WO2025206121A1 - Olefin-based resin, olefin-based resin production method, resin composition, molded article, package for lithium ion batteries, and power storage device - Google Patents

Abstract

The present invention addresses the problem of providing: a new olefin-based resin useful as a compatibilizer between a propylene-based polymer and an ethylene-based polymer, and an application of the olefin-based resin; and a resin composition and a molded article that contain a propylene-based polymer and an ethylene-based polymer, and that exhibit an improved balance between impact resistance and elongation or strength.　An olefin-based resin (β) according to the present invention contains a graft-type olefin-based polymer [R1] having a main chain and a side chain, and satisfies all of requirements (I)-(IV): (I) the main chain of [R1] is formed from an ethylene-propylene copolymer or an ethylene-1-butene copolymer; (II) the side chain of [R1] is formed from a propylene homopolymer or a propylene-ethylene copolymer; (III) in (β), the content of the total P of specific components in components, etc., derived from a side chain material is in a range of 10-80 mass%; and (IV) the limiting viscosity [η] of (β) is 0.5-5.0 dL/g.

Description

Olefin-based resin, method for producing olefin-based resin, resin composition, molded body, packaging body for lithium-ion battery, and electricity storage device

The present invention relates to an olefin-based resin, a method for producing an olefin-based resin, a resin composition, a molded article, a packaging body for lithium-ion batteries, and an electricity storage device.

Plastic products are used in a variety of fields, and products made from polyolefin resin materials are particularly widely used as various containers and are produced in large quantities. While recycling of plastic products has been progressing in recent years, there is also a need for further recycling of used products made from polyolefin resin and discarded plastics.

Propylene-based polymers and ethylene-based polymers are commonly used as polyolefin-based resin materials, but because the two are incompatible, even if they are mixed and recycled, they do not disperse uniformly, resulting in reduced physical properties and limited applications. For this reason, there has been a demand for the development of a method to make propylene-based polymers and ethylene-based polymers compatible.

Methods proposed for compatibilizing or compatibilizing propylene-based polymers and ethylene-based polymers include a method using a crystalline block composite containing i) a crystalline ethylene-based polymer, ii) a crystalline propylene-based polymer, and iii) a block copolymer having a crystalline ethylene-based block and a crystalline propylene block (see Patent Documents 1 to 4), a method using a plastomer, which is an ethylene-α-olefin copolymer with a specific weight-average molecular weight, density, and crystallinity (see Patent Document 5), a method using a thermoplastic random copolymer containing ethylene and propylene and having a specific melting point obtained using a specific catalyst (see Patent Document 6), and more recently, an olefin-based resin containing a graft-type olefin-based polymer (see Patent Documents 7 and 8).

Special table 2016-537449 publication Japanese Patent Application Laid-Open No. 2019-116638 Patent No. 5860043 Patent No. 6783851 Special Publication No. 6-511028 Patent No. 5466986 Special Publication No. 2022-548039 International Publication No. 2023/101004

However, previously reported compatibilizers left room for improvement in the balance between impact resistance and elongation, or the balance between impact resistance and strength. The present invention aims to provide a new olefin-based resin that is useful as a compatibilizer for propylene-based polymers and ethylene-based polymers, and to provide uses for this olefin-based resin. Another objective of the present invention is to provide a resin composition and molded article, as well as a packaging body for lithium-ion batteries and an electricity storage device, that contain a propylene-based polymer and an ethylene-based polymer and have an improved balance between impact resistance and elongation, or the balance between impact resistance and strength.

The present invention relates to, for example, the following [1] to [29].
[1] An olefin resin (β) containing a graft-type olefin polymer [R1] having a main chain and a side chain,
An olefin-based resin (β) that satisfies all of the following requirements (I) to (IV):
(I) The main chain of the graft-type olefin polymer [R1] is composed of an ethylene-propylene copolymer or an ethylene-1-butene copolymer;
(II) The side chain of the graft-type olefin polymer [R1] is composed of a propylene homopolymer or a propylene-ethylene copolymer;
(III) The total content of P of the following components (i) to (iv) in the olefin-based resin (β) is in the range of 10 to 80 mass%:
(i) a propylene homopolymer constituting the side chain of the graft-type olefin polymer [R1];
(ii) a propylene-ethylene copolymer constituting the side chain of the graft-type olefin polymer [R1];
(iii) a terminally unsaturated propylene homopolymer that does not constitute the graft-type olefin polymer [R1];
(iv) a terminally unsaturated propylene-ethylene copolymer that does not constitute the graft-type olefin polymer [R1];
(IV) The intrinsic viscosity [η] of the olefin resin (β) measured in decalin at 135° C. is 0.5 to 5.0 dL/g.

[2] The main chain of the graft type olefin polymer [R1] is an ethylene-propylene copolymer,
the ethylene-propylene copolymer has a structural unit content derived from ethylene of 70 to 99 mol %;
The olefin-based resin (β) according to [1], wherein the content of structural units derived from propylene in the ethylene-propylene copolymer is 1 to 30 mol%.

[3] The olefin resin (β) according to [2], wherein the weight average molecular weight (Mw) of the ethylene-propylene copolymer constituting the main chain of the grafted olefin polymer [R1], as determined by gel permeation chromatography (GPC) in terms of polyethylene, is 50,000 to 250,000.
[4] The olefin-based resin (β) according to [2] or [3], wherein the total P content of the components (i) to (iv) in the olefin-based resin (β) is 10 to 60 mass%.

[5] The olefin-based resin (β) according to any one of [2] to [4], wherein the melt flow rate (MFR) of the olefin-based resin (β) measured in accordance with ASTM D1238 at 190°C under a load of 2.16 kg is 0.01 to 30 g/10 min.
[6] The ethylene-propylene copolymer has a structural unit content derived from ethylene of 75 to 85 mol %,
the ethylene-propylene copolymer has a structural unit content derived from propylene of 15 to 25 mol %,
[2] to [5], wherein the intrinsic viscosity [η] of the olefin resin (β) measured in decalin at 135 ° C. is 0.9 to 1.25 dL / g. [6] The olefin resin (β) according to any one of [2] to [5].

[7] The main chain of the graft type olefin polymer [R1] is an ethylene-1-butene copolymer,
the ethylene-1-butene copolymer has a structural unit content of 70 to 90 mol % derived from ethylene;
the ethylene/1-butene copolymer has a content of structural units derived from 1-butene of 10 to 30 mol %,
The olefin resin (β) according to [1], wherein the weight average molecular weight (Mw) of the ethylene-1-butene copolymer, as calculated as a polyethylene equivalent by gel permeation chromatography (GPC), is 30,000 to 120,000.

[8] The olefin-based resin (β) according to [7], wherein the melt flow rate (MFR) of the olefin-based resin (β) is 2.5 to 30 g/10 min, as measured at 190 ° C. under a load of 2.16 kg in accordance with ASTM D1238.
[9] The ethylene-1-butene copolymer has a structural unit content derived from ethylene of 78 to 87 mol %,
The olefin-based resin (β) according to [7] or [8], wherein the content of structural units derived from 1-butene in the ethylene/1-butene copolymer is 13 to 22 mol%.

[10] The olefin-based resin (β) according to any one of [7] to [9], wherein the intrinsic viscosity [η] of the olefin-based resin (β) measured in decalin at 135 ° C. is 0.5 to 1.25 dL / g.
[11] The content of structural units derived from propylene in the side chains of the graft type olefin polymer [R1] is 80 to 100 mol %,
the content of structural units derived from ethylene in the side chains of the graft type olefin polymer [R1] is 0 to 20 mol %,
The olefin resin (β) according to any one of [1] to [10], wherein the weight average molecular weight (Mw) of the polymer or copolymer constituting the side chain of the grafted olefin polymer [R1], as determined by gel permeation chromatography (GPC) in terms of polypropylene, is in the range of 5,000 to 50,000.

[12] A method for producing the olefin resin (β) according to any one of [1] to [11], comprising the following steps (A) and (B):
(A) In the presence of an olefin polymerization catalyst containing a transition metal compound [A] of Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton,
a step of polymerizing propylene to produce a terminally unsaturated polypropylene, or a step of copolymerizing propylene and ethylene to produce a terminally unsaturated propylene-ethylene copolymer;
(B) in the presence of an olefin polymerization catalyst containing a bridged metallocene compound represented by the following general formula [B]:
A step of copolymerizing the terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer produced in step (A) with ethylene and propylene, or a step of copolymerizing the terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer produced in step (A) with ethylene and 1-butene.
(In formula [B], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a heteroatom-containing group other than a silicon-containing group, and any two adjacent groups among R ¹ to R ⁴ may be bonded to each other to form a ring. R ⁶ and R ¹¹ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group, R ⁷ and R ¹⁰ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group, R ⁶ and R ⁷ may be bonded to each other to form a ring, and R ¹⁰ and R ¹¹ may be bonded to each other to form a ring; provided that R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms. R ¹³ and R ¹⁴ each independently represent an aryl group. ^Y1 represents a carbon atom or a silicon atom. ^M1 represents a zirconium atom or a hafnium atom. Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or non-conjugated diene having 4 to 10 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair, and j represents an integer of 1 to 4, and when j is an integer of 2 or greater, multiple Qs may be the same or different.

[13] An olefin-based resin (β) according to any one of [1] to [11];
a propylene-based polymer (α1);
A resin composition (X) comprising an ethylene polymer (α2).
[14] The main chain of the graft type olefin polymer [R1] in the olefin resin (β) is an ethylene-propylene copolymer,
a ratio ((β)/((α1)+(α2))) of the total mass of the olefin resin (β) to the total mass of the propylene polymer (α1) and the ethylene polymer (α2) is 0.02 to 0.23;
The resin composition (X) according to [13].

[15] The main chain of the graft type olefin polymer [R1] in the olefin resin (β) is an ethylene-propylene copolymer,
the melt flow rate (MFR) of the propylene polymer (α1) measured in accordance with ASTM D1238 at 230°C under a load of 2.16 kg is 0.01 to 20 g/10 min;
The resin composition (X) according to [13] or [14].

