propylene-based polymer having a specific biomass-derived carbon concentration. , The present invention has been completed by finding that the above-mentioned problems can be solved.

The present invention relates to the following [1] to [20].
[1] A propylene homopolymer or a propylene-based polymer which is a copolymer of propylene and ethylene and at least one olefin (b) selected from the group consisting of α-olefins having 4 to 8 carbon atoms. A propylene-based polymer satisfying the following (I) to (II).
(I) At least one olefin (a) selected from the group consisting of propylene, ethylene, and α-olefins having 4 to 8 carbon atoms contained in the raw material of the propylene-based polymer is a biomass-derived olefin (a1) 0. An olefin mixture containing 2% by weight or more and 99% by weight or less and a fossil fuel-derived olefin (a2) of 1% by weight or more and 99.8% by weight or less (total of biomass-derived olefin (a1) and fossil fuel-derived olefin (a2)). Is 100% by weight).
(II) The biomass-derived carbon concentration of the propylene-based polymer is 0.2 pMC (%) or more and 99.0 pMC (%) or less.

[2] The propylene-based polymer is a propylene homopolymer, and 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 according to [2], which is a propylene homopolymer having a biomass degree of 1% or more and 99% or less according to ASTM D 6866.

[4] The propylene-based polymer is a random copolymer of propylene and at least one olefin (b) selected from the group consisting of ethylene and α-olefins having 4 to 8 carbon atoms.
The random copolymer contains 90.0% by weight or more and 99.9% by weight or less of the structural unit derived from propylene and 0.1% by weight or more and 10.0% by weight or less of the structural unit derived from the olefin (b). Including,
The propylene contained in the raw material of the random copolymer contains (I-1) 0.2% by weight or more and 99% by weight or less of biomass-derived propylene and 1% by weight or more and 99.8% by weight or less of propylene derived from fossil fuel. It is a propylene mixture (the total of biomass-derived propylene and fossil fuel-derived propylene is 100% by weight).
The propylene-based polymer according to [1], which also satisfies the following (iii) to (iv).
(Iii) 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 (iv) Melting point is 100 ° C. or more and 160 ° C. or less.

[5] Random copolymerization of propylene having a biomass degree of 1% or more and 99% or less according to ASTM D 6866 and at least one olefin (b) selected from the group consisting of ethylene and α-olefin having 4 to 8 carbon atoms. The propylene-based polymer according to [4], which is a polymer.

[6] The propylene-based polymer is a propylene / ethylene block copolymer.
Propylene contained in the raw material of the propylene / ethylene block copolymer is 0.2% by weight or more and 99% by weight or less of (I-1) biomass-derived propylene, and 1% by weight or more and 99.8% by weight or less of fossil fuel-derived propylene. It is a propylene mixture containing and (the total of biomass-derived propylene and fossil fuel-derived propylene is 100% by weight).
The propylene / ethylene block copolymer
It comprises a propylene homopolymer or a crystalline propylene / ethylene random copolymer containing 95% by weight or more and less than 100% by weight of a structural unit derived from propylene and 5% by weight or less of a structural unit derived from ethylene, as described in (v) below.
(V) The ultimate viscosity [η] is 0.8 (dl / g) or more and 3.0 (dl / g).
Crystalline propylene-based polymer component (c) 55% by weight or more and 95% by weight, which satisfies the above conditions.
Containing 20% by weight or more and 80% by weight or less of the structural unit derived from propylene and 20% by weight or more and 80% by weight of the structural unit derived from ethylene, the following (vi)
(Vi) The ultimate viscosity [η] is 1.0 (dl / g) or more and 10.0 (dl / g).
The propylene-based polymer according to [1], which contains 5% by weight or more and 45% by weight or less of the propylene / ethylene random copolymer component (d) satisfying the above conditions.

[7] The propylene-based polymer according to [6], which is a propylene / ethylene block copolymer having a biomass degree of 1% to 99% according to ASTM D 6866.

[8] Selected from the group consisting of a propylene homopolymer having a biomass-derived carbon concentration of 0.2 pMC (%) or more and 99.0 pMC (%) or less, or a group consisting of propylene, ethylene, and an α-olefin having 4 to 8 carbon atoms. It is a method for producing a propylene-based polymer which is a copolymer with at least one kind of olefin (b).
Including the step of supplying a raw material containing propylene to a polymerizer and polymerizing with a polymerization catalyst.
At least one olefin (a) selected from the group consisting of propylene, ethylene, and α-olefin having 4 to 8 carbon atoms contained in the raw material is 0.2% by weight or more and 99% by weight of the biomass-derived olefin (a1). It is an olefin mixture containing the following and 1% by weight or more and 99.8% by weight or less of the fossil fuel-derived olefin (a2) (the total of the biomass-derived olefin (a1) and the fossil fuel-derived olefin (a2) is 100% by weight). , A method for producing a propylene-based polymer.

[9] The propylene-based polymer is a propylene homopolymer satisfying the following (i) to (ii);
(I) Melt flow rate (MFR) at 230 ° C. and 2.16 kg load 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 Includes a step of supplying propylene, which is a raw material, to a polymerizer and polymerizing with a polymerization catalyst.
The raw material is a propylene mixture containing (I-1) 0.2% by weight or more and 99% by weight or less of biomass-derived propylene and 1% by weight or more and 99.8% by weight or less of fossil fuel-derived propylene (with biomass-derived propylene). The method for producing a propylene-based polymer according to [8], wherein the total amount of propylene derived from fossil fuel is 100% by weight).

[10] The propylene-based polymer comprises at least one olefin (b) selected from the group consisting of propylene and ethylene and an α-olefin having 4 to 8 carbon atoms, which satisfies the following (iii) to (iv). It is a random copolymer and
(Iii) 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 (iv) Melting point is 100 ° C. or higher and 160 ° C. or lower. The method for producing a propylene-based polymer according to [8], wherein the raw material comprises propylene, ethylene, and at least one olefin (b) selected from the group consisting of α-olefins having 4 to 8 carbon atoms.

[11] The random copolymer is composed of 90.0% by weight or more and 99.9% by weight or less of the structural unit derived from propylene and 0.1% by weight or more of the structural unit derived from at least one kind of olefin (b). Including 0.0% by weight or less
The raw material supplied to the polymerizer is
(I-1) Biomass-derived propylene A propylene mixture containing 0.2% by weight or more and 99% by weight or less and fossil fuel-derived propylene by 1% by weight or more and 99.8% by weight or less (total of biomass-derived propylene and fossil fuel-derived propylene). Is 100% by weight), including
[10] The method for producing a propylene-based polymer according to [10].

[12] The propylene-based polymer is a propylene / ethylene block copolymer.
The propylene / ethylene block copolymer
It comprises a propylene homopolymer or a crystalline propylene / ethylene random copolymer containing 95% by weight or more and less than 100% by weight of a structural unit derived from propylene and 5% by weight or less of a structural unit derived from ethylene, as described in (v) below.
(V) The ultimate viscosity [η] is 0.8 (dl / g) or more and 3.0 (dl / g).
Crystalline propylene-based polymer component (c) 55% by weight or more and 95% by weight, which satisfies the above conditions.
Containing 20% by weight or more and 80% by weight or less of the structural unit derived from propylene and 20% by weight or more and 80% by weight of the structural unit derived from ethylene, the following (vi)
(Vi) The ultimate viscosity [η] is 1.0 (dl / g) or more and 10.0 (dl / g).
Contains 5% by weight or more and 45% by weight or less of the propylene / ethylene random copolymer component (d) satisfying the above conditions.
A raw material (1) containing propylene or propylene and ethylene is supplied to a polymerizer and polymerized by a polymerization catalyst.
A crystalline propylene-based polymer comprising a propylene homopolymer or a crystalline propylene / ethylene random copolymer containing 95% by weight or more and less than 100% by weight of a structural unit derived from propylene and 5% by weight or less of a structural unit derived from ethylene. The step (α) for producing the component (c) and the raw material (2) containing propylene and ethylene are supplied to the polymer and polymerized by a polymerization catalyst to prepare the propylene / ethylene random copolymer component (d). The method for producing a propylene-based polymer according to [8], which comprises the step (β).

[13] Propylene contained in the raw materials (1) and (2) supplied to the polymer is 0.2% by weight or more and 99% by weight or less of biomass-derived propylene and 1% by weight or more and 99.8% by weight of fossil fuel-derived propylene. The method for producing a propylene-based polymer according to [12], which is a propylene mixture containing the following (the total of propylene derived from biomass and propylene derived from fossil fuel is 100% by weight).

[14] A resin composition containing the propylene homopolymer according to [2] or [3].

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

[16] A resin composition containing the propylene / ethylene block copolymer according to [6] or [7].

[17] A molded product made of the propylene homopolymer according to [2] or [3].

[18] A molded product made of a random copolymer of propylene and ethylene and at least one olefin (b) selected from the group consisting of α-olefins having 4 to 8 carbon atoms according to [4] or [5]. ..

[19] A molded product made of the propylene / ethylene block copolymer according to [6] or [7].

[20] A molded product made of the resin composition according to any one of [14] to [16].

According to the propylene-based polymer of the present invention and the method for producing the polymer, the environmental load (greenhouse gas generation) in the life cycle can be reduced, and the amount of biomass-derived olefin in the propylene-based polymer can be adjusted. No additional equipment or process is required to mix the propylene-based polymer derived from biomass and the propylene-based polymer derived from fossil fuel. Further, according to the propylene-based polymer of the present invention and the method for producing the polymer, a propylene-based polymer having a desired biomass-derived carbon concentration and having the same performance can be produced, and the market needs and the like are taken into consideration. It is possible to promote the spread of such a propylene-based polymer at a low cost.

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

[Fossil fuel-derived olefin]
Fossil fuel refers to fossil fuel-derived olefins such as oil, coal, natural gas, and shale gas, which are fossilized by volume and pressurization of dead animals and plants over hundreds of millions of years. Ethylene, α-olefin, etc.) are olefins obtained from this fossil fuel. ¹⁴ C is not detected in fossil-derived carbon because it is sufficiently longer than the half-life of the ¹⁴ C isotope, 5,730 years.

[Propene-based polymer (A)]
The propylene-based polymer (A) of the present invention mainly contains a structural unit derived from propylene (typically, the structural unit derived from propylene is contained in an amount of more than 50% by weight, preferably 60% by weight). It is a polymer (including more than). The propylene-based polymer (A) is typically at least one olefin (b) selected from the group consisting of a propylene homopolymer (A1), or a group consisting of propylene, ethylene, and an α-olefin having 4 to 8 carbon atoms. ) (Hereinafter, at least one olefin selected from the group consisting of ethylene and α-olefin having 4 to 8 carbon atoms is also simply referred to as olefin (b)) (hereinafter, propylene-based co-polymer). It is also referred to as a polymer (A2)) and the like.

Examples of the propylene-based copolymer (A2) include a random copolymer (A2-1) of propylene and an olefin (b) (for example, a propylene / ethylene random copolymer and a propylene / α-olefin (4 to 8 carbon atoms). ) Random copolymer, propylene / ethylene / α-olefin (4 to 8 carbon atoms) random copolymer, etc.) (hereinafter, random copolymer (A2-1) of propylene and olefin (b)) Also referred to simply as a propylene-based random copolymer (A2-1)), a propylene homopolymer or a structural unit derived from propylene of 95% by weight or more and less than 100% by weight and a structural unit derived from ethylene of 5% by weight or less. A crystalline propylene-based polymer component (c) composed of a crystalline propylene / ethylene random copolymer, a structural unit derived from propylene of 20% by weight or more and 80% by weight or less, and a structural unit derived from ethylene of 20% by weight or more and 80% by weight or more. Examples thereof include a propylene / ethylene block copolymer (A2-2) containing a propylene / ethylene random copolymer component (d) containing%.

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

(Requirement (I))
The propylene-based polymer (A) of the present invention satisfies the following requirement (I).
Requirement (I): At least one olefin (a) selected from the group consisting of propylene, ethylene, and an α-olefin having 4 to 8 carbon atoms contained in the raw material of the propylene-based polymer (A) (hereinafter, propylene). , Ethylene, and at least one olefin selected from the group consisting of α-olefins having 4 to 8 carbon atoms are also simply referred to as olefin (a)), and the biomass-derived olefin (a1) is 0.2% by weight or more 99. An olefin mixture containing 1% by weight or less of the fossil fuel-derived olefin (a2) and 1% by weight or more and 99.8% by weight or less of the fossil fuel-derived olefin, preferably 1% by weight or more and 95% by weight or less of the biomass-derived olefin (a1). (A2) An olefin mixture containing 5% by weight or more and 99% by weight or less, more preferably 5% by weight or more and 90% by weight or less of the biomass-derived olefin (a1) and 10% by weight or more and 95% by weight of the fossil fuel-derived olefin (a2). % Or less, more preferably an olefin mixture containing 10% by weight or more and 69% by weight or less of the biomass-derived olefin (a1) and 31% by weight or more and 90% by weight or less of the fossil fuel-derived olefin (a2). , Meet. Here, the total of the biomass-derived olefin (a1) and the fossil fuel-derived olefin (a2) is 100% by weight. The biomass-derived olefin (a1) means a biomass-derived olefin contained in the olefin (a), and the fossil fuel-derived olefin (a2) means a fossil fuel-derived olefin contained in the olefin (a).

In order to set the ratio (% by weight) of the biomass-derived olefin (a1) contained in the olefin (a) to the fossil fuel-derived olefin (a2) to a desired ratio, for example, the separately obtained biomass-derived olefin (a1) can be used. And the fossil fuel-derived olefin (a2) may be mixed in a desired ratio (% by weight).

Further, the at least one kind of olefin (a) contained in the raw material is, for example, when the propylene-based polymer (A) is a propylene homopolymer (A1), the raw material propylene is the above requirement (I). When the propylene-based polymer (A) is the propylene-based copolymer (A2), the propylene and the olefin (b) contained as the raw materials of the propylene-based copolymer (A2) are satisfied. (For example, in the case of a propylene / ethylene / α-olefin (4 to 8 carbon atoms) random copolymer, it is composed of propylene, ethylene, and α-olefin (4 to 8 carbon atoms) as raw materials. It means that one or more kinds of olefins (propylene only, ethylene only, both propylene and ethylene, etc.) selected from the group satisfy the above requirement (I).

Since the production cost of the biomass-derived olefin is higher than the production cost of the fossil fuel-derived olefin, a raw material in which the ratio of the biomass-derived olefin (a1) and the fossil fuel-derived olefin (a2) in the olefin mixture satisfies the above range is used. The propylene-based polymer produced in the above can contribute to the reduction of the environmental load in the life cycle and promote the spread of the propylene-based polymer at a low cost.

Requirement (I-1): Propylene is contained as the olefin (a) contained in the raw material of the propylene-based polymer (A) because it is easier to reduce the environmental load and reduce the cost (requirement (I)). ) Shall be a propylene mixture of biomass-derived propylene and fossil fuel-derived propylene in a specified amount ratio). When the propylene-based polymer (A) is the propylene-based copolymer (A2), the olefin species contained in the raw materials other than the type corresponding to the olefin (a) is a fossil fuel even if only the biomass-derived olefin is used. Only the derived olefin may be used. For example, when it is desired to emphasize the improvement of the degree of biomass of the propylene-based polymer (A), it is desirable that the only olefin species other than the type corresponding to the olefin (a) is the biomass-derived olefin. Further, for example, if cost control is emphasized, it is desirable that the olefin species other than the species corresponding to the olefin (a) are only fossil fuel-derived olefins. Further, the olefin corresponding to the olefin (a) can be selected in consideration of the ease of producing the olefin used as the raw material of the propylene-based polymer (A).

The biomass-derived olefin and fossil fuel-derived olefin of the same olefin species have polymerization performance (activity, copolymerizability, stereoregularity, stereoregularity distribution, molecular weight, molecular weight, etc.) under the same polymerization conditions (polymerization catalyst, polymerization temperature, etc.). It is said that there is no significant difference in distribution, etc.).

(Requirement (II))
The propylene-based polymer (A) of the present invention further satisfies the following requirement (II).
The biomass-derived carbon concentration of the propylene-based polymer (A) is 0.2 pMC (%) or more and 99.0 pMC (%) or less, preferably 1.0 pMC (%) or more and 95.0 pMC (%), more preferably. It is 5.0 pMC (%) or more and 90.0 pMC (%) or less, more preferably 10.0 pMC (%) or more and 69.0 pMC (%) or less. The propylene-based polymer (A) whose biomass-derived carbon concentration satisfies this range can promote the spread of the propylene-based polymer at a low cost while contributing to the reduction of the environmental load in the life cycle. In addition, any of the propylene homopolymer (A1), the propylene-based copolymer (A2), the propylene-based random copolymer (A2-1), and the propylene-based block copolymer (A2-2), which will be described later, is also used. It is necessary to meet the requirement (II).

[Measuring method of carbon concentration derived from biomass]
The carbon concentration derived from biomass was taken as the value of pMC (percent Modern Carbon) measured according to ASTM D 6866-21.
pMC refers to the ratio of the 14C concentration of the sample carbon to the standard modern carbon, and is usually a value rounded off to two decimal places.

The principle for determining the biomass-derived carbon concentration from the ¹⁴ C abundance ratio in carbon is, for example, "Evaluation of Biomass Derivativeness of Biomass Plastic by Carbon-14 Measurement Using AMS", Thermal Measurement, 39 (4), 2012. , It is described as follows.

Carbon dioxide in the atmosphere contains carbon-14 in a certain ratio, and this ratio is maintained even when the plant immobilizes carbon dioxide. Carbon-14 is a radioactive isotope with a half-life of 5,730 years, and it decays and decreases at a constant rate. Utilizing this, it is a method of estimating the number of years since the plant immobilized carbon dioxide by measuring the concentration (ratio) of carbon-14. Oil is believed to have been stored underground for a long period of more than one million years. Therefore, even if petroleum is of biological origin, all carbon-14 is destroyed and not contained. On the other hand, plants contain a certain percentage of carbon-14. Whether it is derived from fossil fuels or biomass can be distinguished by whether or not it contains carbon-14. Furthermore, even when biomass raw materials and petroleum raw materials are mixed, it is possible to identify the ratio by measuring the carbon-14 concentration using the dating method and comparing it with the current ratio of carbon-14 in plants. Become. This is the principle of the method for measuring biomass origin by measuring the carbon-14 concentration.

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

[Propene homopolymer (A1)]
The propylene homopolymer (A1) of the present invention is a polymer containing only structural units derived from propylene, and contains only propylene as the olefin which is the raw material of the propylene homopolymer (A1). Therefore, the only olefin (a) that should satisfy the above requirement (I) is propylene, and the raw material propylene may satisfy the above requirement (I) (for example, the propylene contained in the raw material is biomass-derived propylene). It is a propylene mixture containing 0.2% by weight or more and 99% by weight or less and 1% by weight or more and 99.8% by weight or less of fossil fuel-derived propylene (the total of biomass-derived propylene and fossil fuel-derived propylene is 100% by weight). Hereinafter, the same applies to the preferred embodiment of each component weight% described in the description regarding the propylene-based polymer (A).) Since the production cost of biomass-derived propylene is higher than the production cost of fossil fuel-derived propylene, if raw materials that meet this range are used, propylene homopolymers that contribute to reducing the environmental burden and reduce costs will be popularized. Can be promoted.

Since the ratio of the biomass-derived propylene as a raw material to the fossil fuel-derived propylene is prepared for the propylene homopolymer (A1) of the present invention, the biomass-derived carbon concentration of the molding material obtained from the propylene homopolymer is prepared. In addition, there is no need for equipment or steps to dilute the biomass-derived propylene homopolymer obtained only from biomass-derived propylene with the fossil fuel-derived propylene homopolymer obtained only from fossil fuel-derived propylene, and to melt and knead it. Contributes to reducing the environmental load.

The propylene homopolymer (A1) of the present invention preferably satisfies any of the following (i) to (ii), and more preferably satisfies 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 / g. It is less than 10 minutes. When the melt flow rate (MFR) is within this range, the moldability and the performance of the molded product when processing 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, the performance of various molded products is excellent. The isotactic pentad fraction is determined from the ¹³ C-NMR measurement of the polymer.

In the propylene homopolymer (A1) of the present invention, the biomass degree according to ASTM D 6866 is preferably 1% or more and 99% or less, more preferably 1% or more and 95% or less, and further preferably 5% or more and 90% or less. Most preferably, it is 10% or more and 69% or less.

[Measuring method of biomass degree (biobased carbon content)]
According to ASTM D 6866-21, δ ¹³ C (measured the ¹³ C concentration of sample carbon ( ¹³ C / ¹² C) and corrected the deviation from the reference sample by a thousandth deviation (‰)). It was calculated using the pMC obtained. The atmospheric correction factor used was the value for 2019-2021 described in ASTM D6866-21 (latest version) (100.0 pMC).