[16] The main chain of the graft type olefin polymer [R1] in the olefin resin (β) is an ethylene-propylene copolymer,
the melt flow rate (MFR) of the ethylene polymer (α2) is 0.01 to 2.0 g/10 min, as measured at 190°C under a load of 2.16 kg in accordance with ASTM D1238;
[13] The resin composition (X) according to any one of [15] to [16].
[17] The main chain of the graft type olefin polymer [R1] in the olefin resin (β) is an ethylene-1-butene copolymer,
a ratio ((β)/((α1)+(α2))) of the total mass of the olefin resin (β) to the total mass of the propylene polymer (α1) and the ethylene polymer (α2) is 0.08 to 0.20;
The resin composition (X) according to [13].

[18] The main chain of the graft type olefin polymer [R1] in the olefin resin (β) is an ethylene-1-butene copolymer,
the melt flow rate (MFR) of the propylene polymer (α1) measured in accordance with ASTM D1238 at 230°C under a load of 2.16 kg is 0.01 to 25 g/10 min;
The resin composition (X) according to [13] or [17].
[19] The main chain of the graft type olefin polymer [R1] in the olefin resin (β) is an ethylene-1-butene copolymer,
the melt flow rate (MFR) of the ethylene polymer (α2) measured in accordance with ASTM D1238 at 190°C under a load of 2.16 kg is 0.5 to 100 g/10 min;
The resin composition (X) according to [13], [17] or [18].

[20] The main chain of the graft type olefin polymer [R1] in the olefin resin (β) is an ethylene-1-butene copolymer,
The density of the ethylene polymer (α2) measured at 25°C in accordance with ASTM D1505 is 850 to 900 kg/ ^m3 .
[13] and [17] to [19]. The resin composition (X) according to any one of [13] and [17] to [19].
[21] The main chain of the graft type olefin polymer [R1] in the olefin resin (β) is an ethylene-1-butene copolymer,
the melt flow rate (MFR) of the propylene polymer (α1) measured in accordance with ASTM D1238 at 230°C under a load of 2.16 kg is 0.01 to 25 g/10 min;
the density of the ethylene polymer (α2) measured at 25°C in accordance with ASTM D1505 is 850 to 900 kg/ ^m3 ;
[13] and [17] to [20]. The resin composition (X) according to any one of [13] and [17] to [20].

[22] The main chain of the graft type olefin polymer [R1] in the olefin resin (β) is an ethylene-1-butene copolymer,
a ratio ((β)/((α1)+(α2))) of the total mass of the olefin resin (β) to the total mass of the propylene polymer (α1) and the ethylene polymer (α2) is 0.08 to 0.20;
the melt flow rate (MFR) of the ethylene polymer (α2) measured in accordance with ASTM D1238 at 190°C under a load of 2.16 kg is 0.5 to 100 g/10 min;
[13] and [17] to [21]. The resin composition (X) according to any one of [13] and [17] to [21].

[23] The content of structural units derived from propylene in the side chains of the graft olefin polymer [R1] is 80 to 100 mol %,
the content of structural units derived from ethylene in the side chains of the graft type olefin polymer [R1] is 0 to 20 mol %,
the weight-average molecular weight (Mw) of the polymer or copolymer constituting the side chain of the grafted olefin polymer [R1], determined by gel permeation chromatography (GPC) in terms of polypropylene, is in the range of 5,000 to 50,000;
[13] to [22], the resin composition (X).

[24] A packaging material for a lithium ion battery.
The olefin resin (β) according to any one of [1] to [11].
[25] A packaging material for a lithium ion battery.
[13] to [23], the resin composition (X).
[26] A molded article containing the olefin resin (β) according to any one of [1] to [11] or the resin composition (X) according to any one of [13] to [23].

[27] A packaging body for a lithium ion battery, comprising the olefin resin (β) according to any one of [1] to [11], or the resin composition (X) according to any one of [13] to [23].
[28] An electricity storage device comprising the lithium ion battery packaging according to [27].

The present invention provides a novel olefin-based resin that is useful as a compatibilizer for propylene-based polymers and ethylene-based polymers, and provides uses for the olefin-based resin. The present invention also provides a resin composition and molded article, a packaging body for lithium-ion batteries, and an electricity storage device that contain a propylene-based polymer and an ethylene-based polymer and have an improved balance between impact resistance and elongation, or between impact resistance and strength.

FIG. 1 is a transmission electron microscope image of the resin composition (X) obtained in Example 1B. FIG. 2 is a transmission electron microscope image of the resin composition (X) obtained in Reference Example 1B. FIG. 3 is a transmission electron microscope image of the resin composition (X) obtained in Comparative Example 1B. FIG. 4 is a transmission electron microscope image of the resin composition (X) obtained in Example 1C. FIG. 5 is a transmission electron microscope image of the resin composition (X) obtained in Reference Example 1C. FIG. 6 is a transmission electron microscope image of the resin composition (X) obtained in Comparative Example 1C.

The present invention will be specifically described below.
In this specification, a numerical range expressed using "to" means a range that includes the numerical values before and after "to" as the lower and upper limits. A numerical range "A to B" indicates a range from A to B.
In this specification, when the units of the values written before and after "to" indicating a numerical range are the same, the unit of the values written before "to" may be omitted. For example, "851 kg/m ³ to 900 kg/m ³ " may be written as "851 to 900 kg/m ³ ".
In this specification, when referring to the amount of each component in a resin composition, if the resin composition contains multiple substances corresponding to each component, the amount refers to the total amount of the multiple substances present in the resin composition, unless otherwise specified.
As used herein, a combination of two or more preferred embodiments is a more preferred embodiment.
In this specification, unless otherwise specified, each component in the resin composition or each structural unit in the polymer (resin) may be contained in one type or in two or more types.
In the description of groups (atomic groups) in this specification, when there is no indication of substituted or unsubstituted, the notation encompasses both unsubstituted and substituted groups.
In this specification, the term "layer" includes cases where the layer is formed over the entire area when the area in which the layer exists is observed, as well as cases where the layer is formed over only a part of the area.
In this specification, room temperature means 23°C.
In this specification, the term "mainly comprise" means that the content of the target substance exceeds 50% by mass.

<Olefin Resin (β)>
The olefin resin (β) of the present invention contains a graft-type olefin polymer [R1] having a main chain and side chains, and satisfies all of the following requirements (I) to (IV):
(I) The main chain of the graft-type olefin polymer [R1] is composed of an ethylene-propylene copolymer or an ethylene-1-butene copolymer;
(II) The side chain of the graft-type olefin polymer [R1] is composed of a propylene homopolymer or a propylene-ethylene copolymer;
(III) The total P content of the following components (i) to (iv) in the olefin-based resin (β) is in the range of 10 to 80 mass%:
(i) a propylene homopolymer constituting the side chain of the graft-type olefin polymer [R1];
(ii) a propylene-ethylene copolymer constituting the side chain of the graft-type olefin polymer [R1];
(iii) a terminally unsaturated propylene homopolymer that does not constitute the graft-type olefin polymer [R1];
(iv) a terminally unsaturated propylene-ethylene copolymer that does not constitute the graft-type olefin polymer [R1];
(IV) The intrinsic viscosity [η] of the olefin resin (β) measured in decalin at 135° C. is 0.5 to 5.0 dL/g.

In the present invention, the term "graft type olefin polymer" means a polymer in which one or more side chains of the graft type olefin polymer [R1] are bonded to the main chain of the graft type olefin polymer [R1].
The graft type olefin polymer [R1] of the present invention has a structure in which a side chain of a graft type olefin polymer [R1] composed of a propylene homopolymer or a propylene-ethylene copolymer is chemically bonded to the main chain of the graft type olefin polymer [R1] composed of an ethylene-propylene copolymer or an ethylene-1-butene copolymer, and therefore the olefin resin (β) containing the graft type olefin polymer [R1] has high compatibility with both the propylene polymer (α1) and the ethylene polymer (α2) described below.
In the graft type olefin polymer [R1] of the present invention, the number average molecular weight of the main chain and the number average molecular weight of the side chain usually satisfy the relationship "number average molecular weight of the main chain > number average molecular weight of the side chain." Therefore, which of the graft type olefin polymer [R1] is the main chain or the side chain can be determined by measuring the number average molecular weight (Mn).

The graft type olefin polymer [R1] of the present invention satisfies the following requirements (I) and (II).
(I): The main chain of the graft type olefin polymer [R1] is composed of an ethylene-propylene copolymer or an ethylene-1-butene copolymer.
The main chain of the graft type olefin polymer [R1] preferably contains 70 to 99 mol % of structural units derived from ethylene and 1 to 30 mol % of structural units derived from propylene or 1-butene, from the viewpoint that the olefin resin (β) exhibits excellent compatibility with the ethylene polymer (α2) described below and that the resin composition (X) and molded article containing the olefin resin (β) exhibit an excellent balance between impact resistance and elongation or between impact resistance and strength.
When the main chain of the graft-type olefin polymer [R1] is an ethylene-propylene copolymer, from the viewpoint of further improving the whitening resistance of the resin composition (X) containing the olefin resin (β) and the molded article, the content of structural units derived from ethylene is more preferably 72 to 95 mol % and the content of structural units derived from propylene is 5 to 28 mol %, still more preferably 74 to 92 mol % and the content of structural units derived from propylene is 8 to 26 mol %, particularly preferably 74 to 90 mol % and the content of structural units derived from propylene is 10 to 26 mol %, particularly preferably 78 to 87 mol % and the content of structural units derived from propylene is 13 to 22 mol %, and still particularly preferably 75 to 85 mol % and the content of structural units derived from propylene is 15 to 25 mol %.
Furthermore, when the main chain of the graft-type olefin polymer [R1] is an ethylene-1-butene copolymer, from the viewpoint of further improving the whitening resistance of the resin composition (X) containing the olefin resin (β) and the molded article, the content of structural units derived from ethylene is more preferably 79 to 86 mol % and the content of structural units derived from 1-butene is 14 to 21 mol %, and even more preferably the content of structural units derived from ethylene is 79 to 82 mol % and the content of structural units derived from 1-butene is 18 to 21 mol %. The contents of the above structural units can be measured by ¹ H-NMR or ¹³ C-NMR.