The propylene homopolymer (A1) of the present invention may have a specific molecular weight distribution, may have a specific amount of residue such as a catalyst, and may be irradiated with an electron beam even if the low crystal component is a specific amount. May be given. For example, International Publication No. 2020/189676, JP-A-2020-090621, JP-A-2019-167499, JP-A-2019-137847, JP-A-2019-137748, International Publication No. 2016/159069, JP-A-2005- 171169, Japanese Patent Laid-Open No. 2014-181317, Japanese Patent Laid-Open No. 2002-31017, Japanese Patent Laid-Open No. 2007-119760, International Publication No. 2005/097842, Japanese Patent Laid-Open No. 2000-44630, JP-A-11-349635, JP-A-11- 100412, JP-A-8-85711, JP-A-8-73529, JP-A-2014-231604, International Publication No. 2008/088022, JP-A-2006-328300, JP-A-2011-26620, JP-A-10- At least a part of the propylene homopolymer described in Japanese Patent Laid-Open No. 17610, JP-A-6-236709, International Publication No. 1997/045563, etc. is the propylene homopolymer of the present invention so as to have the characteristics described in the above-mentioned publication. After preparing (A1), it can be used in place of the propylene homopolymer (A1).

The stereoregularity of the propylene homopolymer (A1) of the present invention is not particularly limited, and may be, for example, a propylene homopolymer having an isotactic pentad fraction of less than 90.0%, and has a syndiotactic structure. It may be a propylene homopolymer having an atactic structure, or it may be a propylene homopolymer having an atactic structure.

[Propene-based random copolymer (A2-1)]
The propylene-based random copolymer (A2-1) of the present invention is a copolymer obtained by random copolymerizing propylene and olefin (b).
In the propylene-based random copolymer (A2-1), the structural unit derived from propylene is preferably 90.0% by weight or more and 99.9% by weight or less, more preferably 92.0% by weight or more and 99.0% by weight. The constituent units derived from the olefin (b) are preferably 0.1% by weight or more and 10.0% by weight or less, and 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-based random copolymer (A2-1) includes ethylene, 1-butene, and 1- from the viewpoints of ease of polymerization and mechanical strength of the obtained copolymer. Hexene is preferred.

The propylene-based random copolymer (A2-1) also needs to satisfy the above requirement (I). Since the production cost of the biomass-derived olefin is higher than the production cost of the fossil fuel-derived olefin, the propylene-based random copolymer (A2-1) produced using the raw material satisfying the above requirement (I) has an environmental load. It is possible to promote the spread of random copolymers of propylene and olefin (b) at a low cost while contributing to the reduction.

Further, the propylene-based random copolymer (A2-1) also satisfies the above requirement (I-1), that is, propylene as a raw material is contained in the olefin (a), and the propylene is the requirement (I). Is a preferable form.

In the propylene-based random copolymer (A2-1), the olefin (b) as a raw material thereof is required (I-2): as the olefin (a) contained in the raw material of the propylene-based random copolymer (A2-1). At least one olefin (b) is contained (at least one olefin of the olefin (b) is an olefin mixture of a biomass-derived olefin and a fossil fuel-derived olefin in the amount ratio specified in the requirement (I). That), it is preferable to satisfy.

When the propylene-based random copolymer (A2-1) contains a structural unit derived from ethylene, the production cost of ethylene derived from biomass is higher than the production cost of ethylene derived from fossil fuel. Ethylene, which is a raw material, is contained in olefin (a) from the viewpoint of further promoting the spread of propylene-based random copolymer (A2-1), which contributes to the reduction of environmental load and keeps costs down. Satisfies the requirement (I) (for example, ethylene contained in the raw material contains 0.2% by weight or more and 99% by weight or less of ethylene derived from biomass and 1% by weight or more and 99.8% by weight or less of ethylene derived from fossil fuel. It is an ethylene mixture (the total of ethylene derived from biomass and ethylene derived from fossil fuel is 100% by weight). The same applies to the preferred embodiment of each component weight% described in the description of the propylene-based polymer (A) below). This is a preferred form.

When the propylene-based random copolymer (A2-1) contains a structural unit derived from an α-olefin having 4 to 8 carbon atoms, the propylene-based random copolymer contributes to the reduction of the environmental load and suppresses the cost. From the viewpoint of further promoting the spread of the copolymer (A2-1), an α-olefin having 4 to 8 carbon atoms as a raw material is contained in the olefin (a), and the α-olefin having 4 to 8 carbon atoms thereof is contained in the olefin (a). Is a preferable form in which is satisfied with the requirement (I).

All of the olefins that are the raw materials of the propylene-based random copolymer (A2-1) from the viewpoint of further promoting the spread of the propylene-based random copolymer (A2-1) that contributes to the reduction of the environmental load and suppresses the cost. It is also a preferable form that the olefin species of No. 1 satisfies the above requirement (I).

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

(Iv) The melting point is 100 ° C. or higher and 160 ° C. or lower, preferably 115 ° C. or higher and 155 ° C. or lower. When the melting point is within this range, transparency, sealing property, and flexibility are excellent. The melting point is a value measured using a differential scanning calorimeter in accordance with JIS-K7121.

In the propylene-based random copolymer (A2-1) of the present invention, the biomass degree according to ASTM D 6866 is preferably 1% or more and 99% or less, more preferably 1% or more and 95% or less, and further preferably 5%. 90% or more, most preferably 10% or more and 69% or less.

As in the present invention, the same type of olefin contained in the raw material of the propylene-based random copolymer (A2-1) is formed into an olefin mixture of a biomass-derived olefin and a fossil fuel-derived olefin to form a propylene-based random copolymer (A2-1). It is easy to set the physical properties (crystallization degree, melting point, etc.) of A2-1) to the desired physical properties, and to set the polymer-derived carbon concentration or the biomass degree to the desired values. On the other hand, when one kind of olefin contained in the raw material is only a biomass-derived olefin and another one kind of olefin is only a fossil fuel-derived olefin, for example, propylene is only biomass-derived propylene, and 1-hexene is In the case of only fossil fuel-derived 1-hexene, in order to obtain the desired value of the biomass-derived carbon concentration or the degree of biomass in the propylene / 1-hexene random copolymer produced from such raw materials, it is necessary to use propylene in the raw materials. It is necessary to change the ratio with 1-hexene, which changes the crystallinity, melting point, etc. of the propylene random copolymer, which may make it impossible to produce a propylene / 1-hexene random copolymer having desired physical properties. There is. Further, in order to adjust the biomass-derived carbon concentration of the molding material obtained from the propylene-based random copolymer, the biomass-derived propylene-based random copolymer obtained only from the biomass-derived olefin is used as a fossil fuel obtained only from the fossil fuel-derived olefin. There is no need for equipment or steps to dilute, melt and knead with the derived propylene-based random biomass, which also contributes to reducing the environmental load.

The propylene-based random copolymer (A2-1) may have a specific molecular weight distribution, a specific amount of the low crystal component may be used, or electron beam irradiation may be applied. For example, JP-A-4-202409, JP-A-6-239935, JP-A-9-272718, JP-A-10-130336, JP-A-11-021318, JP-A-11-106433, JP-A-11-349635. , International Publication No. 99/001486, JP-A-2000-178320, JP-A-2001-058380, International Publication No. 2000/204733, JP-A-2002-275330, JP-A-2002-363308, JP-A-2006-52314 The propylene-based random copolymer (A2-1) of the present invention is obtained so that at least a part of the propylene-based random copolymer described in Japanese Patent Laid-Open No. 2006-57010 has the characteristics described in the above-mentioned publication. Can be used in place of the propylene-based random copolymer (A2-1).

[Propene / Ethylene Block Copolymer (A2-2)]
The propylene / ethylene block copolymer (A2-2) of the present invention contains 95% by weight or more and less than 100% by weight of the structural unit derived from the propylene homopolymer or propylene and 5% by weight or less of the structural unit derived from ethylene. A crystalline propylene-based polymer component (c) composed of a crystalline propylene / ethylene random copolymer, a structural unit derived from propylene of 20% by weight or more and 80% by weight or less, and a structural unit derived from ethylene of 20% by weight or more and 80% by weight or more. It is a copolymer containing a propylene / ethylene random copolymer component (d) containing%.

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

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

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

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

Also in the propylene / ethylene block copolymer (A2-2), at least one olefin selected from the group consisting of propylene and ethylene as the olefin (a) needs to satisfy the above requirement (I). Since the production cost of biomass-derived olefins is higher than the production cost of fossil fuel-derived olefins, the propylene / ethylene block copolymer (A2-2) produced using the raw material satisfying the above requirement (I) is an environment. It is possible to promote the spread of propylene / ethylene block copolymers at low cost while contributing to load reduction.

Further, the propylene / ethylene block copolymer (A2-2) also satisfies the above requirement (I-1), that is, propylene as a raw material is contained in the olefin (a), and the propylene is the requirement (I). ) (For example, the propylene contained in the raw material is a propylene mixture containing 0.2% by weight or more and 99% by weight or less of propylene derived from biomass and 1% by weight or more and 99.8% by weight or less of propylene derived from fossil fuel. (The total of propylene derived from biomass and propylene derived from fossil fuel is 100% by weight.) Hereinafter, the same applies to the preferred embodiment of each component weight% described in the description of the propylene-based polymer (A)). be.

In the propylene / ethylene block copolymer (A2-2), the production cost of biomass-derived ethylene is higher than the production cost of fossil fuel-derived ethylene, and the cost is suppressed while contributing to the reduction of environmental load. From the viewpoint of further promoting the spread of the propylene / ethylene block copolymer (A2-2), ethylene as a raw material is contained in the olefin (a), and the ethylene satisfies the requirement (I) (for example). , Ethylene contained in the raw material is an ethylene mixture containing 0.2% by weight or more and 99% by weight or less of ethylene derived from biomass and 1% by weight or more and 99.8% by weight or less of ethylene derived from fossil fuel (derived from biomass-derived ethylene and fossil fuel). The total amount of ethylene is 100% by weight). Hereinafter, the same applies to the preferred embodiment of each component weight% described in the description regarding the propylene-based polymer (A)), which is a preferable form.

Further, it is also a preferable form that both ethylene and propylene as raw materials are contained in the olefin (a), and both ethylene and propylene satisfy the requirement (I).

In the present invention, the same type of olefin contained in the raw material of the propylene / ethylene block copolymer (A2-2) is used as an olefin mixture of a biomass-derived olefin and a fossil fuel-derived olefin, and the resulting propylene / ethylene block can be used together. The biomass-derived carbon concentration or the degree of biomass of the polymer can be a desired value. On the other hand, if it is desired to use a biomass-derived propylene / ethylene block copolymer produced from biomass-derived propylene and an ethylene-only raw material as a material having a desired value in biomass-derived carbon concentration or biomass degree, for example, it is derived from fossil fuel. Since it is diluted with a fossil fuel-derived propylene / ethylene block copolymer produced from raw materials of propylene and ethylene only, equipment and processes for performing melt kneading are required. From this point as well, the propylene / ethylene block copolymer (A2-2) of the present invention contributes to the reduction of environmental load.

In the propylene / ethylene block copolymer (A2-2) of the present invention, the biomass degree according to ASTM D 6866 is preferably 1% or more and 99% or less, more preferably 1% or more and 95% or less, still more preferable. The biomass degree is 5% or more and 90% or less, and most preferably the biomass degree is 10% or more and 69% or less.

As in the present invention, the same type of olefin contained in the raw material of the propylene / ethylene block copolymer (A2-2) is made into an olefin mixture of a biomass-derived olefin and a fossil fuel-derived olefin, whereby the propylene / ethylene block common weight is obtained. It is easy to set the physical properties (crystallization degree, glass transition temperature, etc.) of the coalescence (A2-2) to the desired physical properties, and to set the biomass-derived carbon concentration or the biomass degree to the desired values. On the other hand, when one kind of olefin contained in the raw material is only biomass-derived olefin and another one kind of olefin is only fossil fuel-derived olefin, for example, propylene is only biomass-derived propylene and ethylene is fossil fuel. In the case of only derived ethylene, the ratio of propylene to ethylene in the raw material is changed in order to obtain the desired value of the carbon concentration or the degree of biomass derived from the biomass in the propylene / ethylene block copolymer produced from the raw material. Then, the degree of crystallization of the crystalline propylene-based polymer component (c), the propylene / ethylene random copolymer component (d), the glass transition temperature, etc. will change, and propylene having desired physical properties. Ethylene block copolymer may not be produced. Further, in order to prepare the biomass-derived carbon concentration of the molding material obtained from the propylene / ethylene block copolymer, the biomass-derived propylene / ethylene block copolymer obtained only from the biomass-derived olefin can be obtained only from the fossil fuel-derived olefin. There is no need for equipment or processes for diluting, melt-kneading, etc. with fossil fuel-derived propylene / ethylene block copolymers, which also contributes to reducing the environmental burden.

The propylene / ethylene block copolymer (A2-2) may have a specific molecular weight distribution, the residual amount of the catalyst or the like may be a specific amount, or the low crystal component may be a specific amount. Often, the propylene / ethylene random copolymer may have a specific amount, a specific molecular weight (extreme viscosity), or a specific amount of ethylene, or may contain two or more kinds of propylene / ethylene random copolymers. You may apply electron beam irradiation. For example, JP-A-9-286881, JP-A-2001-19826, JP-A-2002-030127, JP-A-2002-30128, JP-A-2004-292683, JP-A-2005-298706, JP-A-2006-28449. , JP-A-2006-124452, JP-A-2006-124453, JP-A-2006-152111, JP-A-2006-8983, International Publication No. 2006/068308, International Publication No. 2007/116709, JP-A-2009-84305 No., International Publication No. 2010/032793, JP-A-2011-190408, JP-A-8-217823, JP-A-10-182764, JP-A-10-330430, International Publication No. 1999/065965, JP-A-2001- At least a part of the propylene / ethylene block copolymer described in JP-A-233923, JP-A-2005-120388, JP-A-2015-178568, etc. After preparing an ethylene block copolymer (A2-2), it can be used in place of the propylene / ethylene block copolymer (A2-2).

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

The propylene-based polymer (A) of the present invention preferably supplies a raw material containing propylene (the raw material contains an olefin (a) satisfying the above requirement (I)) to a polymer, and the raw material is used as a polymerization catalyst. It can be produced by a production method including a step of polymerization.

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

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

Examples of the method for producing biomass-derived propylene include the method described in International Publication No. 2007/05/5361 for producing ethanol obtained from biomass as a raw material, and International Publication No. 2008/06627 for producing a residue of agricultural natural raw materials as a raw material. The method according to International Publication No. 2016/184893, which is produced from any biorenewable source, including, for example, plants or animals, including fungi, yeasts, algae and bacteria, biorenewable. Examples thereof include the method described in International Publication No. 2016/184894, which manufactures raw materials by thermal cracking.

As a method for producing biomass-derived ethylene, for example, the method described in International Publication No. 2007-055361 for producing biomass-derived ethanol as a raw material, or International Publication No. 2008/06279, using a residue of a renewable natural raw material as a raw material. The method according to International Publication No. 2008/67627, which is produced from ethanol produced by fermentation of saccharides obtained by extraction and processing of plant-derived raw materials, and the method according to International Publication No. 2009/070858, which is biorenewable. Examples thereof include the method described in International Publication No. 2016/184893 or International Publication No. 2016/184894, which is produced by thermally cracking raw materials for supply.

Examples of the method for producing biomass-derived 1-butene include the method described in International Publication No. 2008/06627, which produces a residue of agricultural natural raw materials as a raw material, and the method produced by fermentation of saccharides obtained by extraction and processing of plant-derived raw materials. Examples thereof include the method described in International Publication No. 2009/070858 for producing from the above-mentioned ethanol. As a method for producing 1-butene derived from biomass, for example, in the method described in JP-A-58-146518 and International Publication No. 1989/000553, 1-butene is used as the raw material ethylene using ethylene derived from biomass. The method of manufacturing is mentioned.

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

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

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

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

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

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

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

When the olefin (a) is propylene (a propylene mixture of biomass-derived propylene and fossil fuel-derived propylene) and ethylene (an ethylene mixture of biomass-derived ethylene and fossil fuel-derived ethylene), a light naphtha derived from fossil fuel and, for example, Naphtha obtained from any biorenewable source, including the fungi, yeasts, algae and bacteria described in WO 2016/184893, eg plants or animals, is mixed in the desired specific proportions. , This mixture can be prepared by putting it into a thermal decomposition furnace and taking it out as ethylene and propylene from a decomposition gas distiller. The naphtha decomposition device including a pyrolysis furnace and a decomposition gas fractionation device in a series is a device called "ethylene cracker" in the petrochemical industry.

Further, the olefin (a) is an α-olefin having 4 to 8 carbon atoms (an α-olefin mixture of a biomass-derived α-olefin having 4 to 8 carbon atoms and an α-olefinene derived from a fossil fuel having 4 to 8 carbon atoms). In this case, the propylene mixture of biomass-derived propylene and fossil fuel-derived propylene or the ethylene mixture of biomass-derived ethylene and fossil fuel-derived ethylene obtained as described above can be used as a raw material and produced by a known method or a method according to a known method. ..

In the method for producing the propylene-based polymer (A) of the present invention, the raw material containing propylene introduced into the polymerizer is polymerized, and the polymerization is carried out by a bulk polymerization method, a solution polymerization method, a suspension (slurry) polymerization method or the like. It may be carried out by a liquid phase polymerization method or a vapor phase polymerization method. Further, such polymerization may be carried out by combining a plurality of these polymerization methods.

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

In the method for producing the propylene-based polymer (A) of the present invention, the raw material containing propylene introduced into the polymerizer is polymerized using a polymerization catalyst. As the polymerization catalyst, a polymerization catalyst usually used for the polymerization of olefins containing propylene can be used. Examples of such a polymerization catalyst include a Ziegler-Natta catalyst composed of a titanium catalyst component and an organoaluminum compound, a metallocene catalyst, and the like.

The Ziegler-Natta catalyst is usually 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 polymer having high stereoregularity. A catalyst consisting of (external electron donor) is used. As the Ziegler-Natta catalyst, for example, a magnesium chloride-supported solid titanium catalyst containing carboxylic acid esters as an internal donor, an organoaluminum compound, and an olefin polymerization catalyst composed of an organosilicon compound as an external donor are used. (For example, the catalyst for olefin polymerization described in JP-A-08-003215 and JP-A-08-143620). Further, the Ziegler-Natta catalyst may be used in the form of a prepolymerization catalyst obtained by prepolymerization with a raw material olefin or the like.

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

Further, in the Ziegler-Natta catalyst, the organosilicon compound is usually used in an amount of about 0.001 mol to 10 mol, preferably 0.01 mol to 5 mol, based on 1 mol of the aluminum atom of the organoaluminum compound.

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

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

Further, if hydrogen is used during the polymerization of the raw material containing propylene, the molecular weight of the obtained propylene-based polymer (A) can be adjusted, and the polymer having a larger MFR than the case where hydrogen is not added can be obtained. can get.

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

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

According to the method for producing the propylene-based polymer (A) of the present invention, the propylene homopolymer (A1), the propylene-based random copolymer (A2-1) and the propylene / ethylene block copolymer (A2-2) described above are used. ) And the like, and various propylene-based polymers (A) such as the propylene-based copolymer (A2) can be produced.

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

Examples of the Ziegler-Natta catalyst used in the method for producing the propylene-based polymer (A) of the present invention include JP-A-8-034814, JP-A-8-034813, JP-A-9-048814, and JP-A-9-. 048813, JP-A-9-104709, JP-A-8-231630, JP-A-9-328513, JP-A-9-278819, JP-A-9-208615, JP-A-9-031119, JP-A-10-007716 No., JP-A-10-007715, JP-A-9-165414, JP-A-10-030004, JP-A-10-147611, JP-A-10-147610, JP-A-10-158317, JP-A-10-265519. , JP-A-10-060041, JP-A-11-012322, JP-A-11-03562, JP-A-10-316713, JP-A-11-305618, JP-A-11-035622, JP-A-10-287710, JP-A-11-106421, JP-A-11-147907, JP-A-11-158210, JP-A-11-217407, JP-A-11-222504, JP-A-11-302314, JP-A-11-322828, Kaihei 11-116615, JP-A-2000-026521, JP-A-2000-026522, JP-A-2000-044620, JP-A-2000-344818, JP-A-2001-106718, JP-A-2002-09723, JP-A. 2003-026719, JP-A-2003-192718, JP-A-2004-002742, JP-A-2005-112920, JP-A-2005-187550, JP-A-2005-213637, JP-A-2005-126703, JP-A-2006 -199975, JP-A-2014-051669, JP-A-2013-227582, JP-A-2012-233195, JP-A-2008-024751, JP-A-2010-11755, JP-A-2013-249445, JP-A-2010- The polymerization catalyst (catalyst component) according to 248469, International Publication No. 2006/079946, International Publication No. 2006/077944, International Publication No. 2008/010459, International Publication No. 2009/057747, International Publication No. 2009/069483. , Electron donor, etc.).

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

[Method for producing propylene homopolymer (A1)]
The propylene homopolymer (A1) is, for example, propylene as a raw material (propylene satisfying the above condition (I)) according to the description of the above-mentioned method for producing the propylene-based polymer (A) (polymerization conditions such as a polymerization catalyst). It can be produced by supplying a mixture) to a polymerizer and polymerizing this raw material with a polymerization catalyst.

As described above, the propylene homopolymer (A1) contains only propylene as a raw material olefin thereof. Therefore, the only olefin (a) that should satisfy the above requirement (I) is propylene, and the raw material propylene may satisfy the above requirement (I) (for example, the propylene contained in the raw material is biomass-derived propylene). It is a propylene mixture containing 0.2% by weight or more and 99% by weight or less and 1% by weight or more and 99.8% by weight or less of fossil fuel-derived propylene (the total of biomass-derived propylene and fossil fuel-derived propylene is 100% by weight). Hereinafter, the same applies to the preferred embodiment of each component weight% described in the description regarding the propylene-based polymer (A).)