(II): The side chain of the graft type olefin polymer [R1] is composed of a propylene homopolymer or a propylene-ethylene copolymer.
In view of the excellent compatibility of the olefin resin (β) with the propylene polymer (α1) described later and the excellent whitening resistance of the resin composition (X) and molded article containing the olefin resin (β), the side chain of the graft olefin polymer [R1] preferably contains 80 to 100 mol % of structural units derived from propylene and 0 to 20 mol %, more preferably 85 to 100 mol % of structural units derived from propylene and 0 to 20 mol % of structural units derived from ethylene. Preferably, the content of structural units derived from propylene is 0 to 15 mol %, more preferably, the content of structural units derived from propylene is 90 to 100 mol % and the content of structural units derived from ethylene is 0 to 10 mol %, still more preferably, the content of structural units derived from propylene is 95 to 100 mol % and the content of structural units derived from ethylene is 0 to 5 mol %, and particularly preferably, the content of structural units derived from propylene is 100 mol % and the content of structural units derived from ethylene is 0 mol %. The contents of the above structural units can be measured by ¹ H-NMR or ¹³ C-NMR.

The main chain and side chains of the graft-type olefin polymer [R1] may contain structural units (other structural units) other than structural units derived from ethylene and structural units derived from propylene, as long as the effects of the present invention are achieved. The proportion of such structural units is typically 0 to 19 mol%, preferably 0 to 15 mol%, more preferably 0 to 10 mol%, and even more preferably 0 to 5 mol%, of the total structural units in the main chain and side chains of the graft-type olefin polymer [R1]. Examples of structural units other than structural units derived from ethylene and structural units derived from propylene include structural units derived from α-olefins and cyclic olefins having 4 to 20 carbon atoms, preferably α-olefins having 4 to 10 carbon atoms, and more preferably α-olefins having 4 to 8 carbon atoms.

The graft type olefin polymer [R1] has a weight average molecular weight (Mw) of the ethylene-propylene copolymer or ethylene-1-butene copolymer constituting the main chain, which is determined by gel permeation chromatography (GPC) in terms of polyethylene, of usually 5,000 to 250,000, preferably 35,000 to 180,000, and more preferably 40,000 to 140,000.
When the main chain of the graft type olefin polymer [R1] is an ethylene-propylene copolymer, from the viewpoint of the olefin resin (β) exhibiting excellent compatibility with the ethylene polymer (α2) described below and the viewpoint of the resin composition (X) and molded article containing the olefin resin (β) having excellent blushing resistance, the Mw of the ethylene-propylene copolymer constituting the main chain is preferably 50,000 to 250,000, more preferably 55,000 to 200,000, even more preferably 60,000 to 150,000, particularly preferably 65,000 to 100,000, particularly preferably 70,000 to 90,000, and extremely preferably 72,000 to 82,000.
When the main chain of the graft type olefin polymer [R1] is an ethylene/1-butene copolymer, from the viewpoint of the olefin resin (β) exhibiting excellent compatibility with the ethylene polymer (α2) described below and the viewpoint of the resin composition (X) and molded article containing the olefin resin (β) having excellent blushing resistance, the Mw of the ethylene/1-butene copolymer constituting the main chain is preferably 30,000 to 120,000, more preferably 40,000 to 110,000, even more preferably 50,000 to 100,000, particularly preferably 60,000 to 90,000, and particularly preferably 72,000 to 85,000.

Furthermore, the weight-average molecular weight (Mw) of the polymer or copolymer (propylene homopolymer or propylene-ethylene copolymer constituting the side chain) constituting the graft olefin polymer [R1], as determined by gel permeation chromatography (GPC) as a polypropylene-equivalent value, is preferably 5,000 to 50,000, more preferably 7,500 to 50,000, even more preferably 10,000 to 50,000, particularly preferably 12,500 to 40,000, and especially preferably 15,000 to 30,000, from the viewpoint of ensuring that the olefin resin (β) exhibits excellent compatibility with the propylene polymer (α1) described below, and that the resin composition (X) and molded article containing the olefin resin (β) exhibit excellent whitening resistance.

Furthermore, the graft-type olefin polymer [R1] preferably has a total weight-average molecular weight, which is the product of the weight-average molecular weight (Mw) per side chain determined as a polypropylene equivalent value by gel permeation chromatography (GPC) and the number of side chains per main chain, of 5,000 to 150,000, more preferably 6,000 to 110,000, and even more preferably 6,000 to 70,000.

When one or more, preferably two or more, and more preferably all of the weight average molecular weight (Mw) of the main chain, the weight average molecular weight (Mw) of the side chain, and the total weight average molecular weight of the graft-type olefin-based polymer [R1] satisfy the preferred ranges described above, the olefin-based resin (β) containing it will have excellent compatibility with both the propylene-based polymer (α1) and the ethylene-based polymer (α2) described below, and the resin composition (X) and molded article containing the olefin-based resin (β) will have an excellent balance between impact resistance and elongation, or between impact resistance and strength, and will also have excellent whitening resistance.

The olefin resin (β) of the present invention contains a graft-type olefin polymer [R1] and satisfies both of the following requirements (III) and (IV).

(III): The total P content of the following components (i) to (iv) in the olefin resin (β) is 10 to 80 mass %:
(i) A propylene homopolymer constituting the side chain of the graft-type olefin polymer [R1]. (ii) A propylene-ethylene copolymer constituting the side chain of the graft-type olefin polymer [R1]. (iii) A terminally unsaturated propylene homopolymer not constituting the graft-type olefin polymer [R1]. (iv) A terminally unsaturated propylene-ethylene copolymer not constituting the graft-type olefin polymer [R1].

The content of P (the sum of the above components (i) to (iv)) in this olefin-based resin (β) is preferably 10 to 70% by mass, more preferably 10 to 60% by mass, and even more preferably 15 to 55% by mass, from the viewpoint of providing excellent compatibility of the olefin-based resin (β) with both the propylene-based polymer (α1) and the ethylene-based polymer (α2) described below, and from the viewpoint of providing an excellent balance between impact resistance and elongation or between impact resistance and strength in the resin composition (X) and molded articles containing the olefin-based resin (β), and from the viewpoint of providing excellent whitening resistance.

The olefin resin (β) of the present invention may be composed solely of the graft olefin polymer [R1], but may also contain components other than the graft olefin polymer [R1]. For example, it may contain, as part of P, a propylene homopolymer or a propylene-ethylene copolymer that does not constitute the graft olefin polymer [R1] and is an unreacted or by-product of the synthesis of the graft olefin polymer [R1]. Therefore, the components (i) to (iv) constituting P are typically derived from terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer, which are the raw materials for the side chains of the graft olefin polymer [R1]. The component (iii) is typically a terminally unsaturated propylene homopolymer that remains without being incorporated as a side chain during the synthesis of the graft olefin polymer [R1], and the component (iv) is typically a terminally unsaturated propylene-ethylene copolymer that remains without being incorporated as a side chain during the synthesis of the graft olefin polymer [R1]. For example, when olefin resin (β) is produced by the method for producing olefin resin (β) described below, P, which is the sum of (i) to (iv) above, is the sum of components derived from side chain raw materials.

The P content in the olefin resin (β) can be determined by analyzing the olefin resin (β). Components other than P are derived from the main chain; that is, the total amount of P and components derived from the main chain makes up 100% by mass of the olefin resin (β). Therefore, when the olefin resin (β) is produced by the olefin resin (β) production method described below, the P content can be calculated from the difference between the amount of terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer used as the side chain raw material and the amount of the resulting olefin resin (β). The P content can also be calculated by analyzing the olefin resin (β) using the method described in the Examples. The inventors' findings indicate that the P content calculated from the difference between the amount of the olefin resin (β) and the amount of the side chain raw material is very similar to the P content calculated by analyzing the olefin resin (β). Therefore, either method may be used. In the Examples described below, the P content is calculated from the difference between the amount of the olefin resin (β) and the amount of the side chain raw material.

(IV): The intrinsic viscosity [η] measured in decalin at 135°C is 0.5 to 5.0 dL/g.
The intrinsic viscosity [η] of the olefin resin (β) of the present invention measured in decalin at 135°C is preferably 0.5 to 4.0 dL/g, more preferably 0.5 to 3.0 dL/g, and even more preferably 0.7 to 3.0 dL/g, from the viewpoint of providing a resin composition (X) and a molded article containing the olefin resin (β) with an excellent balance between impact resistance and elongation, or a balance between impact resistance and strength, excellent whitening resistance, and excellent resin composition and molding processability.
When the main chain of the graft type olefin polymer [R1] is an ethylene-propylene copolymer, the viscosity is preferably 0.7 to 2.0 dL/g, more preferably 0.7 to 1.6 dL/g, even more preferably 0.9 to 1.35 dL/g, and particularly preferably 0.9 to 1.25 dL/g.
When the main chain of the graft type olefin polymer [R1] is an ethylene-1-butene copolymer, the viscosity is preferably 0.5 to 3.0 dL/g, more preferably 0.5 to 2.0 dL/g, and even more preferably 0.5 to 1.25 dL/g.

The olefin resin (β) of the present invention preferably satisfies the following requirement (V).
(V): The melting point (Tm) measured by differential scanning calorimetry (DSC) is −40 to 165° C.
The Tm of the olefin resin (β) of the present invention measured by differential scanning calorimetry (DSC) is more preferably in the range of -30 to 165°C, and even more preferably in the range of 0 to 165°C.

In the DSC measurement, when there are multiple endothermic peaks, the temperatures of both the lower and higher endothermic peaks are the melting point (Tm) in requirement (V).
The olefin resin (β) contains the graft type olefin polymer [R1] and therefore usually has two melting point peaks. The lower Tm observed in the above range is due to the main chain of the graft type olefin polymer [R1] constituting the olefin resin (β), and the higher Tm is due to the side chain of the graft type olefin polymer [R1] constituting the olefin resin (β).
When Tm is within the above range, the resin composition (X) containing the olefin resin (β) and the molded article thereof become excellent in compatibility with both the propylene-based polymer (α1) and the ethylene-based polymer (α2) described later, and the resin composition (X) containing the olefin resin (β) and the molded article thereof become excellent in balance between impact resistance and elongation or between impact resistance and strength, and further become excellent in whitening resistance.
Examples of a method for adjusting Tm within the above range include a method of adjusting the polymerization temperature, polymerization pressure, or the ratio of the feed amounts of ethylene to propylene or 1-butene in steps (A) and (B) described below.

The olefin resin (β) of the present invention preferably has a melt flow rate (MFR) of 0.01 to 100 g/10 min, measured at 190° C. under a load of 2.16 kg in accordance with ASTM D1238.
When the main chain of the graft type olefin polymer [R1] is an ethylene-propylene copolymer, the MFR of the olefin resin (β) is more preferably 0.01 to 80 g/10 min, even more preferably 0.01 to 50 g/10 min, particularly preferably 0.01 to 30 g/10 min, particularly preferably 0.5 to 30 g/10 min, and extremely preferably 2.0 to 28 g/10 min.
When the main chain of the graft type olefin polymer [R1] is an ethylene-1-butene copolymer, the MFR of the olefin resin (β) is more preferably 2.2 to 50 g/10 min, even more preferably 2.5 to 30 g/10 min, particularly preferably 2.5 to 10 g/10 min, and particularly preferably 2.5 to 8.5 g/10 min.
The MFR of the olefin resin (β) can be adjusted to a desired value by adjusting the production conditions. For example, methods include adjusting the polymerization temperature, polymerization pressure, hydrogen supply amount, etc. in steps (A) and (B) described below. Specifically, for example, the MFR can be increased by increasing the amount of hydrogen supplied relative to the amounts of ethylene, propylene, and 1-butene fed when polymerizing the olefin resin (β), and the MFR can be decreased by decreasing the amount of hydrogen supplied relative to the amounts of ethylene, propylene, and 1-butene fed.
When the MFR of the olefin-based resin (β) satisfies such a range, the resin composition (X) and the molded article containing the olefin-based resin (β) have an excellent balance between impact resistance and elongation, or between impact resistance and strength, excellent whitening resistance, and excellent molding processability, which is preferable.

The olefin resin (β) of the present invention preferably has a glass transition temperature (Tg) of −75 to −40° C. as measured by differential scanning calorimetry (DSC).
When the main chain of the graft type olefin polymer [R1] is an ethylene-propylene copolymer, the Tg of the olefin resin (β) is more preferably −70 to −45° C., even more preferably −65 to −45° C., particularly preferably −60 to −50° C., and particularly preferably −57 to −51° C.
When the main chain of the graft type olefin polymer [R1] is an ethylene-1-butene copolymer, the Tg of the olefin resin (β) is more preferably −72 to −45° C., even more preferably −70 to −50° C., and particularly preferably −70 to −58° C.
When the Tg of the olefin-based resin (β) satisfies such a range, the resin composition (X) and the molded article containing the olefin-based resin (β) have an excellent balance between impact resistance and elongation, or between impact resistance and strength, and are excellent in whitening resistance, which is preferable because they have excellent molding processability.

The olefin resin (β) of the present invention has a density measured at 23°C in accordance with JIS K7112 (density measured by a density gradient tube method) of preferably 850 to 950 kg/ ^m3 , more preferably 850 to 925 kg/ ^m3 , and even more preferably 860 to 900 kg/ ^m3 .
The density of the olefin resin (β) can be adjusted to a desired value by adjusting the production conditions for the olefin resin (β). For example, in step (B) described below, the density of the olefin resin (β) can be adjusted to a desired value by changing the ratio of the feed amounts of ethylene and propylene or 1-butene when polymerizing the olefin resin (β). Specifically, the density can be lowered by increasing the feed amount of propylene or 1-butene relative to the feed amount of ethylene, and the density can be increased by decreasing the feed amount of propylene or 1-butene relative to the feed amount of ethylene. Alternatively, the density of the olefin resin (β) can be adjusted to a desired value by changing the ratio of the main chain content to the P content. Specifically, when the density of the main chain is lower than that of the side chain, the density can be lowered by increasing the content of the main chain; when the density of the side chain is lower than that of the main chain, the density can be lowered by increasing the content of the P; when the density of the main chain is higher than that of the side chain, the density can be increased by increasing the content of the main chain; and when the density of the side chain is higher than that of the main chain, the density can be increased by increasing the content of the P.
When the density of the olefin-based resin (β) satisfies such a range, the resin composition (X) and the molded article containing the olefin-based resin (β) have an excellent balance between impact resistance and elongation, or between impact resistance and strength, and are therefore excellent in whitening resistance, which is preferable.

In terms of compatibility with the propylene-based polymer (α1) and ethylene-based polymer (α2) described below, the olefin-based resin (β) of the present invention preferably contains 10 to 92 mass%, more preferably 15 to 86 mass%, even more preferably 20 to 80 mass%, and particularly preferably 20 to 70 mass%, of structural units derived from ethylene, when the total content of structural units derived from ethylene, structural units derived from propylene or 1-butene, and structural units other than structural units derived from ethylene and structural units derived from propylene or 1-butene (other structural units) in the olefin-based resin (β) containing the graft-type olefin-based polymer [R1] is taken as 100 mass%.

The presence of grafted olefin polymer [R1] in olefin resin (β) can be confirmed by combining the content ratio of the main chain portion (ethylene-propylene copolymer or ethylene-1-butene copolymer) and the side chain portion (propylene homopolymer or propylene-ethylene copolymer) of the grafted olefin polymer [R1] in olefin resin (β) with GPC peak separation. For example, by performing peak separation on a molecular weight distribution curve measured using GPC, the constituent proportions of each portion can be determined, from which the formation of grafted olefin polymer [R1] can be confirmed. Various other analytical methods can also be used to confirm this, and the means of confirmation are not particularly limited.

In the olefin resin (β) of the present invention, when the main chain of the graft-type olefin polymer [R1] is an ethylene-propylene copolymer, the ethylene-propylene copolymer that is the main chain of the graft-type olefin polymer [R1] has a content of structural units derived from ethylene of 51 to 99 mol % and a content of structural units derived from propylene of 1 to 49 mol %, and preferably, the ethylene-propylene copolymer that is the main chain of the graft-type olefin polymer [R1] has a content of structural units derived from ethylene of 70 to 99 mol % and a content of structural units derived from propylene of 1 to 49 mol %. The graft-type olefin polymer [R1] is a copolymer having a content of structural units derived from ethylene of 1 to 30 mol %, and more preferably, the ethylene-propylene copolymer that forms the main chain of the graft-type olefin polymer [R1] has a content of structural units derived from ethylene of 75 to 85 mol %, the ethylene-propylene copolymer that forms the main chain of the graft-type olefin polymer [R1] has a content of structural units derived from propylene of 15 to 25 mol %, and the olefin resin (β) has an intrinsic viscosity [η] of 0.9 to 1.25 dL/g as measured in decalin at 135°C.

Furthermore, when the main chain of the graft type olefin polymer [R1] of the olefin resin (β) of the present invention is an ethylene-1-butene copolymer, it is more preferable that the content of structural units derived from ethylene in the ethylene-1-butene copolymer that is the main chain of the graft type olefin polymer [R1] is 70 to 90 mol %, the content of structural units derived from 1-butene in the ethylene-1-butene copolymer that is the main chain of the graft type olefin polymer [R1] is 10 to 30 mol %, and the weight average molecular weight (Mw) of the ethylene-1-butene copolymer that is the main chain of the graft type olefin polymer [R1], as determined by gel permeation chromatography (GPC) in terms of polyethylene, is 30,000 to 120,000, and further it is preferable that the olefin resin (β) satisfies at least one of the following requirements A to C:
Requirement A: The melt flow rate (MFR) of the olefin resin (β) measured in accordance with ASTM D1238 at 190°C under a load of 2.16 kg is 2.5 to 30 g/10 min.
Requirement B: The content of structural units derived from ethylene in the ethylene-1-butene copolymer that is the main chain of the graft-type olefin polymer [R1] is 78 to 87 mol %, and the content of structural units derived from 1-butene in the ethylene-1-butene copolymer that is the main chain of the graft-type olefin polymer [R1] is 13 to 22 mol %.
Requirement C: The intrinsic viscosity [η] of the olefin resin (β) measured in decalin at 135°C is 0.5 to 1.25 dL/g.

<Method for producing olefin-based resin (β)>
The olefin resin (β) is produced, for example, by a production method including the following steps (A) and (B).
Step (A): A step of polymerizing propylene in the presence of an olefin polymerization catalyst containing a transition metal compound [A] of Group 4 of the periodic table, which contains a ligand having a dimethylsilylbisindenyl skeleton, to produce a terminally unsaturated polypropylene, or a step of copolymerizing propylene and ethylene to produce a terminally unsaturated propylene-ethylene copolymer.
Step (B): A step of copolymerizing the terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer produced in step (A) with ethylene and propylene, or a step of copolymerizing the terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer produced in step (A) with ethylene and 1-butene, in the presence of an olefin polymerization catalyst containing a bridged metallocene compound represented by the following general formula [B]:

(In formula [B], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a heteroatom-containing group other than a silicon-containing group, and any two adjacent groups among R ¹ to R ⁴ may be bonded to each other to form a ring. R ⁶ and R ¹¹ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group, R ⁷ and R ¹⁰ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group, R ⁶ and R ⁷ may be bonded to each other to form a ring, and R ¹⁰ and R ¹¹ may be bonded to each other to form a ring; provided that R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms. R ¹³ and R ¹⁴ each independently represent an aryl group. ^Y1 represents a carbon atom or a silicon atom. ^M1 represents a zirconium atom or a hafnium atom. Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or non-conjugated diene having 4 to 10 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair, and j represents an integer of 1 to 4, and when j is an integer of 2 or greater, multiple Qs may be the same or different.

Steps (A) and (B) will be described below in order.
[Process (A)]
Step (A) is a step for producing a terminally unsaturated polypropylene or a terminally unsaturated propylene-ethylene copolymer, which is a raw material for the side chain of the graft-type olefin polymer [R1], and is a step for producing a terminally unsaturated polypropylene by polymerizing propylene in the presence of an olefin polymerization catalyst containing a transition metal compound [A] of Group 4 of the periodic table, which contains a ligand having a dimethylsilylbisindenyl skeleton, or a step for producing a terminally unsaturated propylene-ethylene copolymer by copolymerizing propylene and ethylene.

[Transition metal compound [A]]
In step (A), an olefin polymerization catalyst is used, which contains a transition metal compound [A] of Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton (hereinafter, also simply referred to as transition metal compound [A]). The transition metal compound [A] functions as a polymerization catalyst for polymerizing propylene or copolymerizing propylene and ethylene, and functions more favorably when used in combination with catalyst component (C) described below.

As the transition metal compound [A], any transition metal compound of Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton can be used. For example, compounds disclosed in JP-A-6-100579, JP-A-2001-525461, JP-A-2005-336091, JP-A-2009-299046, JP-A-11-130807, JP-A-2008-285443, etc. can be suitably used.