In the propylene homopolymer (A1), it is desirable to satisfy the above-mentioned (i) that the MFR is in a specific range. In order to bring the MFR within this specific range, for example, the ratio of propylene to hydrogen supplied to the polymer may be adjusted appropriately (the higher the hydrogen concentration with respect to propylene, the generally the melt flow rate (MFR)). Will grow.).

In the propylene homopolymer (A1), it is desirable to satisfy the above-mentioned (ii) that the isotactic pentad fraction is in 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 condition of the propylene homopolymer (A1), the same conditions as the above-mentioned polymerization condition of the propylene-based polymer (A) can be adopted. Further, as the polymerization condition, a known or known polymerization condition of the propylene-based polymer may be adopted.
For example, the polymerization of propylene introduced into the polymerizer may be carried out by a liquid phase polymerization method such as a bulk polymerization method, a solution polymerization method, or a suspension (slurry) polymerization method, or may be carried out by a vapor phase polymerization method. good. Further, such polymerization may be carried out by combining a plurality of these polymerization methods.

In addition, such polymerization is a batch polymerization in which the propylene concentration supplied to the polymerizer and the hydrogen concentration added as needed are discontinuously changed by one polymerizer; two or more polymerizers are connected in parallel by piping. Polymerization conditions (temperature, pressure, propylene concentration, concentration of hydrogen added as needed, catalyst / catalyst supply amount to be used, type / supply amount of external electron donor, organic aluminum compound Semi-batch polymerization in which the type / supply amount of the polymer, the ratio of the polymer volume to the volume of the liquid substance, etc.) are arbitrarily set; Temperature, pressure, propylene concentration, hydrogen concentration, type / supply amount of external electron donor, type / supply amount of organic aluminum compound, ratio of polymerizer volume to liquid substance volume, etc.) can be set arbitrarily and 1 Either the catalyst to be supplied to the second polymerizer or the continuous polymerization in which the amount of the catalyst supplied per hour is arbitrarily set; may be selected.

Further, in the method for producing the propylene homopolymer (A1), for example, JP-A-63-069809, JP-A-11-12310, JP-A-11-12308, JP-A-2001-48913, JP-A-2004-1759776. No., JP-A-2004-175933, JP-A-2020-090621 can be used for the polymerization method.

[Method for producing propylene-based random copolymer (A2-1)]
The propylene-based random copolymer (A2-1) contains propylene and an olefin (b), for example, according to the above-mentioned description of the method for producing the propylene-based polymer (A) (polymerization conditions such as a polymerization catalyst). The raw material (raw material satisfying the above condition (I)) is supplied to the polymer, and the raw material is supplied.
This raw material can be produced by random copolymerization with a polymerization catalyst.

For the description of the preferred embodiment of the raw material (the preferred embodiment of the olefin (b), the preferred embodiment of the olefin (a) which is an olefin mixture of the biomass-derived olefin (a1) and the fossil fuel-derived olefin (a2), etc.), the propylene-based random The contents are the same as those described in the section of the copolymer (A2-1).

In the propylene-based random copolymer (A2-1), it is desirable to satisfy the above-mentioned (iii) that the MFR is in a specific range. In order to set the MFR within this specific range, for example, the ratio of hydrogen to the olefin (propylene, olefin (b)) which is a raw material to be supplied to the polymerizer may be appropriately adjusted (the hydrogen concentration with respect to propylene is high). Generally, the melt flow rate (MFR) increases.)

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

As the polymerization conditions of the propylene-based random copolymer (A2-1), the same conditions as the above-mentioned polymerization conditions of the propylene-based polymer (A) can be adopted. Further, as the polymerization condition, a known or known polymerization condition of the propylene-based polymer may be adopted.
For example, the polymerization of the raw material containing propylene introduced into the polymerizer 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 vapor phase polymerization method. You may. Further, such polymerization may be carried out by combining a plurality of these polymerization methods.

In addition, such polymerization is a batch polymerization in which the concentration of propylene and olefin (b) supplied to the polymerizer and the concentration of hydrogen added as needed are discontinuously changed by one polymerizer; two or more. Polymerizers are joined in parallel by piping, and the polymerization conditions of each polymer (temperature, pressure, concentration of propylene and olefin (b), concentration of hydrogen added as needed, amount of catalyst / catalyst supplied, external Semi-batch polymerization that arbitrarily sets the type / supply amount of electron donor, type / supply amount of organic aluminum compound, ratio of polymerizer volume to liquid substance volume, etc.; or two or more polymerizers by piping Joined in series, polymerization conditions of each polymer (temperature, pressure, concentration of propylene and olefin (b), hydrogen concentration, type / supply amount of external electron donor, type / supply amount of organic aluminum compound, polymerizer volume The ratio of the polymer to the volume of the liquid substance, etc.) may be arbitrarily set, and either the catalyst supplied to the first polymerizer or the continuous polymerization in which the amount of the catalyst supplied per hour may be arbitrarily set; may be selected.

Further, in the method for producing the propylene-based random copolymer (A2-1), for example, JP-A-63-069809, JP-A-11-12310, JP-A-11-12308, JP-A-2001-48915, and Japanese Patent Laid-Open No. The polymerization methods described in Kai 2004-175976, JP-A-2004-175933, and JP-A-2020-090621 can be adopted.

[Method for producing propylene / ethylene block copolymer (A2-2)]
The propylene / ethylene block copolymer (A2-2) is prepared, for example, according to the above-mentioned description of the method for producing the propylene-based polymer (A) (polymerization conditions such as a polymerization catalyst).
A raw material (1) containing propylene or propylene and ethylene is supplied to a polymerizer and polymerized by a polymerization catalyst.
A crystalline propylene-based polymer comprising a propylene homopolymer or a crystalline propylene / ethylene random copolymer containing 95% by weight or more and less than 100% by weight of a structural unit derived from propylene and 5% by weight or less of a structural unit derived from ethylene. The step (α) for producing the component (c) and the raw material (2) containing propylene and ethylene are supplied to the polymer and polymerized by a polymerization catalyst to prepare the propylene / ethylene random copolymer component (d). It can be manufactured by a manufacturing method including the step (β).

In the method for producing the propylene / ethylene block copolymer (A2-2), at least one olefin selected from the group consisting of propylene and ethylene contained in the raw materials (1) and (2) is required (I). ) (The biomass-derived olefin and the fossil fuel-derived olefin are a mixture of olefins in a specific quantity ratio).

For the description of the preferred embodiment of the raw material (raw materials (1) and (2)) (the preferred embodiment of the olefin (a) which is an olefin mixture of the biomass-derived olefin (a1) and the fossil fuel-derived olefin (a2), etc.), propylene. -The same as the content described in the section of ethylene block copolymer (A2-2).

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

In the step (α), the crystalline propylene-based polymer component (c) contained in the propylene / ethylene block copolymer (A2-2) is produced. It is desirable that the crystalline propylene-based polymer component (c) satisfies the above-mentioned (v) that the ultimate viscosity is in a specific range. When the crystalline propylene-based polymer component (c) is a propylene homopolymer, propylene is supplied to the polymer as a raw material for the polymer. At that time, in order for the ultimate viscosity [η] to satisfy (v), for example, the ratio of hydrogen supplied to the polymerizer to propylene may be appropriately adjusted (the ratio of hydrogen to propylene is The higher the value, the smaller the ultimate viscosity [η]). When the crystalline propylene-based polymer component (c) is a propylene / ethylene random copolymer, propylene and ethylene are supplied to the polymer as a raw material for the polymer. At that time, in order for the ultimate viscosity [η] to satisfy (v), for example, the ratio of hydrogen to propylene supplied to the polymer is appropriate as in the case of producing a propylene homopolymer. It should be adjusted to. When the crystalline propylene-based polymer component (c) is a propylene / ethylene random copolymer, the polymer is charged with a desired value of 95% by weight or more and less than 100% by weight of the structural unit derived from propylene. The ratio of the supplied propylene to ethylene may be adjusted appropriately.

Further, the step (α) for producing the crystalline propylene-based polymer component (c) may be carried out by one-step polymerization carried out in one polymerizer, but may be carried out in two steps carried out in two or more polymerizers. It may be carried out by the above-mentioned polymerization, and when it is carried out by two or more steps of polymerization, the polymerization conditions of each step may be the same or different.

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

Further, the step (β) for producing the propylene / ethylene random copolymer component (d) may be carried out by one-step polymerization carried out in one polymerizer, but may be carried out in two or more polymerizers. It may be carried out by polymerization of two or more steps, and when it is carried out by polymerization of two or more steps, the polymerization conditions of each step may be the same or different.

In order to make the amount ratio of the crystalline propylene polymer component (c) to 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 the step (α), the polymerization activity in the step (β) of polymerizing the propylene / ethylene random copolymer component (d) by appropriately adjusting the residence time of the polymerized particles in the polymerizer, and the polymerizer of the polymerized particles. The internal residence time and the like may be adjusted appropriately.

As the polymerization conditions of the propylene / ethylene block copolymer (A2-2), the same conditions as the above-mentioned polymerization conditions of the propylene-based polymer (A) can be adopted. Further, as the polymerization condition, a known or known polymerization condition of the propylene-based polymer may be adopted.
For example, the polymerization of the raw material containing propylene introduced into the polymerizer 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 vapor phase polymerization method. You may. Further, such polymerization may be carried out by combining a plurality of these polymerization methods.

In addition, such polymerization is a batch polymerization in which the concentration of propylene and ethylene supplied to the polymerizer and the concentration of hydrogen added as needed are discontinuously changed by one polymerizer; two or more polymerizers are used. Polymerization conditions (temperature, pressure, concentration of propylene and ethylene, concentration of hydrogen added as needed, catalyst / catalyst supply amount to be used, type of external electron donor ・Semi-batch polymerization in which the supply amount, type / supply amount of organic aluminum compound, ratio of polymerizer volume to liquid substance volume, etc.) are arbitrarily set; or two or more polymerizers are joined in series by piping, and each Polymerization conditions of the polymer (temperature, pressure, propylene and ethylene concentration, hydrogen concentration, type / supply amount of external electron donor, type / supply amount of organic aluminum compound, ratio of polymer volume to liquid substance volume, Etc.) may be arbitrarily set, and either the catalyst supplied to the first polymerizer or the continuous polymerization in which the amount of catalyst supplied per hour is arbitrarily set; may be selected.

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

[Resin composition]
The propylene-based polymer (A) obtained as described above in the present invention replaces a part or all of the fossil fuel-derived propylene-based polymer obtained by using only the fossil fuel-derived olefin as a raw material, and is a propylene-based polymer. Can be used as a resin composition containing. Depending on the purpose, the resin composition may further contain a biomass-derived propylene-based polymer obtained by using only a biomass-derived olefin as a raw material as the propylene-based polymer. Further, the resin composition may contain only the propylene-based polymer (A) as the propylene-based polymer, or the propylene-based polymer (A) and the fossil fuel as the propylene-based polymer. A mixture with the derived propylene-based polymer may be contained. 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, a part or all of the conventionally known propylene homopolymer is replaced with the propylene homopolymer (A1) of the present invention, and the propylene homopolymer (A1) is contained. This resin composition can be used as a resin composition.

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

The propylene homopolymer (A1) is a propylene homopolymer in which the biomass-derived carbon concentration, the degree of biomass and the like are adjusted to a desired range from the viewpoint of cost control and promotion of diffusion. Therefore, for the purpose of setting the biomass-derived carbon concentration, biomass degree, etc. of the resin composition to desired values, fossil fuel-derived propylene alone is additionally used, as in the resin composition containing the biomass-derived propylene homopolymer described above. It is not necessary to dilute with a polymer. Therefore, in the resin composition containing the propylene homopolymer (A1) of the present invention, the equipment and process can be simplified and the environmental load can be reduced.

As the resin composition containing the propylene homopolymer (A1), the resin composition containing two or more kinds of propylene homopolymers (A1) having different MFR or ultimate viscosity, and the average stereoregularity (pentad fraction) are different. A resin composition containing two or more kinds of propylene homopolymers (A1), a resin composition containing a propylene homopolymer (A1) and a propylene random copolymer, a propylene homopolymer (A1) and a propylene / ethylene block A resin composition containing a polymer, a resin composition containing a propylene homopolymer (A1) and an ethylene-based polymer, a resin composition containing a propylene homopolymer (A1) and a nucleating agent, a propylene homopolymer ( Examples thereof include a resin composition containing A1) and a filler.

Examples of the resin composition containing the propylene homopolymer (A1) include International Publication No. 2002/074855, International Publication No. 2019/00418, JP-A-2002-20560, JP-A-11-255987, JP-A-2019. -137847, JP-A-2019-137878, JP-A-2020-158787, International Publication No. 2020/091051, JP-A-2019-172730, International Publication No. 2017/195787, JP-A-2017-218509, International Publication No. 2016/15969, JP-A-2000-319463, JP-A-2000-302925, JP-A-2004-315582, JP-A-2004-2655, JP-A-1-156353, JP-A-2003-41072. In the resin composition containing a propylene homopolymer, examples of the propylene homopolymer include a resin composition using the propylene homopolymer (A1) of the present invention. The propylene homopolymer contained in these resin compositions may be only the propylene homopolymer (A1), but is a mixture of the propylene homopolymer (A1) and the propylene homopolymer derived from fossil fuel, or propylene. It may be a mixture of the homopolymer (A1) and the biomass-derived propylene homopolymer. When the above resin composition contains an ethylene-based polymer, the ethylene-based polymer may contain a biomass-derived ethylene-based polymer whose raw material is biomass-derived ethylene as an ethylene-based polymer.

[Resin composition containing a propylene-based random copolymer (A2-1)]
In a resin composition containing a propylene-based random copolymer which is a random copolymerization of propylene and an olefin (b) known conventionally, a part or all of the conventionally known propylene-based random copolymer is used in the present invention. A resin composition containing the propylene-based random copolymer (A2-1) can be prepared by replacing it with the propylene-based random copolymer (A2-1), and this resin composition can be used.

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

The propylene-based random copolymer (A2-1) is a propylene-based random copolymer in which the biomass-derived carbon concentration, the degree of biomass, etc. are adjusted to a desired range from the viewpoint of cost control, promotion of diffusion, and the like. Therefore, for the purpose of setting the biomass-derived carbon concentration, biomass degree, etc. of the resin composition to desired values, the resin composition is additionally derived from fossil fuel, as in the resin composition containing the above-mentioned biomass-derived propylene-based random copolymer. Propropylene It is not necessary to dilute with a propylene-based random copolymer. Therefore, in the resin composition containing the propylene-based random copolymer (A2-1) of the present invention, the equipment and process can be simplified and the environmental load can be reduced.

Examples of the resin composition containing the propylene-based random copolymer (A2-1) include a resin composition containing a propylene-based random copolymer (A2-1) and a propylene homopolymer, and an olefin (b) (ethylene). And at least one olefin selected from the group consisting of α-olefins having 4 to 8 carbon atoms), two or more kinds of propylene-based random copolymers (A2-1) compositions having different types and amounts, and propylene-based random co-polymers. A resin composition containing a polymer (A2-1) and a propylene / ethylene block copolymer, and a resin composition containing a propylene-based random copolymer (A2-1) and another body resin such as an ethylene-based polymer. , Propropylene-based random copolymer (A2-1) and various additives such as antioxidants, ultraviolet absorbers, lubricants, nucleating agents, antioxidants, flame retardants, pigments, dyes, inorganic or organic fillers. Examples thereof include a resin composition containing.

Examples of the resin composition containing the propylene-based random copolymer (A2-1) include JP-A-5-31017, JP-A-8-283491, JP-A-9-20846, JP-A-9-194537, and Japanese Patent Laid-Open No. 9-194537. Kaihei 10-168252, JP-A-2000-159946, JP-A-2001-172402, JP-A-2001-151960, JP-A-2002-275333, JP-A-2005-112884, JP-A-2006-036828, JP-A. In the resin composition containing the propylene-based random copolymer described in 2001-31804, International Publication No. 2015/137262, and JP-A-2019-049001, the propylene-based random copolymer of the present invention is used as the propylene-based random copolymer. Examples thereof include a resin composition using a copolymer (A2-1). The propylene-based random copolymer contained in these resin compositions may be only the propylene-based random copolymer (A2-1), but the propylene-based random copolymer (A2-1) and the fossil fuel. It may be a mixture of the derived propylene-based random copolymer or a mixture of the propylene-based random copolymer (A2-1) and the biomass-derived propylene-based random copolymer. When the above resin composition contains an ethylene-based polymer, the ethylene-based polymer may contain a biomass-derived ethylene-based polymer whose raw material is biomass-derived ethylene as the ethylene-based polymer. ..

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

When replacing a conventionally known propylene / ethylene block copolymer with a propylene / ethylene block copolymer (A2-2), the steric regularity, average molecular weight, molecular weight distribution, comonomer species, comonomer amount of the crystalline propylene polymer, The composition distribution, ethylene content of the propylene / ethylene random copolymer, molecular weight ⁽ extreme viscosity), content of each of these components in the entire block polymer, etc. If the properties of these polymers are the same, the performance of the resin composition can be the same even after the replacement. This replacement makes it possible to reduce the environmental load (reduction of greenhouse gas emissions) in the life cycle of polymer production, processing, use, and disposal.

The propylene / ethylene block copolymer (A2-2) is a propylene / ethylene block copolymer in which the biomass-derived carbon concentration, the degree of biomass and the like are adjusted to a desired range from the viewpoint of cost control and promotion of diffusion. Therefore, for the purpose of setting the biomass-derived carbon concentration, the degree of biomass, etc. of the resin composition to desired values, an additional fossil fuel is used as in the resin composition containing the above-mentioned biomass-derived propylene / ethylene block copolymer. It is not necessary to dilute with the derived propylene / ethylene block copolymer. Therefore, in the resin composition containing the propylene / ethylene block copolymer (A2-2) of the present invention, the equipment and process can be simplified and the environmental load can be reduced.

Examples of the resin composition containing the propylene / ethylene block copolymer (A2-2) include a resin composition containing a propylene / ethylene block copolymer (A2-2) and a propylene homopolymer, and a propylene / ethylene block common weight. A resin composition containing a coalescence (A2-2) and a propylene random copolymer, two or more types of propylene having different ethylene contents, molecular weight (extreme viscosity), etc. of the propylene / ethylene random copolymer in the block copolymer. A resin composition containing an ethylene block copolymer (A2-2), a resin composition containing a propylene / ethylene block copolymer (A2-2) and another resin such as an ethylene-based copolymer, a propylene / ethylene block. A resin composition containing a copolymer (A2-2) and a specific additive, a propylene / ethylene block copolymer (A2-2) and talc, glass short fibers, carbon short fibers, glass long fibers, carbon long fibers. Examples thereof include a resin composition containing a filler 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, and JP-A-9-71712. JP-A-9-165477, JP-A-2005-264032, JP-A-2005-264033, International Publication No. 2005/001276, JP-A-2008-163320, International Publication No. 2010/050509, International Publication No. 2014/073510 Issue, International 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 In the resin composition containing the propylene / ethylene block copolymer described, at least a part or all of the propylene / ethylene block copolymer was used as the propylene / ethylene block copolymer (A2-2) of the present invention. Examples include resin compositions. 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) may be used. It may be a mixture of propylene / ethylene block copolymer derived from fossil fuel, or a mixture of propylene / ethylene block copolymer (A2-2) and biomass-derived propylene / ethylene block copolymer. When the above resin composition contains an ethylene-based polymer, the ethylene-based polymer may contain a biomass-derived ethylene-based polymer whose raw material is biomass-derived ethylene as the ethylene-based polymer. ..

[Long fiber reinforced polypropylene resin]
Long fiber reinforced polypropylene resin conventionally known, for example, long fiber reinforced polypropylene described in JP-A-2005-82786, International Publication No. 2006/02809, International Publication No. 2006/043620, International Publication No. 2006/028091. In the resin (manufacturing method), a part or all of the propylene-based polymer can be replaced with the propylene-based polymer (A) of the present invention and used as a long fiber reinforced polypropylene resin. When replacing the propylene-based polymer, the ethylene content and molecular weight (extreme viscosity) of the propylene / ethylene random copolymer, such as the stereoregularity, average molecular weight, molecular weight distribution, comonomer species, comonomer amount, and composition distribution of the propylene-based polymer. If the characteristics of the polymer such as the molecular structure and the contained components other than the presence or absence of the 14C isotope, such as the content in the entire resin, are the same, the performance of the resin composition can be the same even after the replacement. This replacement makes it possible to reduce the environmental load (reduction of greenhouse gas emissions) in the life cycle of polymer production, processing, use, and disposal.

The propylene-based polymer (A) is a propylene-based polymer in which the biomass-derived carbon concentration, the degree of biomass, and the like are adjusted to a desired range from the viewpoint of cost control, promotion of diffusion, and the like. Therefore, for the purpose of setting the biomass-derived carbon concentration, biomass degree, etc. of the resin composition to desired values, an additional fossil fuel-derived propylene-based resin composition, such as the resin composition containing the biomass-derived propylene-based polymer described above, is used. It is not necessary to dilute with a copolymer. Therefore, in the resin composition containing the propylene-based polymer (A) of the present invention, the equipment and process can be simplified and the environmental load can be reduced. The propylene-based polymer contained in these resin compositions may be only the propylene-based polymer (A), but is a mixture of the propylene-based (A) and the propylene-based polymer derived from fossil fuel, or the propylene-based weight. It may be a mixture of the coalescence (A) and a propylene-based polymer derived from biomass.

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

<Additives>
The resin composition containing the propylene-based polymer (A) or the propylene-based polymer (A) of the present invention may contain an additive. Examples of such additives include stabilizers such as heat-resistant stabilizers, weather-resistant stabilizers, and light-resistant stabilizers, fillers such as chloride absorbers and inorganic fillers, α-crystal nucleating agents, β-crystal nucleating agents, and softening agents. Examples thereof 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 salt, 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, corn starch and the like. Among these inorganic fillers, talc, magnesium sulfate fiber, glass fiber, and carbon fiber are preferable. When these inorganic fillers are used as components of the resin composition containing the propylene-based 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-based stabilizers, organic phosphite-based stabilizers, thioether-based stabilizers, hindered amine-based stabilizers, higher fatty acid metal salts such as calcium stearate, and inorganic oxides.

<Surface modifier>
As the surface modifier, those known as antistatic agents are preferably used, and typical examples thereof include fatty acid amides and monoglycerides, with fatty acid amides being preferable. Specific examples of the fatty acid amide include oleic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, palmitic acid amide, myristic acid amide, lauric acid amide, capric acid amide, caproic acid amide, and n-oleyl palmi. Examples thereof include toamide, n-oleyl erukaamide, and dimer thereof, among which oleic acid amide, stearate amide, erucic acid amide and erucic acid amide dimer are preferable, and erucic acid amide is more preferable. .. These can be used alone or in admixture of two or more.

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

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

<Aluminum flakes>
The aluminum flakes can be produced by a known method. Specifically, for example, it can be produced by pulverizing or grinding a material such as atomized powder, aluminum foil, or vapor-deposited aluminum foil with 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 atomizing method with a ball mill are preferable. The purity of aluminum is not particularly limited, and may be an alloy with another metal 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.

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

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

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

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

The propylene-based polymer (A) is a propylene-based polymer in which the biomass-derived carbon concentration, the degree of biomass, and the like are adjusted to a desired range from the viewpoint of cost control, promotion of diffusion, and the like. Therefore, for the purpose of setting the biomass-derived carbon concentration, the degree of biomass, etc. of the material to be the molded body to desired values, the above-mentioned biomass-derived propylene-based polymer (or resin composition containing the biomass-derived propylene-based polymer) can be used. As such, it is not necessary to additionally dilute with a fossil fuel-derived propylene-based polymer. From this, in the molded product of the present invention, it is possible to simplify the equipment and process for manufacturing the molded product, and it is possible to reduce the environmental load.

A propylene copolymer (A) such as the propylene-based polymer (A) of the present invention (propylene homopolymer (A1), propylene-based random copolymer (A2-1), propylene / ethylene block copolymer (A2-2)) ( The resin composition containing A2)) and the propylene-based polymer (A) includes injection molding, extrusion molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, injection stretch blow molding, and press molding (compression molding). , Vacuum molding, calendar molding, foam molding, injection foam molding, foam blow molding, hollow molding and the like, can be molded into various molded bodies.

<Injection molding>
The resin composition containing the propylene-based polymer (A) and the propylene-based polymer (A) of the present invention can be molded into various uses by injection molding.
Examples of the injection molding method 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-A-2005-264833, JP-A-2005-325333, JP-A-2006-307038, International Publication No. 2010/074001, International Publication No. 2010/050509, International Publication No. 2014/073510, International 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, Japanese Patent Laid-Open No. 2021-0250515 The method of injection molding of the propylene-based polymer or the resin composition containing the propylene-based polymer described in 1.

<Injection foam molding>
The resin composition containing the propylene-based polymer (A) and the propylene-based polymer (A) of the present invention can be used for various purposes by injection foam molding.
Examples of the injection foam molding method include JP-A-2002-79545, JP-A-2004-359877, JP-A-2006-159898, JP-A-2004-307665, JP-A-2008-144022, JP-A-2008-163320. No., Japanese Patent Application Laid-Open No. 2014-181317, Japanese Patent Application Laid-Open No. 2015-10102, International Publication No. 2016068164, Japanese Patent Laid-Open No. 2017-217833, JP-A-2017-218509, JP-A-2019-89891, JP-A-2020-152781 Examples thereof include the propylene-based polymer described or a method for injection foam molding of a resin composition containing a propylene-based polymer.

<Hollow molding>
The resin composition containing the propylene-based polymer (A) and the propylene-based polymer (A) of the present invention can be molded into various uses by hollow molding.
Examples of the hollow molding method include the propylenes described in International Publication No. 2011/090101, International Publication No. 2015/137268, JP-A-2015-168788, International Publication No. 2015/137262, and JP-A-2020-090616. Examples thereof include a method of hollow molding of a resin composition containing a based polymer or a propylene based polymer.

<Foam blow molding>
The resin composition containing the propylene-based polymer (A) and the propylene-based polymer (A) of the present invention can be used for various purposes by foam blow molding.
Examples of the foam blow molding method include the method of foam blow molding of the propylene-based polymer or the resin composition containing the propylene-based polymer described in International Publication No. 2011/118281.

<Injection stretch blow molding>
The resin composition containing the propylene-based polymer (A) and the propylene-based polymer (A) of the present invention can be used for various purposes by injection-stretched blow molding.
Examples of the method for injection stretch blow molding include the propylene-based 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 thereof include a method of injection stretch blow molding of a resin composition containing a propylene-based polymer.

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

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

<Biaxial stretched film>
By biaxial stretching molding from the resin composition containing the propylene-based polymer (A) and the propylene-based polymer (A) of the present invention, biaxially stretched films used for various purposes can be molded. Examples of the biaxially stretched film include JP-A-1-156353, JP-A-7-76641, JP-A-2002-275333, JP-A-2004-315582, JP-A-2006-299229, JP-A-2020-105358, and the like. Japanese Patent Application Laid-Open No. 2004-175932, International Publication No. 2016/159044, International Publication No. 2016/017752, International Publication No. 2010/087328, Japanese Patent Application Laid-Open No. 2010-219329, Japanese Patent Application Laid-Open No. 2008-133351, Japanese Patent Application Laid-Open No. 2006-143975 No., JP-A-2006-28761, JP-A-2016-187933, JP-A-2016-187934, JP-A-2017-17769, JP-A-2017-177726, JP-A-2017-177727. Alternatively, it can be produced by a method of molding a biaxially stretched molded film from a resin composition containing a propylene-based polymer. The biaxially stretched film may be a single layer or a laminated body.

<Non-stretched film>
By molding a non-stretched film from the resin composition containing the propylene-based polymer (A) and the propylene-based polymer (A) of the present invention, a non-stretched film used for various purposes can be molded. Examples of the non-stretched film include JP-A-2002-338762, JP-A-7-233290, JP-A-8-85711, JP-A-9-208629, JP-A-9-272718, JP-A-11-106433, and special examples. Kai 2002-317012, International Publication No. 2021 / 0251142, JP-A-2006-52314, JP-A-2000-119480, JP-A-2001-261921, International Publication No. 2019/189486, JP-A-2009-161590, Non-stretched film from the propylene-based polymer or the resin composition containing the propylene-based polymer described in International Publication No. 2014/030594, International Publication No. 2016/158892, JP-A-2015-193181, JP-A-2020-114908. Can be produced by the method of molding. The non-stretched film may be a single layer or a laminated body.

<Sheet / Vacuum Formed>
By molding a resin composition containing the propylene-based polymer (A) and the propylene-based polymer (A) of the present invention into a sheet, sheets used for various purposes can be molded. Further, the sheet can be further vacuum formed to obtain a vacuum formed body used for various purposes. The sheets and vacuum formed bodies are, for example, JP-A-2005-97548, JP-A-2002-284942, JP-A-7-333920, JP-A-2001-2859, JP-A-2015-124362, International Publication No. 2016/114393. No., International Publication No. 2016/114393, JP-A-2010-16852, JP-A-2014-169446. A method for molding a sheet from a propylene-based polymer or a resin composition containing a propylene-based polymer. It can be produced by a method of producing a vacuum-formed body from a sheet. The sheet and the vacuum formed body may be a single layer or a laminated body.

<Effervescent sheet>
By molding a foamed sheet from the resin composition containing the propylene-based polymer (A) and the propylene-based polymer (A) of the present invention, foamed sheets used for various purposes can be molded. The foamed sheet is formed from, for example, the propylene-based polymer described in JP-A-2018-109104, International Publication No. 2006/054715, and JP-A-2009-221473, or a resin composition containing a propylene-based polymer. It can be produced by the method. The foamed sheet may be a single layer or a laminated body.

<Extruded laminated products>
Extruded laminate products used for various purposes can be produced by extrusion laminating molding from the resin composition containing the propylene-based polymer (A) and the propylene-based polymer (A) of the present invention. The extruded laminated product can be produced, for example, by a method for producing an extruded laminated product from a propylene-based polymer or a resin composition containing a propylene-based polymer described in JP-A-2-281555 and JP-A-2017-132134. The laminated layer of the extruded laminated product may be a single layer or a laminated body.

<Fiber / non-woven fabric>
From the resin composition containing the propylene-based polymer (A) and the propylene-based polymer (A) of the present invention, fibers used for various purposes can be obtained by, for example, filament molding with a winder, and for example, melt blown. Nonwoven fabrics used for various purposes can be obtained by molding or spunbond molding. The fiber or non-woven fabric has a resin composition containing, for example, the propylene-based polymer or the 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 a fiber or a non-woven fabric from an object.

<Shrink film>
From the resin composition containing the propylene-based polymer (A) and the propylene-based polymer (A) of the present invention, for example, by forming a stretched film, shrink films used for various purposes can be produced. The shrink film is described in, for example, JP-A-10-168252, JP-A-2002-363308, JP-A-10-152531, JP-A-2001-171001, JP-A-2010-189473, JP-A-2000-159946. It can be produced by a method of producing a shrink film from a propylene-based polymer or a resin composition containing a propylene-based polymer. The shrink film may be a single layer or a laminated body.

<Separator>
From the resin composition containing the propylene-based polymer (A) and the propylene-based polymer (A) of the present invention, for example, by forming a stretched film, separators used for various purposes can be produced. The separator is, for example, a method for preparing a separator from a propylene-based polymer or a resin composition containing a propylene-based polymer according to JP-A-2010-114909, International Publication No. 2014/06331, and International Publication No. 2010/077984. Can be produced by The resin layer constituting the separator may be a single layer or a multilayer.

<Use>
The molded product obtained from the resin composition containing the propylene-based polymer (A) and the propylene-based polymer (A) of the present invention by the above-mentioned method is used for automobile parts, containers for food applications and medical applications, and food applications. It can be applied to various known applications such as packaging materials for electronic materials and electronic materials.

Automotive parts include, for example, automobile exterior parts such as bumpers, side moldings, and aerodynamic undercovers; automobile interior parts such as instrument panels and interior trims; exterior panel parts such as fenders, door panels, and steps; engine covers, fans, and fans. Engine peripheral parts such as shrouds; etc.

Containers for food and medical use include, for example, tableware, retort containers, frozen storage containers, retort pouches, microwave heat-resistant containers, frozen food containers, chilled confectionery cups, cups, beverage bottles and other food containers, retort containers, bottles. Examples include containers, blood transfusion sets, medical bottles, medical containers, medical hollow bottles, medical bags, infusion bags, blood storage bags, infusion bottles, chemical containers, detergent containers, cosmetic containers, perfume containers, toner containers, etc. ..
Examples of packaging materials include food packaging materials, meat packaging materials, processed fish packaging materials, vegetable packaging materials, fruit packaging materials, fermented food packaging materials, confectionery packaging materials, oxygen absorber packaging materials, retort food packaging materials, and freshness. Retention film, pharmaceutical packaging material, cell culture bag, cell test film, bulb packaging material, seed packaging material, vegetable / mushroom cultivation film, heat-resistant vacuum-molded container, side dish container, side dish lid material, commercial wrap film, household use Examples include wrap films and baking cartons.

When the molded body of the present invention is a film, sheet, tape or the like, its use is, for example, a protective film for a polarizing plate, a protective film for a liquid crystal panel, a protective film for an optical component, a protective film for a lens, an electric component. -Protective films for electrical appliances, mobile phones, personal computers, masking films, condenser films, reflective films, laminates (including glass), radiation resistant films, γ-ray resistant films, porous films, etc. And so on.

Other uses of the molded body of the present invention include, for example, housings of home appliances, hoses, tubes, wire coating materials, gaskets for high-pressure electric wires, tubes for cosmetic / perfume sprays, medical tubes, infusion tubes, pipes, wires. Harness, interior materials for motorcycles, railroad vehicles, aircraft, ships, etc., instrument panel skin, door trim skin, rear package trim skin, ceiling skin, rear pillar skin, seat back garnish, console box, armrest, airbag case lid, shift knob , Assist grip, side step mat, reclining cover, seat in trunk, seat belt buckle, inner / outer molding, roof molding, molding material such as belt molding, automobile sealing material such as door seal, body seal, glass run channel, mud Automotive interior / exterior materials such as kicking plates, step mats, number plate housings, automobile hose members, air duct hoses, air duct covers, air intake pipes, air dam skirts, timing belt cover seals, bonnet cushions, door cushions, vibration damping tires. , Static tires, car race tires, special tires such as radiocon tires, packing, automobile dust cover, lamp seal, automobile boot material, rack and pinion boot, timing belt, wire harness, glomet, emblem, air filter packing, furniture・ Skin materials such as footwear, clothing, bags, building materials, building sealants, waterproof sheets, building material sheets, building material gaskets, window films for building materials, iron core protective members, gaskets, doors, door frames, window frames, rims, Gaskets, opening frames, flooring, ceiling materials, wallpaper, health products (eg non-slip mats / sheets, fall prevention films / mats / sheets), health equipment parts, shock absorbing pads, protectors / protective equipment (eg) : Helmets, guards), sports equipment (eg sports grips, protectors), sports armor, rackets, mouth guards, balls, golf balls, hauling tools (eg hauling shock absorbing grips, shock absorbing sheets), vibration damping Pallets, shock absorbers, insulators, shock absorbers for footwear, shock absorbers, shock absorbers such as shock absorbing films, grip materials, miscellaneous goods, toys, soles, sole soles, midsole / inner soles of shoes, Sole, sandals, suckers, toothbrushes, flooring materials, gym mats, power tool parts, agricultural machinery parts, heat dissipation materials, transparent bases Boards, soundproofing materials, cushioning materials, electric wire cables, shape memory materials, medical gaskets, medical caps, chemical plugs, gaskets, baby foods, dairy products, pharmaceuticals, sterile water, etc. are filled in bottles, then boiled and high-pressure steam. Packing materials for high temperature treatment such as sterilization, industrial sealing materials, industrial sewing tables, number plate housings, cap liners such as PET bottle cap liners, stationery, office supplies, OA printer legs, FAX legs, sewing legs, motors Precision equipment such as support mats, audio anti-vibration materials, OA equipment support members, heat-resistant packing for OA, animal cages, beakers, physics and chemistry experimental equipment such as female cylinders, optical measurement cells, costume cases, clear cases, clear files, clear Applications such as sheets, desk mats, and textiles include, for example, non-woven fabrics, elastic non-woven fabrics, fibers, waterproof cloths, breathable textiles and cloths, paper diapers, sanitary goods, sanitary goods, filters, bug filters, dust filters, air. Examples include cleaners, hollow fiber filters, water purification filters, gas separator films, and the like.

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

The propylene-based polymer (A) of the present invention is a propylene-based polymer in which the biomass-derived carbon concentration, the degree of biomass, etc. are adjusted to desired ranges from the viewpoint of cost control, promotion of diffusion, and the like. Therefore, for the purpose of setting the biomass-derived carbon concentration, the degree of biomass, etc. of the molded product to desired values, as in the above-mentioned biomass-derived propylene-based polymer (or resin composition containing the biomass-derived propylene-based polymer), In addition, the step of mixing the fossil fuel-derived propylene-based biomass is unnecessary. For this reason, in order to obtain a material for producing a molded product, no equipment / process for in-line blending and equipment / process for melt-kneading are required. That is, the equipment can be simplified to obtain the molding material for producing the molded product, and the post-process for producing the molding material after producing the biomass-derived propylene-based polymer becomes unnecessary. From these facts, it is considered that the reduction of power consumption contributes to the reduction of environmental load.

The propylene-based polymer (A) of the present invention contains a propylene-based polymer produced by adopting a mass balance method certified by ISCC PLUS certification or the like. The propylene-based polymer product assigned to the biomass product by the mass balance method may not be the propylene-based polymer (A) of the present invention, but it covers the entire production, use, and disposal of various products in the petrochemical industry. For example, it contributes to the reduction of environmental load, and can be used according to the propylene-based polymer (A), the resin composition, and the molded product of the present invention. Even a propylene-based polymer product that is not assigned to a biomass product by the mass balance method may be the propylene-based polymer (A) of the present invention depending on the production method.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded.

<Measurement conditions for various physical properties>
The physical characteristics of the polymer and the physical properties of the molded product described in Reference Examples, Examples and the like were measured according to the following conditions.
(1) Measurement of ¹⁴ C concentration (pMC (percent Modern Carbon)) The measurement was carried out as follows according to ASTM D 6866-21.
The sample was burned to generate carbon dioxide (CO ₂ ) and the carbon dioxide was purified on a vacuum line. The purified carbon dioxide was reduced with hydrogen using iron as a catalyst to produce graphite.
Graphite was packed in a cathode with an inner diameter of 1 mm by a hand press, fitted into a wheel, and attached to a measuring device ( ¹⁴ C-AMS dedicated device based on a tandem accelerator (manufactured by NEC)). With this measuring device, ¹⁴ C count, ¹³ C concentration ( ¹³ C / ¹² C), and ¹⁴ C concentration ( ¹⁴ C / ¹² C) were measured. For the measurement, oxalic acid (HOxII) provided by the National Institute of Standards and Standards (NIST) was used as a standard sample. Measurements of this standard sample and background sample were also performed at the same time.
¹⁴ C concentration (pMC) refers to the ratio of the ¹⁴ C concentration of sample carbon to standard modern carbon.

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

(3) Biomass degree (%) (biobased carbon content (%))
According to ASTM D 6866-21, δ ¹³ C (measured the ¹³ C concentration of sample carbon ( ¹³ C / ¹² C) and corrected the deviation from the reference sample by a thousandth deviation (‰)). It was calculated using the pMC obtained. The value of biomass degree (%) is an integer value rounded to the first decimal place. The atmospheric correction factor used was the value for 2019-2021 described in ASTM D6866-21 (latest version) (100.0 pMC). In the future, the ¹⁴ C concentration in the atmosphere may decrease (change) year by year. In the future, if the value of the atmospheric correction factor described in ASTM D6866 (latest version) is changed from 100.0 pMC, the value described in ASTM D6866 of the year in which the propylene-based polymer according to the present invention was manufactured will be changed to the value described in ASTM D6866. And. When the year of manufacture of the raw material for producing the biomass-derived olefin is unknown, the atmospheric correction coefficient was set to 100.0 pMC.

(4) Biomass-derived olefin (% by weight) in the raw material monomer
A raw material source (1) containing only a biomass-derived olefin of one type of olefin (for example, propylene) and a raw material source (2) containing only a fossil fuel-derived olefin of the same olefin as the one type of olefin are prepared. By adjusting the mixing ratio of the raw material source (1) and the raw material source (2), the weight% of the biomass-derived olefin and the weight% of the fossil fuel-derived olefin in the raw material monomer were adjusted to desired values. When two or more kinds of olefins are olefins (a) (a mixture of biomass-derived olefins and fossil fuel-derived olefins), a raw material source (1') containing only two or more kinds of biomass-derived olefins and two or more kinds of olefins. Mix with a raw material source (2') containing only fossil fuel-derived olefins, and if necessary (for example, if you want to change the weight% of biomass-derived olefins for each olefin species), separately come from one or more biomass-derived sources. A raw material source consisting only of olefins (1'a) or a raw material source consisting only of one or more fossil fuels (2'a) is mixed to obtain a weight% of biomass-derived olefins in the raw material monomer and derived from fossil fuels. The weight% of the olefin may be adjusted to a desired value.

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

(6) Isotactic pentad fraction (mmmm: [%])
The pentad fraction is one of the indexes of the stereoregularity of the polymer, and is a value obtained by examining its microtacticity. The isotactic pentad fraction (mmmm: [%]) of the propylene-based polymer was assigned based on Macromolecules ⁸ , 687 (1975) obtained by carbon-nuclear magnetic resonance analysis ( ¹³ C-NMR). It was calculated from the peak intensity ratio of the NMR spectrum.

< ¹³ C-NMR measuring device and measuring conditions>
Measuring device: AVANCE III type 500 nuclear magnetic resonance device (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)
Repeat time: 5.5 seconds Accumulation number: 256 times Measurement solvent: Ortodichlorobenzene / benzene-d6 (4 / 1v / v)
Sample concentration: ca. 50mg / 0.6mL
Measurement temperature: 120 ° C
Window function: exponential (BF: 0.5Hz)
Chemical shift standard: mmmm (21.59ppm)

(7) Content (weight (%)) of structural units derived from ethylene in the propylene-based polymer
The measurement conditions are the same as those in (6) Isotactic pentad fraction measurement.
From the spectrum obtained by the measurement, the ratio of the monomer chain distribution (triad (triplet) distribution) was determined according to the following document (1), and the ratio in the copolymer (for example, propylene / ethylene random copolymer) was determined. The mole fraction (mol%) of the constituent unit derived from ethylene (hereinafter referred to as E (mol%)) and the molar fraction (mol%) of the constituent unit derived from propylene (hereinafter referred to as P (mol%)) are shown. Calculated.