More specifically, preferred examples of the transition metal compound [A] include compounds selected from the group consisting of bridged bis(indenyl)zirconocenes and hafnocenes. Dimethylsilyl-bridged bis(indenyl)zirconocene or hafnocenes are more preferred. Dimethylsilyl-bridged bis(indenyl)zirconocene is even more preferred. By selecting the zirconocene, an olefin resin (β) containing the desired graft-type olefin polymer [R1] can be efficiently produced.

More specifically, dimethylsilylbis{1-(2-n-propyl-4-(9-phenanthryl)indenyl)}zirconium dichloride, dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride, dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl, and the like can be used as suitable compounds.
The above-mentioned transition metal compounds [A] may be used singly or in combination of two or more.

[Polymerization catalyst]
The olefin polymerization catalyst used in step (A) is not particularly limited as long as it contains the above-mentioned transition metal compound [A] of Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton, but preferably contains, in addition to the transition metal compound [A], a catalyst component (C) selected from (C1) an organometallic compound, (C2) an organoaluminumoxy compound, and (C3) a compound that reacts with the transition metal compound [A] to form an ion pair. Details of the catalyst component (C) are as described below.

[Step (A)]
The polymerization of propylene or the copolymerization of propylene and ethylene in step (A) can be suitably carried out by a known (co)polymerization method for polymerizing or copolymerizing an olefin in the presence of the above-mentioned polymerization catalyst. The polymerization conditions are not particularly limited as long as a solution polymerization process for producing an olefin polymer is used, but for example, a step in which propylene is polymerized alone or propylene and ethylene are copolymerized using an aliphatic hydrocarbon or aromatic hydrocarbon as a polymerization solvent in the presence of an olefin polymerization catalyst containing the above-mentioned transition metal compound [A] to obtain a polymerization reaction liquid is preferred.

Examples of the polymerization solvent for step (A) include aliphatic hydrocarbons and aromatic hydrocarbons. Specific examples include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. These may be used alone or in combination of two or more. The polymerization solvent for step (A) may be the same as or different from the polymerization solvent for step (B) described below.

The polymerization temperature in step (A) is preferably in the range of 15°C to 200°C, more preferably in the range of 20°C to 150°C.
The polymerization pressure in step (A) is usually from atmospheric pressure to 10 MPa gauge pressure, preferably from atmospheric pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out by any of a batch system, a semi-continuous system, and a continuous system.
The reaction time in step (A) (average residence time when the polymerization is carried out by a continuous method) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 5 minutes to 3 hours.

During the polymerization or copolymerization in step (A), it is preferable to supply propylene alone or propylene and ethylene in proportions such that the propylene content is 80 to 100 mol % and the ethylene content is 0 to 20 mol %. Furthermore, in step (A), it is desirable to carry out the polymerization or copolymerization under conditions such that the weight average molecular weight (Mw) of the resulting terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer, as determined by gel permeation chromatography (GPC) in terms of polypropylene, is in the range of 5,000 to 50,000.

The molecular weight of the terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer obtained in step (A) can be adjusted by adding hydrogen to the polymerization system or by changing the polymerization temperature. It can also be adjusted by using catalyst component (C), described below; examples include the use of triisobutylaluminum, methylaluminoxane, and diethylzinc. If hydrogen is added, the amount is appropriately about 0.001 to 100 NL per kg of olefin. To increase the terminal vinyl group content, it is preferable to carry out the reaction in the absence of hydrogen.

The terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer produced in step (A) has a terminal vinyl ratio (the ratio of the number of vinyl groups to the total number of unsaturated carbon-carbon bonds) of usually 40% or more, preferably 50% or more, and more preferably 60% or more.
The proportion of terminal vinyl groups in the terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer produced in step (A) is usually 0.1 to 15, and preferably 0.4 to 15, terminal vinyl groups per 1,000 carbon atoms.

If the terminal vinyl ratio (ratio of the number of vinyl groups to all unsaturated carbon-carbon bonds) and the ratio of terminal vinyl groups per 1,000 carbon atoms are low, the amount of terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer (specifically, propylene homopolymer or propylene-ethylene copolymer having a vinyl group at one end) introduced into the main chain in the subsequent step (B) will be low, resulting in a low amount of graft-type olefin polymer [R1] produced, and the desired effect may not be achieved.

The terminal vinyl ratio (the ratio of the number of vinyl groups to all unsaturated carbon-carbon bonds) and the ratio of terminal vinyl groups per 1000 carbon atoms can be calculated by a conventional method using polymer structure analysis by ¹ H-NMR measurement.

[Process (B)]
Step (B) is a step of copolymerizing the terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer produced in step (A) with ethylene and propylene, or a step of copolymerizing the terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer produced in step (A) with ethylene and 1-butene, in the presence of an olefin polymerization catalyst containing a bridged metallocene compound (transition metal compound [B]) represented by the general formula [B] above.

[Bridged Metallocene Compound]
The bridged metallocene compound used in step (B) is a compound represented by the following general formula [B].

In formula [B], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a heteroatom-containing group other than a silicon-containing group, and any two adjacent groups among R ¹ to R ⁴ may be bonded to each other to form a ring.

As the hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms is preferred, and specific examples include alkyl groups having 1 to 20 carbon atoms, arylalkyl groups having 7 to 20 carbon atoms, aryl groups or substituted aryl groups having 6 to 20 carbon atoms, etc. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an allyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an amyl group, an n-pentyl group, a neopentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decanyl group, a 3-methylpentyl group, a 1,1-diethylpropyl group, a 1,1-dimethylbutyl group, a 1-methyl-1-propylbutyl group, a 1,1-propylbutyl group, a 1,1-dimethyl-2-methylpropyl group, a 1-methyl-1-isopropyl-2-methylpropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, Examples of hydrocarbon groups include norbornyl, adamantyl, phenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, isopropylphenyl, t-butylphenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl, benzyl, and cumyl. Examples of hydrocarbon groups include oxygen-containing groups such as methoxy, ethoxy, and phenoxy; nitrogen-containing groups such as nitro, cyano, N-methylamino, N,N-dimethylamino, and N-phenylamino; boron-containing groups such as boranetriyl and diboranyl; and sulfur-containing groups such as sulfonyl and sulfenyl.

The above hydrocarbon groups may have hydrogen atoms substituted with halogen atoms, and examples include trifluoromethyl groups, trifluoromethylphenyl groups, pentafluorophenyl groups, and chlorophenyl groups.

Silicon-containing groups include silyl groups, siloxy groups, hydrocarbon-substituted silyl groups, and hydrocarbon-substituted siloxy groups. Examples include methylsilyl groups, dimethylsilyl groups, trimethylsilyl groups, ethylsilyl groups, diethylsilyl groups, triethylsilyl groups, diphenylmethylsilyl groups, triphenylsilyl groups, dimethylphenylsilyl groups, dimethyl-t-butylsilyl groups, and dimethyl(pentafluorophenyl)silyl groups.

^R6 and ^R11 are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, and a heteroatom-containing group other than a silicon-containing group, ^R7 and ^R10 are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, and a heteroatom-containing group other than a silicon-containing group, ^R6 and ^R7 may be bonded to each other to form a ring, and ^R10 and ^R11 may be bonded to each other to form a ring, provided that ^R6 , ^R7 , ^R10 , and ^R11 are not all hydrogen atoms.

R ¹³ and R ¹⁴ each independently represent an aryl group.
^M1 represents a zirconium atom or a hafnium atom.
Y ¹ represents a carbon atom or a silicon atom.

Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or non-conjugated diene having 4 to 20 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair, and j represents an integer from 1 to 4. When j is an integer of 2 or greater, multiple Qs may be the same or different.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a chlorine atom being preferred.
The hydrocarbon group is preferably a hydrocarbon group having 1 to 10 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a 2-methylpropyl group, a 1,1-dimethylpropyl group, a 2,2-dimethylpropyl group, a 1,1-diethylpropyl group, a 1-ethyl-1-methylpropyl group, a 1,1,2,2-tetramethylpropyl group, a sec-butyl group, a t-butyl group, a 1,1-dimethylbutyl group, a 1,1,3-trimethylbutyl group, a neopentyl group, a cyclohexylmethyl group, a cyclohexyl group, a 1-methyl-1-cyclohexyl group, and a benzyl group, of which a methyl group, an ethyl group, and a benzyl group are preferred.

As the neutral conjugated or non-conjugated diene having 4 to 20 carbon atoms, a neutral conjugated or non-conjugated diene having 4 to 10 carbon atoms is preferred. Specific examples of neutral conjugated or non-conjugated dienes include s-cis- or s-trans-η ⁴ -1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4-diphenyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -3-methyl-1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4-dibenzyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -2,4-hexadiene, s-cis- or s-trans-η ⁴ -1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4-ditolyl-1,3-butadiene, and s-cis- or s-trans-η ⁴ -1,4-bis(trimethylsilyl)-1,3-butadiene.

Specific examples of anionic ligands include alkoxy groups such as methoxy, t-butoxy, and phenoxy; carboxylate groups such as acetate and benzoate; and sulfonate groups such as mesylate and tosylate.

Specific examples of neutral ligands that can coordinate with lone electron pairs include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, or ethers such as tetrahydrofuran, diethyl ether, dioxane, and 1,2-dimethoxyethane.

Examples of the cyclopentadienyl group having substituents R ¹ to R ⁴ in the above formula [B] include an unsubstituted cyclopentadienyl group in which R ¹ to R ⁴ are hydrogen atoms, 3-substituted cyclopentadienyl groups such as a 3-t-butylcyclopentadienyl group, a 3-methylcyclopentadienyl group, a 3-trimethylsilylcyclopentadienyl group, a 3-phenylcyclopentadienyl group, a 3-adamantylcyclopentadienyl group, a 3-amylcyclopentadienyl group, and a 3-cyclohexylcyclopentadienyl group, and 3-t-butyl-5-methylcyclopentadienyl groups. Examples of cyclopentadienyl groups include, but are not limited to, 3-,5-disubstituted cyclopentadienyl groups such as a 3-t-butyl-5-ethylcyclopentadienyl group, a 3-phenyl-5-methylcyclopentadienyl group, a 3,5-di-t-butylcyclopentadienyl group, a 3,5-dimethylcyclopentadienyl group, a 3-phenyl-5-methylcyclopentadienyl group, and a 3-trimethylsilyl-5-methylcyclopentadienyl group. From the viewpoints of ease of synthesis of the metallocene compound, production costs, and copolymerizability with non-conjugated polyenes, unsubstituted cyclopentadienyl groups (R ¹ to R ⁴ are hydrogen atoms) are preferred.