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

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

(9) Mw / Mn
Measurement by gel permeation chromatography (GPC) method with the following equipment and conditions, and analysis of the obtained chromatogram, Mw (weight average molecular weight) value, Mn (number average molecular weight) value and Mn (number average molecular weight) value in terms of polystyrene and The Mw / Mn value was calculated.

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

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

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

<Measurement conditions>
・ Measurement environment: Nitrogen gas atmosphere ・ Sample amount: 5 mg
-Sample shape: Press film (molded at 230 ° C, thickness 200-400 μm)
-Sample set: Enclosed in an aluminum pan-First step: Raise the temperature from 30 ° C to 240 ° C at 10 ° C / min and hold for 10 minutes.
-Second step: The temperature is lowered to 30 ° C at 10 ° C / min.
・ Third step: The temperature is raised to 240 ° C. at 10 ° C./min.

(11) Decane-soluble portion (% by weight) and decane-insoluble portion (% by weight) in the propylene / ethylene block copolymer.
Place 5 ± 0.05 g of the propylene / ethylene block copolymer in a 1,000 ml eggplant-shaped flask, and add 1 ± 0.05 g of BHT (dibutylhydroxytoluene (phenolic antioxidant)). , Rotor and n-decane 700 ± 10 ml were charged. Next, a cooler 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 is stirred with a stirrer and allowed to cool to room temperature (25 ° C.) (8 hours or more), and then the precipitate is wire meshed. I took it out. The filtrate is further filtered through filter paper and then poured into 2,000 ± 100 ml of methanol contained in a 3,000 ml beaker, and the solution is stirred at room temperature (25 ° C.) with a stirrer. It was left for 2 hours or more. Next, the obtained precipitate was collected by filtration with 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 recover the n-decane soluble portion at 25 ° C.
Regarding the content (x) of the n-decane soluble part at 25 ° C., the sample weight was Ag, and the recovered n-decane soluble part was a propylene / ethylene random copolymer (propylene / ethylene random copolymer component (d)). ) Is Cg, and is expressed as x (% by weight) = 100 × C / A. The amount of the decan insoluble portion (y) is expressed as y (% by weight) = 100-x (% by weight).

(12) Extreme viscosity ([η] (dl / g))
About 20 mg of the sample was dissolved in 15 ml of decalin, and the specific viscosity η _sp was measured in an oil bath at 135 ° C. After diluting with 5 ml of decalin solvent added to this decalin solution, the specific viscosity η _sp was measured in the same manner. This dilution operation was repeated twice more, and the value of η _sp / C when the concentration (C) was extrapolated to 0 was determined as the ultimate viscosity [η].
[Η] = lim (η _sp / C) (C → 0)

(13) Biaxially stretched film transverse stretching load Shown by the descending load when laterally stretching with a table tenter during biaxially stretched film molding.

(14) All film haze Measured according to JIS K-7105.

(15) Film tensile elastic modulus The film tensile elastic modulus (MPa) was measured under the following conditions in accordance with JIS K7127.

<Measurement conditions>
-The evaluation film was cut into strips with a width of 10 mm and a length of 150 mm.-Tensile at a crosshead speed of 500 mm / min by a tensile test.-The machine direction was set to MD and the direction perpendicular to MD was set to TD.

(16) Film heat seal temperature The film heat seal temperature (° C.) was measured according to JIS K-1707. The fusion conditions are described below. The temperature of the heat seal bar is calibrated by a surface thermometer. After sealing, it was left at room temperature for a whole day and night, and then the peeling speed was set to 200 mm / min at room temperature, and the peeling strength was measured by the T-type peeling method. The heat seal temperature was obtained by calculating the temperature at which the peel strength becomes 300 g / 15 mm from the seal strength-peeling strength curve.

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

(17) Film Impact Strength The film impact strength was evaluated by the impact fracture strength using a 1/2 inch impact head in a film impact tester manufactured by Toyo Seiki Seisakusho.

(18) Tensile breaking elongation and tensile breaking strength of the injection molded product The tensile breaking elongation (%) and the tensile breaking strength (MPa) of the injection molded product were measured under the following conditions in accordance with ASTM D638.

<Measurement conditions>
Specimen: ASTM-1 dumbbell (19 mm (width) x 3.2 mm (thickness) x 165 mm (length))
Tensile speed: 50 mm / min Distance between spans: 115 mm
The molded product obtained from the 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 4 mm)
Tensile rate: 5 mm / min Temperature: 23 ° C

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

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

(20) Izod Impact Strength of Injection Molded Izod Impact Strength of the injection molded product was measured under the following conditions in accordance with ASTM D256.

<Measurement conditions>
Temperature: 23 ° C
Specimen: 12.7 mm (width) x 6.4 mm (thickness) x 64 mm (length) (notched; notch machined)

(21) Charpy impact test of injection-molded article The Charpy impact value (kJ / m ² ) of the injection-molded article was measured under the following conditions in accordance with JIS K7111.

<Measurement conditions>
Temperature: -30 ° C
Specimen: 10 mm (width) x 80 mm (length) x 4 mm (thickness) (with notch; notch is machined)

(22) Rockwell hardness of the 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>
Specimen: 30 mm (width) x 30 mm (length) x 2 mm (thickness)
Two test pieces were stacked and measured.

(23) Weld strength of the injection molded product The weld strength of the injection molded product was measured under the following conditions in accordance with JIS K7171, and the maximum load of the bending test centering on the weld portion was taken as the weld strength.

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

Raw materials other than the propylene-based polymer (A) <Ethylene / α-olefin copolymer (B)>
Ethylene 1-butene random copolymer (manufactured by Mitsui Chemicals, Inc., Toughmer (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 Flour Milling Co., Ltd.) Average particle diameter determined by laser diffraction method is about 4 μm

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

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

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

[Reference Example 1] (Fossil fuel-derived propylene homopolymer: PP-1-0)
(1-1) Preparation of Magnesium Compound After sufficiently replacing a glass reactor with a stirrer with an internal volume of 12 liters with nitrogen gas, about 4,860 g of ethanol, 32 g of iodine and 320 g of metallic magnesium were added and stirred. While reacting under reflux conditions, a solid reaction product was obtained. The reaction solution containing this solid reaction product was dried under reduced pressure to obtain a magnesium compound (solid product).

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

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

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

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

<Melting and kneading conditions>
Extruder: Part number Toshiba Machine Co., Ltd. twin-screw extruder "TEM-35"
Nitrogen seal cylinder temperature of hopper: 210 ℃
Screw rotation speed: 150 rpm
Extrusion amount: 15 kg / h

(1-6) Preparation of Biaxial Stretched Film Next, using a 35 mmφ sheet forming machine manufactured by Shinko Kikai Seisakusho, the above resin composition obtained in (1-5) was subjected to the conditions of a resin temperature of 260 ° C. and a chill roll temperature of 30 ° C. After forming the sheet, this sheet is longitudinally stretched by a roll stretching machine manufactured by Iwamoto Seisakusho under the conditions of a stretching temperature of 145 ° C. and a stretching ratio of 5 times, and then by a table tenter manufactured by Iwamoto Seisakusho, 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 lateral stretching under the conditions of a stretching speed of 90% / sec and a stretching ratio of 10 times. Subsequently, this biaxially stretched film was surface-treated with a roll electrode type corona discharge processor manufactured by Kasuga Electric Co., Ltd. The wettability of the treated surface was 42 yne / cm. The evaluation results of this biaxially stretched film are shown in Table 1.

[Example 1] (Propylene homopolymer (A1): PP-1-1)
Reference Example 1 (1-4) Reference except that a propylene mixture containing 10% by weight of biomass-derived propylene and 90% by weight of fossil fuel-derived propylene was used as propylene in place of propylene derived from fossil fuel. A propylene homopolymer (PP-1-1), which is a propylene homopolymer (A1), was obtained in the same manner as in Examples 1 (1-1) to (1-4). Table 1 shows the resin physical characteristics 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), the (1-5) additive formulation and granulation of Reference Example 1 A polypropylene resin composition (granulated product) was prepared according to the above (1-6), and a biaxially stretched film was prepared according to the same (1-6). Table 1 shows the physical characteristics of the obtained biaxially stretched film.

[Example 2] (Propylene homopolymer (A1): PP-1-2)
Reference Example 1 (1-4) Reference except that a propylene mixture containing 30% by weight of biomass-derived propylene and 70% by weight of fossil fuel-derived propylene was used as propylene in place of propylene derived from fossil fuel. A propylene homopolymer (PP-1-2), which is a propylene homopolymer (A1), was obtained in the same manner as in Examples 1 (1-1) to (1-4). Table 1 shows the resin physical characteristics 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), the (1-5) additive formulation and granulation of Reference Example 1 A polypropylene resin composition (granulated product) was prepared according to the above (1-6), and a biaxially stretched film was prepared according to the same (1-6). Table 1 shows the physical characteristics of the obtained biaxially stretched film.

[Example 3] (Propylene homopolymer (A1): PP-1-3)
Reference Example 1 (1-4) Reference Example except that a propylene mixture containing 65% by weight of biomass-derived propylene and 35% by weight of fossil fuel-derived propylene was used as propylene in place of propylene derived from fossil fuel. A propylene homopolymer (PP-1-3), which is a propylene homopolymer (A1), was obtained in the same manner as in (1-1) to (1-4) of 1. Table 1 shows the resin physical characteristics of the obtained propylene homopolymer (PP-1-3).
Using the propylene homopolymer (PP-1-3) obtained in place of the fossil fuel-derived propylene homopolymer (PP-1-0), the (1-5) additive formulation and granulation of Reference Example 1 A polypropylene resin composition (granulated product) was prepared according to the above (1-6), and a biaxially stretched film was prepared according to the same (1-6). Table 1 shows the physical characteristics of the obtained biaxially stretched film.

[Reference Example 2] (Fossil fuel-derived propylene-based random copolymer: PP-2-0)
(2-1) Preparation of magnesium compound The reaction vessel with a stirrer (internal 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 stirred. The reaction was carried out under reflux conditions until the generation of hydrogen gas disappeared from the system to obtain a solid reaction product. The reaction solution containing this solid reaction product was dried under reduced pressure to obtain the desired magnesium compound (carrier of solid catalyst).

(2-2) Preparation of solid catalyst component In a reaction vessel with a stirrer (internal volume 500 liters) sufficiently replaced with nitrogen gas, 30 kg of the magnesium compound (not crushed) obtained in (2-1). , 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., 144 liters of titanium tetrachloride was added while stirring, and the mixture was reacted at 110 ° C. for 2 hours, then the solid component was separated and washed with purified heptane at 80 ° C. Further, 228 liters of titanium tetrachloride was added and 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 put into a reaction vessel with a stirrer having an internal volume of 500 liters, and 25 kg of the solid catalyst component obtained in (2-2) was added to the titanium atom in the solid catalyst component. However, triethylaluminum was supplied at a ratio of 1.0 mol / mol and dicyclopentyldimethoxysilane was supplied at a ratio of 1.8 mol / mol. Then, propylene was introduced at a partial pressure of propylene until it reached 0.3 kg / cm ² G, and the reaction was carried out at 25 ° C. for 4 hours. After completion of the stirring reaction, the solid catalyst component was washed with purified heptane several times, carbon dioxide was further supplied, and the mixture was stirred for 24 hours. As propylene, fossil fuel-derived propylene was used.

(2-4) Main Polymerization A polymerizer with an internal volume of 200 liters is supplied with the treated solid catalyst component of (2-3) above at 3 mmol / hr in terms of titanium atom and triethylaluminum at 120 mmol / hr. Then, propylene and ethylene were reacted at a polymerization temperature of 80 ° C. and a polymerization pressure (total pressure) of 28 kg / cm ² G. At this time, the supply amount of ethylene and the supply amount of hydrogen were adjusted so as to have the desired ethylene content and molecular weight, and propylene, ethylene and hydrogen were continuously supplied to the polymerization apparatus. The ethylene concentration of the composition analysis value (gas chromatographic analysis) of the gas portion in the polymerization apparatus was 3.4 mol%, and the hydrogen concentration was 2.4 mol%. 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. The MFR was measured using the granulated product obtained in (2-5) below.

(2-5) Additive formulation and granulation 1000 ppm of Irganox 1010 manufactured by Ciba Geigy Co., Ltd. as an antioxidant is added to the propylene / ethylene random copolymer (PP-2-0) powder thus obtained in (2-4). Ilgafos 168 manufactured by Ciba Geigy Co., Ltd. was formulated at 1000 ppm, calcium stearate at 1000 ppm as a neutralizing agent, silica-based antiblocking agent at 2300 ppm, and erucic acid amide as a slip agent at 500 ppm. Granulation was performed to prepare a resin composition (granulated product) containing a propylene-based random copolymer.

<Melting and kneading conditions>
Extruder: Part number Toshiba Machine Co., Ltd. twin-screw extruder "TEM-35"
Nitrogen seal cylinder temperature of hopper: 210 ℃
Screw rotation speed: 150 rpm
Extrusion amount: 15 kg / h

(2-6) Preparation of Film Next, using a 75 mmφ molding machine manufactured by Mitsubishi Heavy Industries, a film having a film thickness of 30 μm was prepared from the above resin composition obtained in (2-5) under the following molding conditions.

<Molding conditions>
Processing temperature: 243 ° C
Chill roll temperature: 25 ° C
Pick-up speed: 125m / min
The obtained film was adjusted for 16 hours or more at a temperature of 23 ± 2 ° C. and a humidity of 50 ± 10%, and then the physical properties of the film were measured under the same temperature and humidity conditions. Table 2 shows the physical characteristics of the obtained film.

[Example 4] (Propylene-based random copolymer (A2-1): PP-2-1)
In (2-4) main polymerization of Reference Example 2, a propylene mixture containing 10% by weight of biomass-derived propylene and 90% by weight of fossil fuel-derived propylene was used as propylene instead of propylene derived from fossil fuel, and the ethylene was fossilized. Same as (2-1) to (2-4) of Reference Example 2 except that an ethylene mixture containing 10% by weight of ethylene derived from biomass and 90% by weight of ethylene derived from fossil fuel was used instead of ethylene derived from fuel. 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) of Reference Example 2 using a propylene / ethylene random copolymer (PP-2-1) obtained in place of the fossil fuel-derived propylene-based random copolymer (PP-2-0). A polypropylene resin composition (granulated product) was prepared according to the agent formulation and granulation, and a film having a thickness of 30 μm was prepared according to the preparation of the same (2-6) film. Table 2 shows the physical characteristics of the obtained film.

[Example 5] (Propylene-based random copolymer (A2-1): PP-2-2)
In (2-4) main polymerization of Reference Example 2, a propylene mixture containing 30% by weight of biomass-derived propylene and 70% by weight of fossil fuel-derived propylene was used as propylene instead of propylene derived from fossil fuel, and the ethylene was fossilized. Same as (2-1) to (2-4) of Reference Example 2 except that an ethylene mixture containing 30% by weight of ethylene derived from biomass and 70% by weight of ethylene derived from fossil fuel was used instead of ethylene derived from fuel. A propylene / ethylene random copolymer (PP-2-2), 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.
Addition of (2-5) of Reference Example 2 using a propylene / ethylene random copolymer (PP-2-2) obtained in place of the fossil fuel-derived propylene-based random copolymer (PP-2-0). A polypropylene resin composition (granulated product) was prepared according to the agent formulation and granulation, and a film having a thickness of 30 μm was prepared according to the preparation of the same (2-6) film. Table 2 shows the physical characteristics of the obtained film.

[Example 6] (Propylene-based random copolymer (A2-1): PP-2-3)
In (2-4) main polymerization of Reference Example 2, a propylene mixture containing 65% by weight of biomass-derived propylene and 35% by weight of fossil fuel-derived propylene was used as propylene instead of propylene derived from fossil fuel, and the ethylene was fossilized. Same as (2-1) to (2-4) of Reference Example 2 except that an ethylene mixture containing 65% by weight of ethylene derived from biomass and 35% by weight of ethylene derived from fossil fuel was used instead of ethylene derived from fuel. A propylene / ethylene random copolymer (PP-2-3), 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.
Addition of (2-5) of Reference Example 2 using a propylene / ethylene random copolymer (PP-2-3) obtained in place of the fossil fuel-derived propylene-based random copolymer (PP-2-0). A polypropylene resin composition (granulated product) was prepared according to the agent formulation and granulation, and a film having a thickness of 30 μm was prepared according to the preparation of the same (2-6) film. Table 2 shows the physical characteristics 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 prepare a uniform 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 phthalic anhydride.
After cooling the uniform solution thus obtained to 23 ° C., 750 ml of this uniform solution was added dropwise to 2000 ml of titanium tetrachloride kept at −20 ° C. for 1 hour. After the dropping, the temperature of the obtained mixed solution was raised to 110 ° C. over 4 hours, 52.2 g of diisobutyl phthalate (DIBP) was added when the temperature reached 110 ° C., and the same temperature was stirred for 2 hours. Held in. Then, the solid part was collected by hot filtration, the solid part was resuspended in 2750 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours.

After the heating was completed, the solid part 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 is stored as a hexane slurry, and a part of the solid titanium catalyst component was dried to examine the catalyst composition. The solid titanium catalyst component contained titanium in an amount of 2% by weight, chlorine in an amount of 57% by weight, magnesium in an amount of 21% by weight, and DIBP in an amount of 20% by weight.

(3-2) 70 g of solid titanium catalyst component obtained in (3-1) pretreatment, 44.0 mL of triethylaluminum, 15.0 mL of 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 80 L of heptane Was inserted into an autoclave with a stirrer having an internal volume of 200 L, 700 g of propylene was inserted at an internal temperature of 5 ° C., and the mixture was reacted with stirring for 60 minutes. After the completion of the polymerization, the solid component was allowed to settle, the supernatant was removed, and the washing with heptane was performed twice. The obtained prepolymerization 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 prepolymerization catalyst contained 10 g of polypropylene per 1 g of solid titanium catalyst component. In addition, propylene derived from fossil fuel was used as propylene.

(3-3) Main Polymerization The product was sent to a Vessel polymerizer (1) with a stirrer having an internal capacity of 1000 L, and propylene was supplied at 133 kg / hour and hydrogen was supplied so that the hydrogen concentration in the gas phase portion was 8.0 mol%. The prepolymerization catalyst obtained in (3-2) was continuously supplied with 0.8 g / hour as a solid titanium catalyst component, 15.3 g / hour of triethylaluminum, and 1.5 mL / hour of dicyclopentyldimethoxysilane for polymerization. Polymerization was carried out at a temperature of 70 ° C. and a pressure of 3.4 MPa / G. As propylene, fossil fuel-derived propylene was used (the same applies to the following steps).

The slurry containing the polymer obtained in the polymerizer (1) was sent to another Vessel polymerizer (2) with a stirrer having an internal capacity of 500 L, and further polymerization was carried out. Propylene was supplied to the polymerizer (2) at 21 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase portion 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 polymerizer (2) was sent to another Vessel polymerizer (3) with a stirrer having an internal capacity of 500 L, and further polymerization was carried out. Propylene was supplied to the polymerizer (3) at 17 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase portion was 6.0 mol%. Polymerization was carried out at a polymerization temperature of 70 ° C. and a pressure of 3.3 MPa / G.
A part of the slurry obtained in the polymerizer (3) is sampled and filtered before the ethylene / propylene block copolymerization (step of producing the propylene / ethylene random copolymer component (d)), and air-dried for 5 hours or more. Then, after drying in a vacuum dryer at 100 ± 5 ° C. for 240 to 270 minutes, the MFR, melting point, pentad fraction, and Mw / Mn were measured. At the time of MFR measurement, 1000 ppm of Irganox 1010 manufactured by Ciba Geigy and 1000 ppm of Ilgafos 168 manufactured by Ciba Geigy were added as antioxidants.

The slurry obtained in the polymerizer (3) is sent to another Vessel polymerizer (4) with a stirrer having an internal capacity of 500 L to carry out copolymerization (preparation of the propylene / ethylene random copolymer component (d)). rice field. Propylene was supplied to the polymerizer (4) at 15 kg / hour, ethylene was supplied at 17 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase portion was 5.0 mol%. Polymerization was carried out at a polymerization temperature of 60 ° C. and a pressure of 3.2 MPa / G. In addition, ethylene derived from fossil fuel was used as ethylene.
After vaporizing the slurry obtained in the polymer (4), air-solid separation was carried out 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. The MFR was measured using the granulated product obtained in (3-4) below.

(3-4) Additive formulation and granulation 1000 ppm of Irganox 1010 manufactured by Ciba Geigy Co., Ltd. as an antioxidant is added to the propylene / ethylene block copolymer (PP-3-0) powder thus obtained in (3-3). Ilgafos 168 manufactured by Ciba Geigy Co., Ltd. was formulated at 1000 ppm and calcium stearate at 1000 ppm as a neutralizing agent was formulated, and these were mixed with a tumbler and then granulated under the following conditions to prepare a polypropylene resin composition (granulated product).