The fluorenyl group having substituents R ⁵ to R ¹² in formula [B] includes an unsubstituted fluorenyl group in which R ⁵ to R ¹² are hydrogen atoms, a 2-position mono-substituted fluorenyl group such as a 2-methylfluorenyl group, a 2-t-butylfluorenyl group, or a 2-phenylfluorenyl group, a 4-position mono-substituted fluorenyl group such as a 4-methylfluorenyl group, a 4-t-butylfluorenyl group, or a 4-phenylfluorenyl group, a 2-position di-substituted fluorenyl group or a 3,6-position di-substituted fluorenyl group such as a 2,7-di-t-butylfluorenyl group or a 3,6-di-t-butylfluorenyl group, a 2,3,6,7-position tetra-substituted fluorenyl group such as a 2,7-dimethyl-3,6-di-t-butylfluorenyl group or a 2,7-diphenyl-3,6-di-t-butylfluorenyl group, or a ring-substituted fluorenyl group represented by the following general formulas [V-I] and [V-II] in which R ⁶ and R ⁷ are bonded to each other to form a ring, and R Examples include, but are not limited to, 2-, 3-, 6-, and 7-tetrasubstituted fluorenyl groups in which ^{R 10} and R ¹¹ are bonded to each other to form a ring.

In formulas [V-I] and [V-II], ^R5 , ^R8 , ^R9 , and ^R12 are the same as defined in general formula [B] above, and Ra, ^Rb , Rc, ^Rd , ^Re , ^Rf , ^{Rg ,} and ^Rh each independently ^represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, which may be bonded to adjacent substituents to form a ring. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an amyl group, and an n-pentyl group. In addition, in formula [VI-I], R ^x and R ^y each independently represent a hydrocarbon group having 1 to 3 carbon atoms which may have an unsaturated bond, and R ^x may form a double bond together with the carbon to which R ^a or R ^c is bonded, and R ^y may form a double bond together with the carbon to which R ^e or R ^g is bonded, and it is preferable that both R ^x and R ^y are saturated or unsaturated hydrocarbon groups having 1 or 2 carbon atoms.

Specific examples of groups represented by the above general formula [V-I] or [V-II] include an octamethyloctahydrodibenzofluorenyl group represented by formula [V-III], a tetramethyldodecahydrodibenzofluorenyl group represented by formula [V-IV], an octamethyltetrahydrodicyclopentafluorenyl group represented by formula [V-V], a hexamethyldihydrodicyclopentafluorenyl group represented by formula [V-VI], and a b,h-dibenzofluorenyl group represented by formula [V-VII].

Although all of these bridged metallocene compounds represented by the general formula [B] containing fluorenyl groups are excellent in copolymerization ability with non-conjugated polyenes, when ^Y1 is a silicon atom, transition metal compounds having di-substituted fluorenyl groups at the 2,7-positions, di-substituted fluorenyl groups at the 3,6-positions, tetra-substituted fluorenyl groups at the 2,3,6,7-positions, and tetra-substituted fluorenyl groups at the 2,3,6,7-positions represented by the general formula ^[ V-I] are particularly excellent.When Y is a carbon atom, metallocene compounds having an unsubstituted fluorenyl group, di-substituted fluorenyl groups at the ^3,6 -positions, tetra-substituted fluorenyl groups at the 2,3,6,7-positions, and tetra-substituted fluorenyl groups at the 2,3,6,7-positions represented by the general formula [V-I] are particularly excellent, in which R5 to R12 are hydrogen atoms.

In the present invention, in the bridged metallocene compound represented by the above general formula [B], when ^Y1 is a silicon atom and ^R5 to ^R12 are all hydrogen atoms, ^R13 and ^R14 are selected from groups other than a methyl group, a butyl group, a phenyl group, a silicon-substituted phenyl group, a cyclohexyl group, and a benzyl group;
When ^Y1 is a silicon atom, ^R6 and ^R11 are both t-butyl groups, and ^R5 , ^R7 , ^R8 , ^R9 , ^R10 , and ^R12 are not t-butyl groups, ^R13 and ^R14 are selected from groups other than a benzyl group and a silicon-substituted phenyl group;
When Y ¹ is a carbon atom and R ⁵ to R ¹² are all hydrogen atoms, R ¹³ and R ¹⁴ are selected from groups other than a methyl group, an isopropyl group, a t-butyl group, an isobutyl group, a phenyl group, a p-t-butylphenyl group, a p-n-butylphenyl group, a silicon-substituted phenyl group, a 4-biphenyl group, a p-tolyl group, a naphthyl group, a benzyl group, a cyclopentyl group, a cyclohexyl group, and a xylyl group;
When Y ¹ is a carbon atom, R ⁶ and R ¹¹ are a common group selected from a t-butyl group, a methyl group, or a phenyl group, and are groups or atoms different from R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹² , R ¹³ and R ¹⁴ are selected from groups other than a methyl group, a phenyl group, a p-t-butylphenyl group, a p-n-butylphenyl group, a silicon-substituted phenyl group, and a benzyl group;
When ^Y1 is a carbon atom, ^R6 is a dimethylamino group, a methoxy group, or a methyl group, and ^R5 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 , and ^R12 are groups or atoms different from ^R6 , ^R13 and ^R14 are selected from groups other than a methyl group and a phenyl group;
When Y ¹ is a carbon atom and the moiety consisting of the fluorenyl group and R ⁵ to R ¹² is b,h-dibenzofluorenyl or a,i-dibenzofluorenyl, R ¹³ and R ¹⁴ are preferably selected from groups other than methyl and phenyl groups.

Specific examples of the bridged metallocene compound represented by the above general formula [B] are shown below, but the scope of the present invention is not particularly limited by these.
Specific examples of the bridged metallocene compound represented by the general formula [B] include:
When Y is a silicon atom,
Diphenylsilylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, diphenylsilylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, diphenylsilylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, diphenylsilylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, diphenylsilylene(cyclopentadienyl)(octamethicone) diphenylsilylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, diphenylsilylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, diphenylsilylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, diphenylsilylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride,

Di(p-tolyl)silylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(p-tolyl)silylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, di(p-tolyl)silylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, di(p-tolyl)silylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(p-tolyl)silylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(p-tolyl) Silylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, di(p-tolyl)silylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, di(p-tolyl)silylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, di(p-tolyl)silylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, di(p-tolyl)silylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride, di(m di(m-tolyl)silylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(m-tolyl)silylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, di(m-tolyl)silylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, di(m-tolyl)silylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(m-tolyl)silylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(m-tolyl)silylene Examples of silylene include di(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, di(m-tolyl)silylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, di(m-tolyl)silylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, di(m-tolyl)silylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, and di(m-tolyl)silylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride.

When Y is a carbon atom, diphenylmethylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride,

Di(p-tolyl)methylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(2,7-diphenyl-3, 6-di-t-butylfluorenyl)zirconium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride,
Di(p-tolyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride, di(m-tolyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(m-tolyl)methylene(cyclo di(m-tolyl)methylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, di(m-tolyl)methylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, di(m-tolyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(m-tolyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride di(m-tolyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(m-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, di(m-tolyl)methylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, di(m-tolyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, di(m-tolyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, di(m-tolyl)methylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride,

Di(p-t-butylphenyl)methylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, di(p-t-butylphenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(p-t-butylphenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(p-t-butylphenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride chloride, di(p-t-butylphenyl)methylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, di(p-t-butylphenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, di(p-t-butylphenyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, di(p-t-butylphenyl)methylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride,

Di(4-biphenyl)methylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, di(4-biphenyl)methylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, di(4-biphenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(4-biphenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(4-biphenyl)methylene(cyclopentadienyl)(octa Di(4-biphenyl)methylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, di(4-biphenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, di(4-biphenyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, di(4-biphenyl)methylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride,

Di(p-chlorophenyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride, Di(m-chlorophenyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(m-chloro Di(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride,

Di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride,

Di(2-naphthyl)methylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(octamethyl Examples include di(2-naphthyl)methylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, and di(2-naphthyl)methylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride.

Furthermore, examples of the bridged metallocene compound represented by the above general formula [B] include those in which the zirconium atom of M ¹ in the general formula [B] in the above specific examples is replaced by a hafnium atom.

As examples of the structural formulas of these metallocene compounds, the structural formulas of di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride ((A) below) and di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride ((B) below) are shown below.

The bridged metallocene compounds may be used singly or in combination of two or more.

The bridged metallocene compound represented by formula [B] used in step (B) can be produced by any method without particular limitation. For example, it can be produced in accordance with the methods described in J. Organomet. Chem., 63,509 (1996), WO2005/100410, WO2006/123759, WO01/27124, JP 2004-168744, JP 2004-175759, JP 2000-212194, etc.

[Polymerization catalyst]
The olefin polymerization catalyst used in step (B) is not particularly limited as long as it contains a bridged metallocene compound represented by the above general formula [B], but it preferably contains, in addition to the bridged metallocene compound, a catalyst component (C) selected from (C1) an organometallic compound, (C2) an organoaluminum oxy compound, and (C3) a compound that reacts with the transition metal compound [A] to form an ion pair. Details of the catalyst component (C) are as described below.

[Process (B)]
Step (B) is a step of copolymerizing the terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer produced in step (A) with ethylene and propylene, or a step of copolymerizing the terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer produced in step (A) with ethylene and 1-butene, in the presence of the polymerization catalyst described above.
The polymerization form in step (B) is not particularly limited, but can preferably be carried out by solution (dissolution) polymerization. The polymerization conditions are not particularly limited as long as a solution polymerization process for producing an olefin polymer is used. For example, a preferred step is one in which ethylene and propylene, or ethylene and 1-butene, and the terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer produced in step (A) are copolymerized using an aliphatic hydrocarbon or aromatic hydrocarbon as a polymerization solvent in the presence of an olefin polymerization catalyst containing a bridged metallocene compound represented by general formula [B] above, to obtain a polymerization reaction solution containing the graft-type olefin polymer [R1].

In step (B), the terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer produced in step (A) is typically fed to the reactor in step (B) in the form of a solution or slurry. The feeding method is not particularly limited, and the polymerization reaction liquid obtained in step (A) may be continuously fed to the reactor for step (B), or the polymerization reaction liquid obtained in step (A) may be temporarily stored in a buffer tank or the like and then fed to step (B).

Examples of the polymerization solvent for step (B) include aliphatic hydrocarbons and aromatic hydrocarbons. Specific examples include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. These solvents may be used alone or in combination of two or more. The polymerization solvent for step (B) may be the same as or different from the polymerization solvent for step (A).
The polymerization temperature in step (B) is usually in the range of 50 to 200°C, preferably 80 to 200°C, and more preferably 90 to 200°C.

The polymerization pressure in step (B) is typically between atmospheric pressure and 10 MPa gauge pressure, preferably between atmospheric pressure and 5 MPa gauge pressure, and the polymerization reaction can be carried out batchwise, semi-continuously, or continuously. It is also possible to carry out the polymerization in two or more stages with different reaction conditions. In the present invention, it is preferable to employ a method in which the monomers are continuously supplied to the reactor to carry out the copolymerization.

The reaction time in step (B) (average residence time if copolymerization is carried out continuously) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 5 minutes to 3 hours.

The polymer concentration in step (B) during steady-state operation is, for example, 0.5 to 40% by mass, and preferably 1 to 35% by mass. From the standpoints of viscosity limitations in polymerization capacity, the load on post-treatment steps (solvent removal), and productivity, a concentration of 1.5 to 35% by mass is preferred.

In step (B), when the terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer produced in step (A) is copolymerized with ethylene and propylene or ethylene and 1-butene, the amounts of ethylene and propylene or ethylene and 1-butene used are preferably such that, relative to a total of 100 mol % of ethylene and propylene or ethylene and 1-butene, the amount of ethylene is 70 to 99 mol % and the amount of propylene or 1-butene is 1 to 30 mol %. Furthermore, in step (B), it is desirable to carry out copolymerization under conditions such that the weight-average molecular weight (Mw) of the ethylene-propylene polymer portion or ethylene-1-butene polymer portion that forms the main chain of the resulting graft olefin polymer [R1], as determined by gel permeation chromatography (GPC) in terms of polyethylene, is in the range of 30,000 to 200,000.

The molecular weight of the resulting copolymer, the graft-type olefin polymer [R1], can be adjusted by adding hydrogen to the polymerization system or by changing the polymerization temperature. It can also be adjusted by the amount of catalyst component (C1) used, which will be described later. Specific examples include triisobutylaluminum, methylaluminoxane, and diethylzinc. When hydrogen is added, the appropriate amount is approximately 0.001 to 100 NL per kg of olefin.

[Catalyst component (C)]
In the method for producing an olefin resin (β) of the present invention, it is also preferable that the olefin polymerization catalyst used in the above-mentioned steps (A) and (B) contains a catalyst component (C). The catalyst component (C) may be used as a catalyst component of the olefin polymerization catalyst in both steps (A) and (B), or may be used as a catalyst component of the olefin polymerization catalyst in either step (A) or step (B). When the catalyst component (C) is used as a catalyst component of the olefin polymerization catalyst in both steps (A) and (B), the catalyst components (C) used in steps (A) and (B) may be the same or different.

The catalyst component (C) is one or more compounds selected from (C1) organometallic compounds, (C2) organoaluminum oxy-compounds, and (C3) compounds that react with a transition metal compound contained in an olefin polymerization catalyst to form an ion pair.
The compounds (C1) to (C3) will be explained in order below.

((C1) Organometallic compound)
Specific examples of the organometallic compound (C1) used in the present invention include organoaluminum compounds represented by the following general formula (C1-a), complex alkyl compounds of a metal of Group 1 of the periodic table with aluminum represented by the general formula (C1-b), and dialkyl compounds of a metal of Group 2 or Group 12 of the periodic table represented by the general formula (C1-c). Note that the organometallic compound (C1) does not include the organoaluminum oxy compound (C2) described below.

R ^a _p Al(OR ^b ) _q H _r Y _s …(C1-a)
In the general formula (C1-a), R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms; Y represents a halogen atom; p is a number that satisfies 0<p≦3, q is a number that satisfies 0≦q<3, r is a number that satisfies 0≦r<3, s is a number that satisfies 0≦s<3, and p+q+r+s=3.

M ³ AlR ^c ₄ ...(C1-b)
In the above general formula (C1-b), ^M3 represents Li, Na, or K, and ^Rc represents a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms.

R ^d R ^e M ⁴ …(C1-c)
In the above general formula (C1-c), R ^d and R ^e may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms, and M ⁴ represents Mg, Zn, or Cd.

Examples of the organoaluminum compound represented by the above general formula (C1-a) include compounds represented by the following general formulas (C-1a-1) to (C-1a-4).
R ^ap _Al (OR ^b ) _3-p ...(C-1a-1)
(in formula (C-1a-1), R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms, and p is preferably a number satisfying 1.5≦p≦3),

R ^ap _{AlY 3-p} ...(C-1a-2)
(in formula (C-1a-2), R ^a represents a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms, Y represents a halon atom, and p is preferably a number satisfying 0<p<3),
R ^ap _{AlH 3-p} ...(C-1a-3)
(in formula (C-1a-3), R ^a represents a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms, and p is preferably a number satisfying 2≦p<3),

R ^a _p Al (OR ^b ) _q Y _s … (C-1a-4)
(In formula (C-1a-4), R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms; Y represents a halogen atom; p is a number that satisfies 0<p≦3, q is a number that satisfies 0≦q<3, s is a number that satisfies 0≦s<3, and p+q+s=3.)

More specific examples of the organoaluminum compound of general formula (C1-a) include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum; tri-branched alkylaluminums such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, and tri-2-ethylhexylaluminum; tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminums such as triphenylaluminum and tritolylaluminum; dialkylaluminum hydrides such as diisobutylaluminum hydride; (i-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (wherein x, y, and z are positive numbers, and z≧2x); alkylaluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide, and isobutylaluminum isopropoxide; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, and dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; partially alkoxylated alkylaluminums having an average composition represented by R ^a _2.5 Al(OR ^b ) _0.5 (wherein R ^a and R ^b 's may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms; dialkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), and isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide); dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, and diisobutylaluminum chloride; ethylaluminum sesquichloride, butylaluminum partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide; dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride; other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride; and partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide.

Compounds similar to (C1-a) can also be used in the present invention, such as organoaluminum compounds in which two or more aluminum compounds are bonded via nitrogen atoms, such as ( _C2H5 ) _{2AlN ( C2H5} ) _Al ( _C2H5 ) _{2 .}

Examples of compounds belonging to the general formula (C1-b) include LiAl(C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ .
Examples of the compound belonging to the general formula (C1-c) include dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butylethyl magnesium, dimethyl zinc, diethyl zinc, diphenyl zinc, di-n-propyl zinc, diisopropyl zinc, di-n-butyl zinc, diisobutyl zinc, bis(pentafluorophenyl)zinc, dimethyl cadmium, and diethyl cadmium.

In addition, other organometallic compounds (C1) that can be used include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, and butylmagnesium chloride.

Furthermore, compounds that form the above-mentioned organoaluminum compound in the polymerization system, such as a combination of an aluminum halide and an alkyllithium, or a combination of an aluminum halide and an alkylmagnesium, can also be used as the organometallic compound (C1).
The organometallic compounds (C1) as described above may be used singly or in combination of two or more.
The organometallic compound (C1) is used in an amount such that the molar ratio (C1/M) of the organometallic compound (C1) to the transition metal atom (M) in the transition metal compound contained in the olefin polymerization catalyst is usually 0.01 to 100,000, and preferably 0.05 to 50,000.

((C2) Organoaluminum oxy compound)
The organoaluminum oxy compound (C2) used in the present invention may be a conventionally known aluminoxane, or may be a benzene-insoluble organoaluminum oxy compound such as those exemplified in JP-A No. 2-78687. Specific examples of the organoaluminum oxy compound (C2) include methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane.
Conventionally known aluminoxanes can be produced, for example, by the following methods (1) to (3), and are usually obtained as a solution in a hydrocarbon solvent.

(1) A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension of a compound containing adsorbed water or a salt containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, or cerous chloride hydrate, to react the adsorbed water or water of crystallization with the organoaluminum compound.
(2) A method in which water, ice or water vapor is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method in which an organoaluminum compound such as trialkylaluminum is reacted with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene, or toluene.

The aluminoxane may contain a small amount of an organometallic component. After the solvent or unreacted organoaluminum compound is removed by distillation from the recovered aluminoxane solution, the resulting aluminoxane may be redissolved in a solvent or suspended in a poor solvent for the aluminoxane.
Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the above general formula (C1-a).
Among these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred.The above organoaluminum compounds may be used singly or in combination of two or more.

Solvents used in the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane; petroleum fractions such as gasoline, kerosene, and diesel; and hydrocarbon solvents such as halides, especially chlorinated and brominated versions, of the above aromatic, aliphatic, and alicyclic hydrocarbons. Ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

The benzene-insoluble organoaluminum oxy-compound used in the present invention preferably has an Al component soluble in benzene at 60°C in an amount of usually 10% or less, preferably 5% or less, and particularly preferably 2% or less, calculated as Al atoms. In other words, the organoaluminum oxy-compound is preferably insoluble or poorly soluble in benzene.
The organoaluminum oxy compound (C2) used in the present invention may also include boron-containing organoaluminum oxy compounds represented by the following general formula (III).

(In general formula (III), R ¹⁷ represents a hydrocarbon group having 1 to 10 carbon atoms, and four R ¹⁸ may be the same or different and represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.)

The boron-containing organoaluminum oxy compound represented by the above general formula (III) can be produced by reacting an alkylboronic acid represented by the following general formula (IV) with an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of −80° C. to room temperature for 1 minute to 24 hours.
^R19 -B(OH) ₂ ...(IV)
(In general formula (IV), R ¹⁹ represents the same group as R ¹⁷ in general formula (III) above.)