<Melting and kneading conditions>
Same-direction twin-screw kneader: Part number NR2-36 (manufactured by Nakatani Machinery Co., Ltd.)
Kneading temperature: 230 ° C
Screw rotation speed: 200 rpm
Feeder speed: 500 rpm

(3-5) Injection molding Using the granulated product obtained in (3-4), an ASTM test piece (injection molded product) was used with an injection molding machine [Product number IS100 (manufactured by Toshiba Machine Co., Ltd.)] under the following conditions. ) Was molded. Table 3 shows the physical characteristics of the injection-molded article made of a propylene / ethylene block copolymer (PP-3-0).

<Injection molding conditions>
Injection molding machine: Part number IS100 (manufactured by Toshiba Machine Co., Ltd.)
Cylinder temperature: 190 ° C
Mold temperature: 40 ° C
Injection time-holding time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds

[Example 7] (Propylene / ethylene block copolymer (A2-2): PP-3-1)
In (3-3) main polymerization of Reference Example 3, a propylene mixture containing 10% by weight of biomass-derived propylene and 90% by weight of fossil fuel-derived propylene was used as propylene instead of propylene derived from fossil fuel, and the ethylene was fossilized. Same as (3-1) to (3-3) of Reference Example 3 except that an ethylene mixture containing 10% by weight of ethylene derived from biomass and 90% by weight of ethylene derived from fossil fuel was used instead of ethylene derived from fuel. 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).
Using a propylene / ethylene block copolymer (PP-3-1) obtained in place of the fossil fuel-derived propylene / ethylene block copolymer (PP-3-0), Reference Example 3 (3-4) A polypropylene resin composition (granulated product) was prepared according to the additive formulation and granulation, and an injection-molded body was prepared according to the same (3-5) injection molding. Table 3 shows the physical characteristics of the obtained injection molded product.

[Example 8] (Propylene / ethylene block copolymer (A2-2): PP-3-2)
In the main polymerization of Reference Example 3 (3-3), a propylene mixture containing 30% by weight of biomass-derived propylene and 70% by weight of fossil fuel-derived propylene was used as ethylene instead of propylene derived from fossil fuel. Same as (3-1) to (3-3) of Reference Example 3 except that an ethylene mixture containing 30% by weight of ethylene derived from biomass and 70% by weight of ethylene derived from fossil fuel was used instead of ethylene derived from fossil fuel. A propylene / ethylene block copolymer (PP-3-2), 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-3-2).
Using a propylene / ethylene block copolymer (PP-3-2) obtained in place of the fossil fuel-derived propylene / ethylene block copolymer (PP-3-0), Reference Example 3 (3-4) A polypropylene resin composition (granulated product) was prepared according to the additive formulation and granulation, and an injection-molded body was prepared according to the same (3-5) injection molding. Table 3 shows the physical characteristics of the obtained injection molded product.

[Example 9] (Propylene / ethylene block copolymer (A2-2): PP-3-3)
In (3-3) main polymerization of Reference Example 3, a propylene mixture containing 65% by weight of biomass-derived propylene and 35% by weight of fossil fuel-derived propylene was used as propylene instead of propylene derived from fossil fuel, and the ethylene was fossilized. Same as (3-1) to (3-3) of Reference Example 3 except that an ethylene mixture containing 65% by weight of ethylene derived from biomass and 35% by weight of ethylene derived from fossil fuel was used instead of ethylene derived from fuel. A propylene / ethylene block copolymer (PP-3-3) was obtained. Table 3 shows the resin physical properties of the obtained propylene / ethylene block copolymer (PP-3-3).
Using a propylene / ethylene block copolymer (PP-3-3) obtained in place of the fossil fuel-derived propylene / ethylene block copolymer (PP-3-0), Reference Example 3 (3-4) A polypropylene resin composition (granulated product) was prepared according to the additive formulation and granulation, and an injection-molded body was prepared according to the same (3-5) injection molding. Table 3 shows the physical characteristics of the obtained injection molded product.

[Reference Example 4] (Fossil fuel-derived propylene homopolymer, resin composition containing the propylene homopolymer)
<Preparation of fossil fuel-derived propylene homopolymer (PP-4-0)>
(4-1) Preparation of Solid Titanium Catalyst Component 95.2 g of anhydrous magnesium chloride, 442 ml of decan and 390.6 g of 2-ethylhexyl alcohol were heated at 130 ° C. for 2 hours to prepare a uniform solution. 21.3 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 phthalic anhydride.
After cooling the uniform solution thus obtained to room temperature, 75 ml of this uniform solution was added dropwise over 200 ml of titanium tetrachloride kept at −20 ° C. for 1 hour. After the charging is completed, the temperature of this mixed solution is raised to 110 ° C. over 4 hours, 5.22 g of diisobutyl phthalate (DIBP) is added when the temperature reaches 110 ° C., and the mixture is stirred at the same temperature for 2 hours. Retained.
After the reaction for 2 hours was completed, the solid part was collected by hot filtration, the solid part was resuspended in 275 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours. After completion of the reaction, the solid part was collected again by hot filtration and washed thoroughly with decane and hexane at 110 ° C. until no free titanium compound was detected in the solution.
Here, the detection of this free titanium compound was confirmed by the following method. 10 ml of the supernatant liquid of the above solid catalyst component was collected by a syringe and charged into 100 ml of Candelabra with nitrogen substituted in advance. Next, the solvent hexane was dried in a nitrogen stream and vacuum dried for another 30 minutes. 40 ml of ion-exchanged water and 10 ml of 50% by volume sulfuric acid were charged therein and stirred for 30 minutes. Transfer this aqueous solution to a 100 ml volumetric flask through a 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 color-developing reagent for titanium, and further add ion-exchanged water to 100 ml. The volumetric flask was shaken up, and after 20 minutes, the absorbance at 420 nm was observed using UV, 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 decan slurry, and a part of the solid titanium catalyst component was dried for the purpose of examining 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) Pretreatment for Polymerization 100 g of the solid titanium catalyst component, 39.3 mL of triethylaluminum, and 100 L of heptane obtained in (4-1) are inserted into an autoclave with a stirrer having an internal capacity of 200 L, and the internal temperature is 15 to 20. Keeping the temperature at ° C., 600 g of propylene was inserted and reacted with stirring for 60 minutes to obtain a catalytic slurry. In addition, propylene derived from fossil fuel was used as propylene.

(4-3) Main Polymerization In a circulating tubular polymerizer with a jacket having an internal capacity of 58 L, propylene was 43 kg / hour, hydrogen was 177 NL / hour, 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 supplied and polymerized in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 70 ° C. and the pressure was 3.53 MPa / G. Fossil fuel-derived propylene was used as the propylene (the same applies to the following steps).
The slurry obtained by the tubular polymerizer was sent to a Vessel polymerizer equipped with a stirrer having an internal capacity of 100 L, and further polymerization was carried out. Propylene was supplied to the polymerizer at 45 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase portion 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. At the time of MFR measurement, 1000 ppm of Irganox 1010 manufactured by Ciba Geigy and 1000 ppm of Ilgafos 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 the propylene homopolymer (PP-4-0) powder thus obtained in (4-3) and 25% by weight of the ethylene / α-olefin copolymer (B). In addition, 1000 ppm of Irganox 1010 manufactured by Ciba Geigy Co., Ltd. and Irgafoss manufactured by Ciba Geigy Co., Ltd. as an antioxidant are added to the total of the propylene homopolymer (PP-4-0) and the ethylene / α-olefin copolymer (B). A resin composition containing a propylene homopolymer (4B-0) was formulated with 1000 ppm of 168 and 1000 ppm of calcium stearate as a neutralizing agent, mixed with a tumbler, and then melt-kneaded with a twin-screw extruder under the following conditions. Pellets were prepared.

<Melting and kneading conditions>
Same-direction twin-screw kneader: Part number KZW-15 (manufactured by Technobel Co., Ltd.)
Kneading temperature: 190 ° C
Screw rotation speed: 500 rpm
Feeder speed: 40 rpm

(4-5) Injection molding Using the pellets obtained in (4-4), a JIS test piece (injection molded body) is molded by an injection molding machine [Product number EC40 (manufactured by Toshiba Machine Co., Ltd.)] under the following conditions. Molded. Table 4 shows the physical characteristics of the injection-molded article made of the resin composition (4B-0).

<Injection molding conditions>
Injection molding machine: Part number EC40 (manufactured by Toshiba Machine Co., Ltd.)
Cylinder temperature: 190 ° C
Mold temperature: 40 ° C
Injection time-holding time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds

[Example 10] (Polypropylene homopolymer (A1): PP-4-1, a resin composition containing the propylene homopolymer (A1))
Reference Example 4 (4-3) Reference except that a propylene mixture containing 10% by weight of biomass-derived propylene and 90% by weight of fossil fuel-derived propylene was used as propylene in place of propylene derived from fossil fuel. A propylene homopolymer (PP-4-1), which is a propylene homopolymer (A1), was obtained in the same manner as in Examples 4 (4-1) to (4-3). Table 4 shows the resin physical characteristics 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), the (4-4) additive formulation and granulation of Reference Example 4 were used. According to this, pellets of the resin composition (4B-1) containing the propylene homopolymer (PP-4-1) and the ethylene / α-olefin copolymer (B) were prepared, and subjected to the same (4-5) injection molding. Therefore, an injection polymer was prepared from the pellets of the resin composition (4B-1). Table 4 shows the physical characteristics of the obtained injection molded product.

[Example 11] (Polypropylene homopolymer (A1): PP-4-2, a resin composition containing the propylene homopolymer (A1))
Reference Example 4 (4-3) Reference except that a propylene mixture containing 30% by weight of biomass-derived propylene and 70% by weight of fossil fuel-derived propylene was used as propylene in place of propylene derived from fossil fuel. A propylene homopolymer (PP-4-2), which is a propylene homopolymer (A1), was obtained in the same manner as in Examples 4 (4-1) to (4-3). Table 4 shows the resin physical 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), the (4-4) additive formulation and granulation of Reference Example 4 were used. According to this, pellets of the resin composition (4B-2) containing the propylene homopolymer (PP-4-2) and the ethylene / α-olefin copolymer (B) were prepared, and subjected to the same (4-5) injection molding. Therefore, an injection polymer was prepared from the pellets of the resin composition (4B-2). Table 4 shows the physical characteristics of the obtained injection molded product.

[Example 12] (Polypropylene homopolymer (A1): PP-4-3, a resin composition containing the propylene homopolymer (A1))
Reference Example 4 (4-3) Reference except that a propylene mixture containing 65% by weight of biomass-derived propylene and 35% by weight of fossil fuel-derived propylene was used as propylene in place of propylene derived from fossil fuel. A propylene homopolymer (PP-4-3), which is a propylene homopolymer (A1), was obtained in the same manner as in Examples 4 (4-1) to (4-3). Table 4 shows the resin physical characteristics of the obtained propylene homopolymer.
Using the propylene homopolymer (PP-4-3) obtained in place of the fossil fuel-derived propylene homopolymer (PP-4-0), the (4-4) additive formulation and granulation of Reference Example 4 were used. According to this, pellets of the resin composition (4B-3) containing the propylene homopolymer (PP-4-3) and the ethylene / α-olefin copolymer (B) were prepared, and subjected to the same (4-5) injection molding. Therefore, an injection polymer was prepared from the pellets of the resin composition (4B-3). Table 4 shows the physical characteristics of the obtained injection molded product.

[Reference Example 5] (Fossil fuel-derived propylene homopolymer, resin composition containing the propylene homopolymer)
<Preparation of fossil fuel-derived propylene homopolymer (PP-5-0)>
(5-1) Preparation of Solid Titanium Catalyst Component 1.3% by weight of titanium and 20% by weight of magnesium in the same manner as in [Example 1] ([0157] to [0161]) of International Publication No. 2019/004418. , 13.8% by weight of diisobutyl phthalate and 0.8% by weight of diethyl phthalate were obtained as a solid titanium catalyst component (i-1). In addition, the present inventor may use the diethyl phthalate detected in the solid titanium catalyst component (i-1) to produce diisobutyl phthalate and solid titanium in the process of producing the solid titanium catalyst component. It is speculated that this may be due to the accompanying transesterification with the ethanol used.

(5-2) 90.0 g of the solid titanium catalyst component (i-1) obtained in the polymerization pretreatment (5-1), 66.7 mL of triethylaluminum, 15.6 mL of isopropylpyrrolidinodimethoxysilane, and 10 L of heptane. It was inserted into an autoclave with a stirrer having an internal volume of 20 L, 900 g of propylene was inserted at an internal temperature of 15 to 20 ° C., and the reaction was carried out while stirring for 100 minutes. After the completion of the polymerization, the solid component was allowed to settle, the supernatant was removed, and the washing with heptane was performed twice. The obtained solid component was resuspended in purified heptane and adjusted with heptane so that the concentration of the solid catalyst component was 1.0 g / L to obtain a catalyst. As propylene, fossil fuel-derived propylene was used.

(5-3) Main Polymerization 300 L of liquefied propylene was charged into a polymerization tank equipped with a stirrer having an internal volume of 500 L, and the catalyst obtained with 100 kg / h of liquefied propylene (5-2) while maintaining this liquid level. 0 g / h, triethylaluminum 8.9 mL / h and isopropylpyrrolidinodimethoxysilane 2.8 mL / h were continuously supplied and polymerized at a temperature of 70 ° C. Further, hydrogen was continuously supplied so that the hydrogen concentration in the gas phase portion in the polymerization tank was 6.9 mol%. As propylene, fossil fuel-derived propylene was used. After deactivating the obtained slurry, propylene was evaporated to obtain a powdery propylene polymer (PP-5-0). The obtained propylene homopolymer was vacuum dried at 80 ° C. Table 5 shows the resin physical properties of the propylene homopolymer (PP-5-0) thus obtained. At the time of MFR measurement, 1000 ppm of Irganox 1010 manufactured by Ciba Geigy and 1000 ppm of Ilgafos 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 80% by weight of the propylene homopolymer powder thus obtained in (5-3), 20% by weight of talc (C), as an antioxidant with respect to the propylene homopolymer. 1000 ppm of Irganox 1010 manufactured by Ciba Geigy, 1000 ppm of Ilgafos 168 manufactured by Ciba Geigy, and 1000 ppm of calcium stearate as a neutralizing agent are prescribed, and these are mixed by a tumbler and then melt-kneaded under the following conditions by a twin-screw extruder. Pellets of the resin composition (5B-0) containing the propylene homopolymer were prepared.

<Melting and kneading conditions>
Same-direction twin-screw kneader: Part number KZW-15 (manufactured by Technobel Co., Ltd.)
Kneading temperature: 190 ° C
Screw rotation speed: 500 rpm
Feeder speed: 50 rpm

(5-5) Injection molding Using the pellets obtained in (5-4), a JIS test piece (injection molded body) is molded by an injection molding machine [Product number EC40 (manufactured by Toshiba Machine Co., Ltd.)] under the following conditions. Molded. Table 5 shows the physical characteristics of the injection-molded article made of the resin composition (5B-0).

<Injection molding conditions>
Injection molding machine: Part number EC40 (manufactured by Toshiba Machine Co., Ltd.)
Cylinder temperature: 190 ° C
Mold temperature: 40 ° C
Injection time-holding time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds

[Example 13] (Polypropylene homopolymer (A1): PP-5-1, a resin composition containing the propylene homopolymer (A1))
Reference Example 5 (5-3) Reference except that a propylene mixture containing 10% by weight of biomass-derived propylene and 90% by weight of fossil fuel-derived propylene was used as propylene in place of propylene derived from fossil fuel. A propylene homopolymer (PP-5-1), which is a propylene homopolymer (A1), was obtained in the same manner as in Examples 5 (5-1) to (5-3). Table 5 shows the resin physical characteristics 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), the (5-4) additive formulation and granulation of Reference Example 5 According to (5-5), pellets of the resin composition (5B-1) containing the propylene homopolymer (PP-5-1) and talc (C) were prepared, and the resin composition (5B-) was subjected to the same (5-5) injection molding. An injection molded product was prepared from the pellets of 1). Table 5 shows the physical characteristics of the obtained injection molded product.

[Example 14] (Polypropylene homopolymer (A1): PP-5-2, a resin composition containing the propylene homopolymer (A1))
Reference Example 5 (5-3) Reference except that a propylene mixture containing 30% by weight of biomass-derived propylene and 70% by weight of fossil fuel-derived propylene was used as propylene in place of propylene derived from fossil fuel. A propylene homopolymer (PP-5-2), which is a propylene homopolymer (A1), was obtained in the same manner as in Examples 5 (5-1) to (5-3). 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), the (5-4) additive formulation and granulation of Reference Example 5 According to (5-5), pellets of the resin composition (5B-2) containing the propylene homopolymer (PP-5-2) and talc (C) were prepared, and the resin composition (5B-) was subjected to the same (5-5) injection molding. An injection molded product was prepared from the pellet of 2). Table 5 shows the physical characteristics of the obtained injection molded product.

[Example 15] (Polypropylene homopolymer (A1): PP-5-3, a resin composition containing the propylene homopolymer (A1))
Reference Example 5 (5-3) Reference except that a propylene mixture containing 65% by weight of biomass-derived propylene and 35% by weight of fossil fuel-derived propylene was used as propylene instead of fossil fuel-derived propylene. A propylene homopolymer (PP-5-3), which is a propylene homopolymer (A1), was obtained in the same manner as in Examples 5 (5-1) to (5-3). Table 5 shows the resin physical properties of the obtained propylene homopolymer (PP-5-3).
Using the propylene homopolymer (PP-5-3) obtained in place of the fossil fuel-derived propylene homopolymer (PP-5-0), the (5-4) additive formulation and granulation of Reference Example 5 According to the same procedure, pellets of the resin composition (5B-3) containing the propylene homopolymer (PP-5-3) and talc (C) were prepared, and according to the same (5-5) injection molding, the resin composition (5B-) was prepared. An injection molded product was prepared from the pellets of 3). Table 5 shows the physical characteristics of the obtained injection molded product.

[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 prepare a uniform 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 phthalic anhydride.
After cooling the uniform solution thus obtained to 23 ° C., 750 ml of this uniform solution was added dropwise to 2000 ml of titanium tetrachloride kept at −20 ° C. for 1 hour. After the dropping, the temperature of the obtained mixed solution was raised to 110 ° C. over 4 hours, 52.2 g of diisobutyl phthalate (DIBP) was added when the temperature reached 110 ° C., and the same temperature was stirred for 2 hours. Held in. Then, the solid part was collected by hot filtration, the solid part was resuspended in 2750 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours.
After the heating was completed, the solid part 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 is stored as a hexane slurry, and a part of the solid titanium catalyst component was dried to examine the catalyst composition. The solid titanium catalyst component contained titanium in an amount of 2% by weight, chlorine in an amount of 57% by weight, magnesium in an amount of 21% by weight, and DIBP in an amount of 20% 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 inserted into an autoclave with a stirrer having an internal capacity of 200 L and set to an internal temperature of 5 ° C. 560 g of retaining propylene was inserted and reacted with stirring for 60 minutes. After the completion of the polymerization, the solid component was allowed to settle, the supernatant was removed, and the washing with heptane was performed twice. The obtained prepolymerization catalyst was resuspended in purified heptane and adjusted with heptane so that the titanium catalyst component concentration was 0.7 g / L. This prepolymerization catalyst contained 10 g of polypropylene per 1 g of the solid titanium catalyst component. As propylene, fossil fuel-derived propylene was used.

(6-3) Main Polymerization In a circulating tubular polymerizer with a jacket having a content of 58 L, propylene was 30 kg / hour, hydrogen was 33 NL / hour, the catalyst slurry was 0.6 g / hour as a titanium catalyst component, and triethylaluminum 1.9 ml / hour. For hours, 1.1 ml / hour of cyclohexylmethyldimethoxysilane was continuously supplied, and polymerization was carried out in a full liquid state in which no gas phase was present. 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 polymerizer with a stirrer having an internal capacity of 100 L for further polymerization. Propylene was supplied to the polymerizer at 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase portion was 2.2 mol%. Polymerization was carried out at a polymerization temperature of 70 ° C. and a pressure of 3.1 MPa / G. As propylene, fossil fuel-derived propylene was used.
After vaporizing the obtained slurry, air-solid separation was carried out 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. At the time of MFR measurement, 1000 ppm of Irganox 1010 manufactured by Ciba Geigy and 1000 ppm of Ilgafos 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 To 79% by weight of the propylene homopolymer (PP-6-0) powder thus obtained in (6-3) and 1% by weight of maleic anhydride-modified polypropylene (F). , 1000 ppm of Ciba Geigy's Irganox 1010 and 1000 ppm of Ciba Geigy's Ilgafos 168 as antioxidants, based on the total of propylene homopolymer (PP-6-0) and maleic anhydride-modified polypropylene (F). 1000 ppm of calcium stearate is prescribed as a neutralizing agent, these are mixed by a tumbler, then quantitatively supplied to the hopper part by a fixed-quantity feeder, melt-kneaded by a twin-screw extruder under the following conditions, and further side of the twin-screw extruder. 20% by weight of glass short fibers (D) is quantitatively supplied to the above components melt-kneaded from the feed port by a fixed-quantity feeder, and further melt-kneaded to pellet the resin composition (6B-0) containing a polypropylene homopolymer. Was prepared.

<Melting and kneading conditions>
Same-direction twin-screw kneader: Part number TEX-30α (manufactured by Japan Steel Works, Ltd.)
Kneading temperature: 210 ° C

(6-5) Injection Molding Using the pellets obtained in (6-4), a test piece (injection molded product) was molded by an injection molding machine under the following conditions. Table 6 shows the physical characteristics of the injection-molded article made of the resin composition (6B-0).

<Injection molding conditions>
Injection molding machine: Part number ROBOSHOT α-100B (manufactured by FANUC Co., Ltd.)
Cylinder temperature: 230 ° C
Mold temperature: 40 ° C

[Example 16] (Polypropylene homopolymer (A1): PP-6-1, a resin composition containing the propylene homopolymer (A1))
Reference Example 6 (6-3) Reference except that a propylene mixture containing 10% by weight of biomass-derived propylene and 90% by weight of fossil fuel-derived propylene was used as propylene in place of propylene derived from fossil fuel. A propylene homopolymer (PP-6-1), which is a propylene homopolymer (A1), was obtained in the same manner as in Examples 6 (6-1) to (6-3). Table 6 shows the resin physical properties of the obtained propylene homopolymer (PP-6-1).
Using the polypropylene homopolymer (PP-6-1) obtained in place of the fossil fuel-derived polypropylene homopolymer (PP-6-0), the additive formulation and kneading of Reference Example 6 (6-4) were carried out. According to the granulation, pellets of the resin composition (6B-1) containing the propylene homopolymer (PP-6-1), maleic anhydride-modified polypropylene (F), and short glass fibers (D) were prepared, and the same (6B-1) was prepared. 6-5) An injection polymer was prepared from the pellets of the resin composition (6B-1) according to injection molding. Table 6 shows the physical characteristics of the obtained injection molded product.

[Example 17] (Polypropylene homopolymer (A1): PP-6-2, a resin composition containing the propylene homopolymer (A1))
Reference Example 6 (6-3) Reference except that a propylene mixture containing 30% by weight of biomass-derived propylene and 70% by weight of fossil fuel-derived propylene was used as propylene in place of propylene derived from fossil fuel. A propylene homopolymer (PP-6-2), which is a propylene homopolymer (A1), was obtained in the same manner as in Examples 6 (6-1) to (6-3). 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 polypropylene homopolymer (PP-6-0), the (6-4) additive formulation and kneading of Reference Example 6 According to the granulation, pellets of the resin composition (6B-2) containing the propylene homopolymer (PP-6-2), maleic anhydride-modified polypropylene (F), and short glass fibers (D) were prepared, and the same (6B-2) was prepared. 6-5) An injection polymer was prepared from the pellets of the resin composition (6B-2) according to injection molding. Table 6 shows the physical characteristics of the obtained injection molded product.

[Example 18] (Polypropylene homopolymer (A1): PP-6-3, a resin composition containing the propylene homopolymer (A1))
Reference Example 6 (6-3) Reference except that a propylene mixture containing 65% by weight of biomass-derived propylene and 35% by weight of fossil fuel-derived propylene was used as propylene in place of propylene derived from fossil fuel. A propylene homopolymer (PP-6-3), which is a propylene homopolymer (A1), was obtained in the same manner as in Examples 6 (6-1) to (6-3). Table 6 shows the resin physical properties of the obtained propylene homopolymer (PP-6-3).
Using the polypropylene homopolymer (PP-6-3) obtained in place of the fossil fuel-derived polypropylene homopolymer (PP-6-0), the additive formulation and kneading of Reference Example 6 (6-4) were carried out. According to the granulation, pellets of the resin composition (6B-3) containing the propylene homopolymer (PP-6-3), maleic anhydride-modified polypropylene (F), and short glass fibers (D) were prepared, and the same (6B-3) was prepared. 6-5) An injection polymer was prepared from the pellets of the resin composition (6B-3) according to injection molding. Table 6 shows the physical characteristics of the obtained injection molded product.

[Reference Example 7] (Fossil fuel-derived propylene homopolymer, resin composition containing the propylene homopolymer)
<Preparation of fossil fuel-derived propylene homopolymer (PP-7-0)>
(7-1) Preparation of solid titanium catalyst component Reference example (6-1) Similar to the preparation of solid titanium catalyst component, titanium is 2% by weight, chlorine is 57% by weight, magnesium is 21% by weight and DIBP. Was prepared in an amount of 20% by weight to prepare a solid titanium catalyst component.

(7-2) Polymerization pretreatment 180 g of solid titanium catalyst component, 30.9 mL of triethylaluminum, and 120 L of heptane were charged into an autoclave with a stirrer having an internal capacity of 200 L, and 1080 g of propylene was charged at an internal temperature of 5 ° C. The reaction was carried out with stirring for 60 minutes. After the completion of the polymerization, the solid component was allowed to settle, the supernatant was removed, and the washing with heptane was performed twice. The obtained prepolymerization catalyst was resuspended in purified heptane and adjusted with heptane so that the titanium catalyst component concentration was 1.5 g / L. This prepolymerization catalyst contained 6 g of polypropylene per 1 g of solid titanium catalyst component. As propylene, fossil fuel-derived propylene was used.

(7-3) Main Polymerization To a Vessel polymerizer (1) with a stirrer having an internal capacity of 100 L, propylene was supplied at 110 kg / h and hydrogen was supplied so that the hydrogen concentration in the gas phase portion was 0.8 mol%. The slurry of the prepolymerization catalyst produced in (7-2) was continuously supplied with 1.4 g / h as a solid titanium catalyst component, 5.8 ml / h of triethylaluminum, and 2.7 ml / h of dicyclopentyl dimethoxysilane. The polymerization temperature was 73 ° C. and the pressure was 3.2 MPa / G. As propylene, fossil fuel-derived propylene was used. (The same applies to the following steps.)
The slurry obtained in the Vessel polymerizer (1) was sent to another Vessel polymerizer (2) with a stirrer having an internal capacity of 1000 L for further polymerization. Propylene was supplied to the vessel polymerizer (2) at 30 kg / h, and hydrogen was supplied so that the hydrogen concentration in the gas phase portion 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 polymerizer (2) was sent to another Vessel polymerizer (3) with a stirrer having an internal capacity of 500 L for further polymerization. Propylene was supplied to the vessel polymerizer (3) at 45 kg / h, and hydrogen was supplied so that the hydrogen concentration in the gas phase portion 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, air-solid separation was carried out to obtain a powdery propylene homopolymer (PP-7-0). The propylene homopolymer was vacuum dried at 80 ° C. Table 7 shows the resin physical properties of the propylene homopolymer (PP-7-0) thus obtained. At the time of MFR measurement, 1000 ppm of Irganox 1010 manufactured by Ciba Geigy and 1000 ppm of Ilgafos 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 anhydrous maleic acid-modified polypropylene (F), 1000 ppm of Irganox 1010 manufactured by Ciba Geigy as an antioxidant with respect to the total of propylene homopolymer (PP-7-0) and maleic anhydride-modified polypropylene (F) in 10% by weight of carbon monofiber (E). A resin composition containing 1000 ppm of Ilgafos 168 manufactured by Ciba Geigy and 1000 ppm of calcium stearate as a neutralizing agent, mixed with a tumbler, and then melt-kneaded with a single-screw extruder under the following conditions to contain a polypropylene homopolymer. Pellets of (7B-0) were prepared.

<Melting and kneading conditions>
Single-screw kneader: Part number Labplast Mill 10M100 (manufactured by Toyo Seiki Co., Ltd.)
Kneading temperature: 220 ° C
Screw rotation speed: 60 rpm
Pellet length: about 5 mm

(7-5) Injection molding Using the pellets obtained in (7-4), a test piece (injection molded body) was molded by an injection molding machine under the following conditions. Table 7 shows the physical characteristics of the injection-molded article made of the resin composition (7B-0).

<Injection molding conditions>
Injection molding machine: Part number EC40 (manufactured by Toshiba Machine Co., Ltd.)
Cylinder temperature: 210 ° C
Mold temperature: 40 ° C
Injection time-holding time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds

[Example 19] (Polypropylene homopolymer (A1): PP-7-1, a resin composition containing the propylene homopolymer (A1))
Reference Example 7 (7-3) Reference except that a propylene mixture containing 10% by weight of biomass-derived propylene and 90% by weight of fossil fuel-derived propylene was used as propylene in place of propylene derived from fossil fuel. A propylene homopolymer (PP-7-1), which is a propylene homopolymer (A1), was obtained in the same manner as in Examples 7 (7-1) to (7-3). 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 polypropylene homopolymer (PP-7-0), the (7-4) additive formulation and kneading of Reference Example 7 were carried out. According to the granulation, pellets of the resin composition (7B-1) containing the propylene homopolymer (PP-7-1), maleic anhydride-modified polypropylene (F), and carbon monofilament (E) were prepared, and the same (7B-1) was prepared. 7-5) An injection polymer was prepared from the pellets of the resin composition (7B-1) according to injection molding. Table 7 shows the physical characteristics of the obtained injection molded product.

[Example 20] (Polypropylene homopolymer (A1): PP-7-2, a resin composition containing the propylene homopolymer (A1))
In the main polymerization of Reference Example 7 (7-3), except that a propylene mixture containing 30% by weight of biomass-derived propylene and 70% by weight of fossil fuel-derived propylene was used as propylene instead of fossil fuel-derived propylene. A propylene homopolymer (PP-7-2), which is a propylene homopolymer (A1), was obtained in the same manner as in Reference Example 7 (7-1) to (7-3). 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 polypropylene homopolymer (PP-7-0), the (7-4) additive formulation and kneading of Reference Example 7 were carried out. According to the granulation, pellets of the resin composition (7B-2) containing the propylene homopolymer (PP-7-2), maleic anhydride-modified polypropylene (F), and carbon monofilament (E) were prepared, and the same (7B-2) was prepared. 7-5) An injection polymer was prepared from the pellets of the resin composition (7B-2) according to injection molding. Table 7 shows the physical characteristics of the obtained injection molded product.

[Example 21] (Polypropylene homopolymer (A1): PP-7-3, a resin composition containing the propylene homopolymer (A1))
Reference Example 7 (7-3) Reference except that a propylene mixture containing 65% by weight of biomass-derived propylene and 35% by weight of fossil fuel-derived propylene was used as propylene in place of propylene derived from fossil fuel. A propylene homopolymer (PP-7-3), which is a propylene homopolymer (A1), was obtained in the same manner as in Examples 7 (7-1) to (7-3). Table 7 shows the resin physical properties of the obtained propylene homopolymer (PP-7-3).
Using the propylene homopolymer (PP-7-3) obtained in place of the fossil fuel-derived polypropylene homopolymer (PP-7-0), the (7-4) additive formulation and kneading of Reference Example 7 were carried out. According to the granulation, pellets of the resin composition (7B-3) containing the propylene homopolymer (PP-7-3), maleic anhydride-modified polypropylene (F), and carbon monofilament (E) were prepared, and the same (7B-3) was prepared. 7-5) An injection polymer was prepared from the pellets of the resin composition (7B-3) according to injection molding. Table 7 shows the physical characteristics of the obtained injection molded product.

[Reference Example 8] (Fossil fuel-derived propylene-based random copolymer, resin composition containing the propylene-based random copolymer)
<Preparation of fossil fuel-derived propylene-based random copolymer (PP-8-0)>
(8-1) Preparation of Magnesium Compound A magnesium compound (carrier of a solid catalyst) 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 put into a reaction vessel with a stirrer having an internal volume of 500 liters, 25 kg of the solid catalyst component was added, and 1 triethylaluminum was added to the titanium atom in the solid catalyst component. 0.0 mol / mol and dicyclopentyl dimethoxysilane were supplied at a ratio of 1.8 mol / mol. Then, propylene was introduced at a partial pressure of propylene until it reached 0.03 MPa-G, and the reaction was carried out at 25 ° C. for 4 hours. After completion of the reaction, the solid catalyst component was washed with purified heptane several times, carbon dioxide was further supplied, and the mixture was stirred for 24 hours. As propylene, fossil fuel-derived propylene was used.

(8-4) Main Polymerization In a polymerization apparatus with a stirrer with an internal capacity of 200 liters, the treated solid catalyst component of (8-3) above was added to the components in terms of titanium atoms at 3 mmol / hr and triethylaluminum was 2.5 mmol / hr. Dicyclopentyldimethoxysilane was supplied at 0.25 mmol / kg-PP at kg-PP, respectively. Then, propylene, ethylene, and 1-butene were continuously supplied at 46.0 kg / hr and 2.0 kg / hr, 2.4 kg / hr, respectively, at a polymerization temperature of 82 ° C. and a polymerization pressure of 2.8 MPa-G, and reacted. rice field. At this time, the ethylene concentration in the polymerization was 2.4 mol%, the 1-butene concentration was 1.8 mol%, and the hydrogen concentration was 8.2 mol%. 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. At the time of MFR measurement, 1000 ppm of Irganox 1010 manufactured by Ciba Geigy and 1000 ppm of Ilgafos 168 manufactured by Ciba Geigy were added as antioxidants.

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

<Melting and kneading conditions>
Same-direction twin-screw kneader: Part number KZW-15 (manufactured by Technobel Co., Ltd.)
Kneading temperature: 190 ° C
Screw rotation speed: 500 rpm
Feeder speed: 40 rpm

(8-6) Injection molding Using the pellets obtained in (8-5), a JIS test piece (injection molded body) was molded by an injection molding machine under the following conditions. Table 8 shows the physical characteristics of the injection-molded article made of the resin composition (8B-0).

<Injection molding conditions>
Injection molding machine: Part number EC40 (manufactured by Toshiba Machine Co., Ltd.)
Cylinder temperature: 190 ° C
Mold temperature: 40 ° C
Injection time-holding time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds

[Example 22] (Resin composition containing propylene-based random copolymer (A2-1): PP-8-1, the propylene-based random copolymer (A2-1))
In (8-4) main polymerization of Reference Example 8, a propylene mixture containing 10% by weight of biomass-derived propylene and 90% by weight of fossil fuel-derived propylene was used as propylene instead of fossil fuel-derived propylene, and ethylene was derived from biomass. Using an ethylene mixture containing 10% by weight of ethylene and 90% by weight of ethylene derived from fossil fuel, a 1-butene mixture containing 10% by weight of biomass-derived 1-butene and 90% by weight of 1-butene derived from fossil fuel was used as 1-butene. A propylene / ethylene / 1-butene random copolymer (A2-1), which is a propylene-based random copolymer (A2-1), is the same as in Reference Examples 8 (8-1) to (8-4) except that it is used. PP-8-1) was obtained. Table 8 shows the resin physical properties of the obtained propylene / ethylene / 1-butene random copolymer (PP-8-1).
(8-5) Additive of Reference Example 8 using a propylene-based random copolymer (PP-8-1) obtained in place of the fossil fuel-derived propylene-based random copolymer (PP-8-0). Pellets of the resin composition (8B-1) containing the propylene-based random copolymer (PP-8-1) and the ethylene / α-olefin copolymer (B) were prepared according to the formulation and kneading / granulation. An injection polymer was prepared from the pellets of the resin composition (8B-1) according to the same (8-6) injection molding. Table 8 shows the physical characteristics of the obtained injection molded product.

[Example 23] (Resin composition containing propylene-based random copolymer (A2-1): PP-8-2, the propylene-based random copolymer (A2-1))
In (8-4) main polymerization of Reference Example 8, a propylene mixture containing 30% by weight of biomass-derived propylene and 70% by weight of fossil fuel-derived propylene was used as propylene instead of fossil fuel-derived propylene, and ethylene was derived from biomass. Using an ethylene mixture containing 30% by weight of ethylene and 70% by weight of ethylene derived from fossil fuel, a 1-butene mixture containing 30% by weight of biomass-derived 1-butene and 70% by weight of 1-butene derived from fossil fuel was used as 1-butene. A propylene / ethylene / 1-butene random copolymer (A2-1), which is a propylene-based random copolymer (A2-1), is the same as in Reference Examples 8 (8-1) to (8-4) except that it is used. PP-8-2) was obtained. Table 8 shows the resin physical properties of the obtained propylene / ethylene / 1-butene random copolymer (PP-8-2).
(8-5) Additive of Reference Example 8 using a propylene-based random copolymer (PP-8-2) obtained in place of the fossil fuel-derived propylene-based random copolymer (PP-8-0). Pellets of a resin composition (8B-2) containing a propylene-based random copolymer (PP-8-2) and an ethylene / α-olefin copolymer (B) were prepared according to the formulation and kneading / granulation. An injection polymer was prepared from the pellets of the resin composition (8B-2) according to the same (8-6) injection molding. Table 8 shows the physical characteristics of the obtained injection molded product.

[Example 24] (Resin composition containing propylene-based random copolymer (A2-1): PP-8-3, the propylene-based random copolymer (A2-1))
In (8-4) main polymerization of Reference Example 8, a propylene mixture containing 65% by weight of biomass-derived propylene and 35% by weight of fossil fuel-derived propylene was used as propylene instead of fossil fuel-derived propylene, and ethylene was derived from biomass. Using an ethylene mixture containing 65% by weight of ethylene and 35% by weight of ethylene derived from fossil fuel, a 1-butene mixture containing 65% by weight of biomass-derived 1-butene and 35% by weight of 1-butene derived from fossil fuel was used as 1-butene. A propylene / ethylene / 1-butene random copolymer (A2-1), which is a propylene-based random copolymer (A2-1), is the same as in Reference Examples 8 (8-1) to (8-4) except that it is used. PP-8-3) was obtained. Table 8 shows the resin physical properties of the obtained propylene / ethylene / 1-butene random copolymer (PP-8-3).
(8-5) Additive of Reference Example 8 using a propylene-based random copolymer (PP-8-3) obtained in place of the fossil fuel-derived propylene-based random copolymer (PP-8-0). Pellets of a resin composition (8B-3) containing a propylene-based random copolymer (PP-8-3) and an ethylene / α-olefin copolymer (B) were prepared according to the formulation and kneading / granulation. An injection polymer was prepared from the pellets of the resin composition (8B-3) according to the same (8-6) injection molding. Table 8 shows the physical characteristics of the obtained injection molded product.

[Reference Example 9] (Fossil fuel-derived propylene / ethylene block copolymer, resin composition containing the propylene / ethylene block copolymer)
<Preparation of fossil fuel-derived propylene / ethylene block copolymer (PP-9-0)>
(9-1) Preparation of Solid Titanium Catalyst Component A solid titanium catalyst component was obtained in the same manner as in (4-1) of Reference Example 4.

(9-2) Prepolymerization Treatment 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 circulating tubular polymerizer with a jacket having an internal capacity of 58 L, propylene was 43 kg / hour, hydrogen was 300 NL / hour, and the catalyst slurry produced in (9-2) was used as a solid titanium catalyst component. 55 g / hour, 2.9 ml / hour of triethylaluminum and 3.1 ml / hour of dicyclopentyldimethoxysilane were continuously supplied, and the mixture was polymerized in a full liquid state in which no gas phase was present. The temperature of the tubular polymerizer was 70 ° C. and the pressure was 3.74 MPa / G. As propylene, fossil fuel-derived propylene was used. (The same applies to the following steps.)
The slurry obtained by the cyclic tubular polymerizer was sent to a Vessel polymerizer equipped with a stirrer having an internal capacity of 100 L, and further polymerization was carried out. Propylene was supplied to the polymerizer at 45 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase portion 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 by the Vessel polymerizer is transferred to a liquid transfer tube having an internal volume of 2.4 L, the slurry is gasified, and air-solid separation is performed. It was sent to a phase polymerizer and subjected to ethylene / propylene block copolymerization (preparation of propylene / ethylene random copolymer component (d)). At this time, the powder before the copolymerization was sampled, and the MFR, melting point, pentad fraction, and Mw / Mn were measured. At the time of MFR measurement, 1000 ppm of Irganox 1010 manufactured by Ciba Geigy and 1000 ppm of Ilgafos 168 manufactured by Ciba Geigy were added as antioxidants.

Propylene, ethylene, and hydrogen are continuously added so that the gas composition in the gas phase polymerizer is 0.23 (molar ratio) as ethylene / (ethylene + propylene) and 0.031 (molar ratio) as hydrogen / ethylene. Supplied. Polymerization was carried out at a polymerization temperature of 70 ° C. and a pressure of 1.0 MPa / G. In addition, ethylene derived from fossil fuel was used as ethylene.
After vaporizing the slurry obtained in the gas phase polymerizer, air-solid separation was carried out 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 Co., Ltd. and 1000 ppm of Ilgafos 168 manufactured by Ciba Geigy Co., Ltd. were added as antioxidants, and 1000 ppm of calcium stearate was 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 To 75% by weight of the propylene / ethylene block copolymer powder thus obtained in (9-3) and 25% by weight of the ethylene / α-olefin copolymer (B). To the total of the propylene / ethylene block copolymer and the ethylene / α-olefin copolymer (B), 1000 ppm of Irganox 1010 manufactured by Ciba Geigy and 1000 ppm of Ilgafos 168 manufactured by Ciba Geigy were neutralized as antioxidants. 1000 ppm of calcium stearate is prescribed as an agent, and these are mixed by a tumbler and then melt-kneaded under the following conditions by a twin-screw extruder to prepare pellets of a resin composition (9B-0) containing a propylene / ethylene block copolymer. did.

<Melting and kneading conditions>
Same-direction twin-screw kneader: Part number KZW-15 (manufactured by Technobel Co., Ltd.)
Kneading temperature: 190 ° C
Screw rotation speed: 500 rpm
Feeder speed: 40 rpm

(9-5) Injection molding Using the pellets obtained in (9-4), a JIS test piece (injection molded body) is molded by an injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.] under the following conditions. did. Table 9 shows the physical characteristics of the injection-molded article made of the resin composition (9B-0).

<Injection molding conditions>
Injection molding machine: Part number EC40 (manufactured by Toshiba Machine Co., Ltd.)
Cylinder temperature: 190 ° C
Mold temperature: 40 ° C
Injection time-holding time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds

[Example 25]
In (9-3) main polymerization of Reference Example 9, a propylene mixture containing 10% by weight of biomass-derived propylene and 90% by weight of fossil fuel-derived propylene was used as propylene instead of fossil fuel-derived propylene, and ethylene was derived from biomass. Propylene-ethylene block copolymer in the same manner as in Reference Examples 9 (9-1) to (9-3) except that an ethylene mixture containing 10% by weight of ethylene and 90% by weight of ethylene derived from fossil fuel was used. A propylene / ethylene block copolymer (PP-9-1) which is (A2-2) was obtained. Table 9 shows the resin physical properties of the obtained propylene / ethylene block copolymer (PP-9-1).

Using a propylene / ethylene block copolymer (PP-9-1) obtained in place of the fossil fuel-derived propylene / ethylene block copolymer (PP-9-0), Reference Example 9 (9-4) Pellets of the resin composition (9B-1) containing the propylene / ethylene block copolymer (PP-9-1) and the ethylene / α-olefin copolymer (B) according to the additive formulation and kneading / granulation are prepared. Preparations were made, and an injection polymer was prepared from pellets of the resin composition (9B-1) according to the same (9-5) injection molding. Table 9 shows the physical characteristics of the obtained injection molded product.

[Example 26]
In (9-3) main polymerization of Reference Example 9, a propylene mixture containing 30% by weight of biomass-derived propylene and 70% by weight of fossil fuel-derived propylene was used as propylene in place of propylene derived from fossil fuel, and the ethylene was derived from biomass. Propylene-ethylene block copolymer in the same manner as in Reference Examples 9 (9-1) to (9-3) except that an ethylene mixture containing 30% by weight of ethylene and 70% by weight of ethylene derived from fossil fuel was used. A propylene / ethylene block copolymer (PP-9-2), which is (A2-2), was obtained. Table 9 shows the resin physical properties of the obtained propylene / ethylene block copolymer (PP-9-2).

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

[Example 27]
In (9-3) main polymerization of Reference Example 9, a propylene mixture containing 65% by weight of biomass-derived propylene and 35% by weight of fossil fuel-derived propylene was used as propylene instead of propylene derived from fossil fuel, and ethylene was derived from biomass. Propylene-ethylene block copolymer in the same manner as in Reference Examples 9 (9-1) to (9-3) except that an ethylene mixture containing 65% by weight of ethylene and 35% by weight of ethylene derived from fossil fuel was used. A propylene / ethylene block copolymer (PP-9-3), which is (A2-2), was obtained. Table 9 shows the resin physical properties of the obtained propylene / ethylene block copolymer (PP-9-3).

Using a propylene / ethylene block copolymer (PP-9-3) obtained in place of the fossil fuel-derived propylene / ethylene block copolymer (PP-9-0), Reference Example 9 (9-4) Pellets of the resin composition (9B-3) containing the propylene / ethylene block copolymer (PP-9-3) and the ethylene / α-olefin copolymer (B) according to the additive formulation and kneading / granulation are prepared. Preparations were made, and an injection polymer was prepared from pellets of the resin composition (9B-3) according to the same (9-5) injection molding. Table 9 shows the physical characteristics of the obtained injection molded product.

[Reference Example 10] (Fossil fuel-derived propylene / ethylene block copolymer, resin composition containing the propylene / ethylene block copolymer)
<Preparation of fossil fuel-derived propylene / ethylene block copolymer (PP-10-0)>
(10-1) Preparation of Solid Titanium Catalyst Component A solid titanium catalyst component was obtained in the same manner as in (4-1) of Reference Example 4.

(10-2) Pretreatment for Polymerization 100 g of the solid titanium catalyst component, 131 mL of triethylaluminum, 37.3 ml of diethylaminotriethoxysilane, and 14.3 L of heptane obtained in (10-1) are inserted into an autoclave with a stirrer having an content of 20 L. Then, the internal temperature was maintained at 15 to 20 ° C., 1000 g of propylene was inserted, and the reaction was carried out with stirring for 120 minutes. After the completion of the polymerization, the solid component was allowed to settle, the supernatant was removed, and the washing with heptane was performed twice. The obtained prepolymerization catalyst was resuspended in purified heptane and adjusted with heptane so that the concentration of the solid titanium catalyst component was 1.0 g / L to obtain a catalyst slurry.

(10-3) Main Polymerization In a circulating tubular polymerizer with a jacket having an internal capacity of 58 L, propylene was 43 kg / hour, hydrogen was 256 NL / hour, and the catalyst slurry produced in (10-2) was used as a solid titanium catalyst component. Triethylaluminum was continuously supplied at 49 g / hour, triethylaluminum at 4.5 ml / hour, and diethylaminotriethoxysilane at 1.8 ml / hour, and polymerization was carried out in a full liquid state in which no gas phase was present. The temperature of the tubular polymerizer was 70 ° C. and the pressure was 3.57 MPa / G. As propylene, fossil fuel-derived propylene was used (the same applies to the following steps).
The slurry obtained by the tubular polymerizer was sent to a Vessel polymerizer equipped with a stirrer having an internal capacity of 100 L for further polymerization. Propylene was supplied to the polymerizer at 45 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase portion 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 by the Vessel polymerizer was transferred to a liquid transfer tube having an internal volume of 2.4 L, the slurry was gasified, and the air-solid separation was performed. It was sent to a gas phase polymerizer to perform ethylene / propylene block copolymerization (preparation of propylene / ethylene random copolymer component (d)). At this time, the powder before the copolymerization was sampled, and the MFR, melting point, pentad fraction, and Mw / Mn were measured. At the time of MFR measurement, 1000 ppm of Irganox 1010 manufactured by Ciba Geigy and 1000 ppm of Ilgafos 168 manufactured by Ciba Geigy were added as antioxidants.

Propylene, ethylene, and hydrogen are continuously added so that the gas composition in the gas phase polymerizer is 0.20 (molar ratio) as ethylene / (ethylene + propylene) and 0.0063 (molar ratio) as hydrogen / ethylene. Supplied. Polymerization was carried out at a polymerization temperature of 70 ° C. and a pressure of 1.40 MPa / G. In addition, ethylene derived from fossil fuel was used as ethylene.
After vaporizing the slurry obtained in the gas phase polymerizer, air-solid separation was carried out 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 Co., Ltd. and 1000 ppm of Ilgafos 168 manufactured by Ciba Geigy Co., Ltd. were added as antioxidants, and 1000 ppm of calcium stearate was 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 thus obtained in (10-3), 20% by weight of the ethylene / α-olefin copolymer (B), talc. (C) To 20% by weight, 1000 ppm of Irganox 1010 manufactured by Ciba Geigy Co., Ltd. and Ciba Geigy Co., Ltd. as an antioxidant are added to the total of the propylene / ethylene block copolymer and the ethylene / α-olefin copolymer (B). Irgafos 168 is formulated at 1000 ppm and calcium stearate at 1000 ppm as a neutralizing agent is formulated, and these are mixed by a tumbler and then melt-kneaded under the following conditions by a twin-screw extruder to contain a resin composition containing a propylene / ethylene block copolymer (a resin composition containing a propylene / ethylene block copolymer). 10B-0) pellets were prepared.

<Melting and kneading conditions>
Same-direction twin-screw kneader: Part number KZW-15 (manufactured by Technobel Co., Ltd.)
Kneading temperature: 190 ° C
Screw rotation speed: 500 rpm
Feeder speed: 40 rpm

(10-5) Injection molding Using the pellets obtained in (10-4), a JIS test piece (injection molded body) was molded by an injection molding machine under the following conditions. Table 10 shows the physical characteristics of the injection-molded article made of the resin composition (10B-0).

<Injection molding conditions>
Injection molding machine: Part number EC40 (manufactured by Toshiba Machine Co., Ltd.)
Cylinder temperature: 190 ° C
Mold temperature: 40 ° C
Injection time-holding time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds

[Example 28]
In (10-3) main polymerization of Reference Example 10, a propylene mixture containing 10% by weight of biomass-derived propylene and 90% by weight of fossil fuel-derived propylene was used as propylene instead of fossil fuel-derived propylene, and ethylene was derived from biomass. Propylene-ethylene block copolymer in the same manner as in Reference Example 10 (10-1) to (10-3) except that an ethylene mixture containing 10% by weight of ethylene and 90% by weight of ethylene derived from fossil fuel was used. A propylene / ethylene block copolymer (PP-10-1) which is (A2-2) was obtained. Table 10 shows the resin physical properties of the obtained propylene / ethylene block copolymer (PP-10-1).

Using a propylene / ethylene block copolymer (PP-10-1) obtained in place of the fossil fuel-derived propylene / ethylene block copolymer (PP-10-0), Reference Example 10 (10-4) Resin composition (10B-) containing propylene / ethylene block copolymer (PP-9-1), ethylene / α-olefin copolymer (B), and talc (C) according to additive formulation and kneading / granulation. The pellets of 1) were prepared, and an injection polymer was prepared from the pellets of the resin composition (10B-1) according to the same (10-5) injection molding. Table 10 shows the physical characteristics of the obtained injection molded product.

[Example 29]
In (10-3) main polymerization of Reference Example 10, a propylene mixture containing 30% by weight of biomass-derived propylene and 70% by weight of fossil fuel-derived propylene was used as propylene in place of propylene derived from fossil fuel, and the ethylene was derived from biomass. Propylene-ethylene block copolymer in the same manner as in Reference Example 10 (10-1) to (10-3) except that an ethylene mixture containing 30% by weight of ethylene and 70% by weight of ethylene derived from fossil fuel was used. A propylene / ethylene block copolymer (PP-10-2), which is (A2-2), was obtained. Table 10 shows the resin physical properties of the obtained propylene / ethylene block copolymer (PP-10-2).

Using a propylene / ethylene block copolymer (PP-10-2) obtained in place of the fossil fuel-derived propylene / ethylene block copolymer (PP-10-0), Reference Example 10 (10-4) Resin composition (10B-) containing propylene / ethylene block copolymer (PP-9-2), ethylene / α-olefin copolymer (B), and talc (C) according to additive formulation and kneading / granulation. The pellets of 2) were prepared, and an injection polymer was prepared from the pellets of the resin composition (10B-2) according to the same (10-5) injection molding. Table 10 shows the physical characteristics of the obtained injection molded product.

[Example 30]
In (10-3) main polymerization of Reference Example 10, a propylene mixture containing 65% by weight of biomass-derived propylene and 35% by weight of fossil fuel-derived propylene was used as propylene instead of fossil fuel-derived propylene, and ethylene was derived from biomass. Propylene-ethylene block copolymer in the same manner as in Reference Example 10 (10-1) to (10-3) except that an ethylene mixture containing 65% by weight of ethylene and 35% by weight of ethylene derived from fossil fuel was used. A propylene / ethylene block copolymer (PP-10-3), which is (A2-2), was obtained. Table 10 shows the resin physical properties of the obtained propylene / ethylene block copolymer (PP-10-3).

Using a propylene / ethylene block copolymer (PP-10-3) obtained in place of the fossil fuel-derived propylene / ethylene block copolymer (PP-10-0), Reference Example 10 (10-4) Resin composition (10B-) containing propylene / ethylene block copolymer (PP-9-3), ethylene / α-olefin copolymer (B), and talc (C) according to additive formulation and kneading / granulation. The pellets of 3) were prepared, and an injection polymer was prepared from the pellets of the resin composition (10B-3) according to the same (10-5) injection molding. Table 10 shows the physical characteristics of the obtained injection molded product.

From the results of Tables 1 to 10, the resin composition containing the propylene-based polymer (A) and the propylene-based polymer (A) of the present invention is an existing fossil fuel having a large environmental load and whose raw material is a fossil fuel-derived olefin. It has the same performance as the derived propylene-based polymer and the resin composition containing the propylene-based polymer. On the other hand, the propylene-based polymer (A) of the present invention can be obtained by using only the biomass-derived olefin as a raw material, or can be derived from any desired biomass without diluting the biomass-derived propylene-based polymer with the fossil fuel-derived propylene-based polymer. The carbon concentration can be any desired biomass degree. INDUSTRIAL APPLICABILITY According to the present invention, it is possible to reduce the environmental load, reduce the cost, and promote the spread of propylene-based polymers having the effect of reducing the environmental load.

Claims (20)

It is a propylene homopolymer or a propylene-based polymer which is a copolymer of propylene and ethylene and at least one olefin (b) selected from the group consisting of α-olefin having 4 to 8 carbon atoms, and is described below (I). )-(II) is satisfied with the propylene-based polymer.
(I) At least one olefin (a) selected from the group consisting of propylene, ethylene, and α-olefins having 4 to 8 carbon atoms contained in the raw material of the propylene-based polymer is a biomass-derived olefin (a1) 0. An olefin mixture containing 2% by weight or more and 99% by weight or less and a fossil fuel-derived olefin (a2) of 1% by weight or more and 99.8% by weight or less (total of biomass-derived olefin (a1) and fossil fuel-derived olefin (a2)). Is 100% by weight).
(II) The biomass-derived carbon concentration of the propylene-based polymer is 0.2 pMC (%) or more and 99.0 pMC (%) or less. The propylene-based polymer is a propylene homopolymer and
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 according to claim 2, which is a propylene homopolymer having a biomass degree of 1% or more and 99% or less according to ASTM D 6866. The propylene-based polymer is a random copolymer of propylene and at least one olefin (b) selected from the group consisting of ethylene and α-olefins having 4 to 8 carbon atoms.
The random copolymer contains 90.0% by weight or more and 99.9% by weight or less of the structural unit derived from propylene and 0.1% by weight or more and 10.0% by weight or less of the structural unit derived from the olefin (b). Including,
The propylene contained in the raw material of the random copolymer contains (I-1) 0.2% by weight or more and 99% by weight or less of biomass-derived propylene and 1% by weight or more and 99.8% by weight or less of propylene derived from fossil fuel. It is a propylene mixture (the total of biomass-derived propylene and fossil fuel-derived propylene is 100% by weight).
The propylene-based polymer according to claim 1, which also satisfies the following (iii) to (iv).
(Iii) 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 (iv) Melting point is 100 ° C. or more and 160 ° C. or less. A random copolymer of propylene having a biomass degree of 1% or more and 99% or less according to ASTM D 6866 and at least one olefin (b) selected from the group consisting of ethylene and α-olefins having 4 to 8 carbon atoms. The propylene-based polymer according to claim 4. The propylene-based polymer is a propylene / ethylene block copolymer, and is
The propylene contained in the raw material of the propylene / ethylene block copolymer is (I-1).
) Biomass-derived propylene A propylene mixture containing 0.2% by weight or more and 99% by weight or less and fossil fuel-derived propylene by 1% by weight or more and 99.8% by weight or less (the total of biomass-derived propylene and fossil fuel-derived propylene is 100). By weight%),
The propylene / ethylene block copolymer
It comprises a propylene homopolymer or a crystalline propylene / ethylene random copolymer containing 95% by weight or more and less than 100% by weight of a structural unit derived from propylene and 5% by weight or less of a structural unit derived from ethylene, as described in (v) below.
(V) The ultimate viscosity [η] is 0.8 (dl / g) or more and 3.0 (dl / g).
Crystalline propylene-based polymer component (c) 55% by weight or more and 95% by weight, which satisfies the above conditions.
Containing 20% by weight or more and 80% by weight or less of the structural unit derived from propylene and 20% by weight or more and 80% by weight of the structural unit derived from ethylene, the following (vi)
(Vi) The ultimate viscosity [η] is 1.0 (dl / g) or more and 10.0 (dl / g).
The propylene-based polymer according to claim 1, which contains 5% by weight or more and 45% by weight or less of the propylene / ethylene random copolymer component (d) satisfying the above conditions. The propylene-based polymer according to claim 6, which is a propylene / ethylene block copolymer having a biomass degree of 1% to 99% according to ASTM D 6866. At least one selected from the group consisting of a propylene homopolymer having a biomass-derived carbon concentration of 0.2 pMC (%) or more and 99.0 pMC (%) or less, or an α-olefin having 4 to 8 carbon atoms of propylene and ethylene. Is a method for producing a propylene-based polymer which is a copolymer with the olefin (b) of the above.
Including the step of supplying a raw material containing propylene to a polymerizer and polymerizing with a polymerization catalyst.
At least one olefin (a) selected from the group consisting of propylene, ethylene, and α-olefin having 4 to 8 carbon atoms contained in the raw material is 0.2% by weight or more and 99% by weight of the biomass-derived olefin (a1). It is an olefin mixture containing the following and 1% by weight or more and 99.8% by weight or less of the fossil fuel-derived olefin (a2) (the total of the biomass-derived olefin (a1) and the fossil fuel-derived olefin (a2) is 100% by weight). , A method for producing a propylene-based polymer. The propylene-based polymer is a propylene homopolymer satisfying the following (i) to (ii);
(I) Melt flow rate (MFR) at 230 ° C. and 2.16 kg load 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 Includes a step of supplying propylene, which is a raw material, to a polymerizer and polymerizing with a polymerization catalyst.
The raw material is a propylene mixture containing (I-1) 0.2% by weight or more and 99% by weight or less of biomass-derived propylene and 1% by weight or more and 99.8% by weight or less of fossil fuel-derived propylene (with biomass-derived propylene). The method for producing a propylene-based polymer according to claim 8, wherein the total amount of the fossil fuel-derived propylene and the propylene is 100% by weight. The propylene-based polymer has a random common weight with at least one olefin (b) selected from the group consisting of propylene and ethylene and an α-olefin having 4 to 8 carbon atoms, which satisfies the following (iii) to (iv). It is a coalescence,
(Iii) 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 (iv) Melting point is 100 ° C. or higher and 160 ° C. or lower. The method for producing a propylene-based polymer according to claim 8, wherein the raw material comprises propylene, ethylene, and at least one olefin (b) selected from the group consisting of α-olefins having 4 to 8 carbon atoms. The random copolymer is composed of 90.0% by weight or more and 99.9% by weight or less of the structural unit derived from propylene and 0.1% by weight or more and 10.0% by weight of the structural unit derived from at least one olefin (b). Including% or less
The raw material supplied to the polymerizer is
(I-1) Biomass-derived propylene A propylene mixture containing 0.2% by weight or more and 99% by weight or less and fossil fuel-derived propylene by 1% by weight or more and 99.8% by weight or less (total of biomass-derived propylene and fossil fuel-derived propylene). Is 100% by weight), including
The method for producing a propylene-based polymer according to claim 10. The propylene-based polymer is a propylene / ethylene block copolymer, and is
The propylene / ethylene block copolymer
It comprises a propylene homopolymer or a crystalline propylene / ethylene random copolymer containing 95% by weight or more and less than 100% by weight of a structural unit derived from propylene and 5% by weight or less of a structural unit derived from ethylene, as described in (v) below.
(V) The ultimate viscosity [η] is 0.8 (dl / g) or more and 3.0 (dl / g).
Crystalline propylene-based polymer component (c) 55% by weight or more and 95% by weight, which satisfies the above conditions.
Containing 20% by weight or more and 80% by weight or less of the structural unit derived from propylene and 20% by weight or more and 80% by weight of the structural unit derived from ethylene, the following (vi)
(Vi) The ultimate viscosity [η] is 1.0 (dl / g) or more and 10.0 (dl / g).
Contains 5% by weight or more and 45% by weight or less of the propylene / ethylene random copolymer component (d) satisfying the above conditions.
A raw material (1) containing propylene or propylene and ethylene is supplied to a polymerizer and polymerized by a polymerization catalyst.
A crystalline propylene-based polymer comprising a propylene homopolymer or a crystalline propylene / ethylene random copolymer containing 95% by weight or more and less than 100% by weight of a structural unit derived from propylene and 5% by weight or less of a structural unit derived from ethylene. The step (α) for producing the component (c) and the raw material (2) containing propylene and ethylene are supplied to the polymer and polymerized by a polymerization catalyst to prepare the propylene / ethylene random copolymer component (d). The method for producing a propylene-based polymer according to claim 8, which comprises the step (β). Propylene contained in the raw materials (1) and (2) supplied to the polymer is 0.2% by weight or more and 99% by weight or less of propylene derived from biomass and 1% by weight or more and 99.8% by weight or less of propylene derived from fossil fuel. The method for producing a propylene-based polymer according to claim 12, which is a propylene mixture containing propylene (the total of propylene derived from biomass and propylene derived from fossil fuel is 100% by weight). A resin composition containing the propylene homopolymer according to claim 2 or 3. A resin composition comprising a random copolymer of propylene according to claim 4 or 5 and at least one olefin (b) selected from the group consisting of ethylene and α-olefins having 4 to 8 carbon atoms. A resin composition containing the propylene / ethylene block copolymer according to claim 6 or 7. A molded product made of the propylene homopolymer according to claim 2 or 3. A molded product composed of a random copolymer of propylene according to claim 4 or 5 and at least one olefin (b) selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms. A molded product made of the propylene / ethylene block copolymer according to claim 6 or 7. A molded product made of the resin composition according to any one of claims 14 to 16.