Specific examples of alkylboronic acids represented by the above general formula (IV) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, and 3,5-bis(trifluoromethyl)phenylboronic acid. Of these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These may be used alone or in combination of two or more.

Specific examples of organoaluminum compounds to be reacted with such alkylboronic acids include the same organoaluminum compounds as those exemplified as organoaluminum compounds belonging to general formula (C1-a) above.

The organoaluminum compound is preferably a trialkylaluminum or a tricycloalkylaluminum, and more preferably trimethylaluminum, triethylaluminum, or triisobutylaluminum, which may be used singly or in combination.
It is preferable that the olefin polymerization catalyst contains (C2) an organoaluminum oxy compound, since this will result in high polymerization activity for olefin compounds.

The organoaluminum oxy compounds (C2) as described above may be used singly or in combination of two or more.
The organoaluminum oxy compound (C2) is used in an amount such that the molar ratio (C2/M) of aluminum atoms in the organoaluminum oxy compound (C2) to the transition metal atoms (M) in the transition metal compound contained in the olefin polymerization catalyst is generally 10 to 500,000, preferably 20 to 100,000.

((C3) Compounds that react with transition metal compounds to form ion pairs)
The compound (C3) that reacts with a transition metal compound to form an ion pair is a compound that reacts with a transition metal compound contained in an olefin polymerization catalyst to form an ion pair. The transition metal compound contained in an olefin polymerization catalyst means the transition metal compound [A] of Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton used in the above-mentioned step (A), or the transition metal compound [B] of Group 4 of the periodic table containing a bridged metallocene compound used in the step (B).

(C3) Examples of compounds used in the present invention that react with transition metal compounds to form ion pairs (hereinafter referred to as "ionizing ionic compounds") include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-T-1-501950, JP-T-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and USP-5321106. Further examples include heteropoly compounds and isopoly compounds.

Specifically, the Lewis acid includes compounds represented by BR ₃ (R is fluorine or a phenyl group which may have a substituent such as fluorine, a methyl group, or a trifluoromethyl group), such as trifluoroboron, triphenylboron, tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron, tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron, and tris(3,5-dimethylphenyl)boron.
The ionic compound may, for example, be a compound represented by the following general formula (V).

(In general formula (V), R ²⁰ represents H ⁺ , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, or a ferrocenium cation having a transition metal, and R ²¹ to R ²⁴ may be the same or different and represent an organic group, preferably an aryl group or a substituted aryl group.)

Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri(n-butyl)ammonium cation; N,N-dialkylanilinium cations such as N,N-dimethylanilinium cation, N,N-diethylanilinium cation, and N,N-2,4,6-pentamethylanilinium cation; and dialkylammonium cations such as di(isopropyl)ammonium cation and dicyclohexylammonium cation.

Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation.
As R ²⁰ , a carbonium cation or an ammonium cation is preferred, and a triphenylcarbonium cation, an N,N-dimethylanilinium cation, or an N,N-diethylanilinium cation is particularly preferred.

Further examples of ionic compounds include trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

Specific examples of the above-mentioned trialkyl-substituted ammonium salts include triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tri(n-butyl)ammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(m,m-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(p-trifluoromethylphenyl)boron, tri(n-butyl)ammonium tetra(3,5-ditrifluoromethylphenyl)boron, and tri(n-butyl)ammonium tetra(o-tolyl)boron.

Specific examples of the N,N-dialkylanilinium salt include N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, and N,N,2,4,6-pentamethylanilinium tetra(phenyl)boron.
Specific examples of the dialkylammonium salt include di(1-propyl)ammonium tetra(pentafluorophenyl)boron and dicyclohexylammonium tetra(phenyl)boron.

Further examples of ionic compounds include triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, ferrocenium tetra(pentafluorophenyl)borate, triphenylcarbenium pentaphenylcyclopentadienyl complex, N,N-diethylanilinium pentaphenylcyclopentadienyl complex, and boron compounds represented by the following formula (VI) or (VII):

(In formula (VI), Et represents an ethyl group.)

(In formula (VII), Et represents an ethyl group.)

Specific examples of borane compounds, which are ionizable ionic compounds (compound [C3]), include decaborane; salts of anions such as bis[tri(n-butyl)ammonium]nonaborate, bis[tri(n-butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium]undecaborate, bis[tri(n-butyl)ammonium]dodecaborate, bis[tri(n-butyl)ammonium]decachlorodecaborate, and bis[tri(n-butyl)ammonium]dodecachlorododecaborate; and salts of metal borane anions such as tri(n-butyl)ammonium bis(dodecahydridedodecaborate)cobaltate(III) and bis[tri(n-butyl)ammonium]bis(dodecahydridedodecaborate)nickelate(III).

Specific examples of carborane compounds, which are examples of ionizable ionic compounds, include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane, and undecahydride-7,8-dimethyl. 1-methyl-7,8-dicarboxaundecaborane, dodecahydride-11-methyl-2,7-dicarboxaundecaborane, tri(n-butyl)ammonium 1-carbadecaborate, tri(n-butyl)ammonium 1-carbaundecaborate, tri(n-butyl)ammonium 1-carbadodecaborate, tri(n-butyl)ammonium 1-trimethylsilyl-1-carbadecaborate, tri(n-butyl)ammonium bromo-1-carbadodecaborate, tri(n-butyl)ammonium 6-carbadecaborate, tri(n-butyl)ammonium 6-carbadecaborate, tri(n-butyl)ammonium 7-carbaundecaborate, tri(n-butyl)ammonium 7,8-dicarbaundecaborate, tri(n-butyl)ammonium 2,9-dicarbaundecaborate, tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate Salts of anions such as carbaundecaborate, tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, and tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carbaundecaborate;
Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)ferrate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)nickelate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)cuprate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)aurate(III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbandecaborate)ferrate salt (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarboxamdecaborate)chromate (III), tri(n-butyl)ammonium bis(tribromooctahydride-7,8-dicarboxamdecaborate)cobaltate (III), tris[tri(n-butyl)ammonium]bis(undecahydride-7-carboudecaborate)chromate (III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboudecaborate)manganate (IV), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboudecaborate)cobaltate (III), and bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboudecaborate)nickelate (IV).

Heteropoly compounds, which are examples of ionized ionic compounds, are compounds containing atoms selected from silicon, phosphorus, titanium, germanium, arsenic, and tin, and one or more atoms selected from vanadium, niobium, molybdenum, and tungsten. Specific examples include, but are not limited to, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanomolybdic acid, germanomolybdic acid, arsenic molybdic acid, tinmolybdic acid, phosphotungstic acid, germanotungstic acid, tintungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid, phosphomolybdotungstic acid, phosphomolybdoniobic acid, and salts of these acids. Examples of the salts include salts of the above acids with metals from Group 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc., and organic salts such as triphenylethyl salts.

Isopoly compounds, which are examples of ionized ionic compounds, are compounds composed of metal ions of one type of atom selected from vanadium, niobium, molybdenum, and tungsten, and can be considered to be molecular ionic species of metal oxides. Specific examples include, but are not limited to, vanadic acid, niobic acid, molybdic acid, tungstic acid, and salts of these acids. Furthermore, examples of the salts include salts of the above acids with metals from Group 1 or 2 of the periodic table, such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, and barium, as well as organic salts such as triphenylethyl salts.

The above-mentioned ionizing ionic compounds (compounds that react with the transition metal compound contained in the olefin polymerization catalyst (C3) to form an ion pair) may be used singly or in combination of two or more.
The ionizing ionic compound (C3) is used in an amount such that the molar ratio (C3/M) of the ionizing ionic compound (C3) to the transition metal atom (M) in the transition metal compound contained in the olefin polymerization catalyst is usually 1 to 10, preferably 1 to 5.

〔monomer〕
In the present invention, in the polymerization step, at least one monomer selected from α-olefins having 3 to 20 carbon atoms may be used as a copolymerization component together with ethylene and propylene, or ethylene and 1-butene, within the scope of the present invention, as long as the object of the present invention is not impaired. Specific examples of the α-olefins having 3 to 20 carbon atoms used as a copolymerization component include propylene, 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, and methyl-1-hexene. Examples of the α-olefins include 1-butene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl-1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene. Of these, the α-olefins 1-butene, 1-pentene, 1-hexene, and 1-octene can be preferably used.
The ethylene, propylene, 1-butene, and α-olefins having 3 to 20 carbon atoms may be naphtha-derived raw materials, bionaphtha-derived raw materials, or a combination of naphtha-derived raw materials and bionaphtha-derived raw materials. Furthermore, the raw materials may contain one or more chemically recycled raw materials.

[Other steps]
The method for producing the olefin resin (β) of the present invention may, in addition to the above-mentioned steps (A) and (B), optionally include a step of recovering the polymer produced in either step (A) or (B), or both steps (A) and (B). This step is a step of separating the organic solvent used in steps (A) and (B) to extract the polymer, and is not particularly limited as long as it is a known step such as solvent concentration, extrusion degassing, pelletizing, or crystallization.

<Resin composition (X)>
The resin composition (X) of the present invention is a composition containing the above-mentioned olefin resin (β), a propylene polymer (α1), and an ethylene polymer (α2). The propylene polymer (α1) is a polymer or copolymer mainly having structural units derived from propylene, and the ethylene polymer (α2) is a polymer or copolymer mainly having structural units derived from ethylene.

[Propylene polymer (α1)]
The resin composition (X) of the present invention may contain a propylene polymer (α1).
Examples of the propylene polymer (α1) include a propylene homopolymer (homopolypropylene) and a copolymer of propylene and an α-olefin other than propylene having 2 to 20 carbon atoms. The copolymer of propylene and the above α-olefin may be a random copolymer (random polypropylene) or a block copolymer (block polypropylene).

Here, specific examples of α-olefins having 2 to 20 carbon atoms other than propylene include ethylene, 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, and methyl-1-hexene. Examples of suitable olefins include 1-pentene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl-1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene. Among these, α-olefins having 2 to 10 carbon atoms other than propylene, such as ethylene, 1-butene, 1-pentene, 1-hexene, and 1-octene, are preferred.

The α-olefins other than propylene having 2 to 20 carbon atoms may be one type alone or two or more types. From the viewpoint of providing the resin composition (X) containing the olefin resin (β) and the molded article with excellent whitening resistance, the α-olefins other than propylene having 2 to 20 carbon atoms are preferably one type or two or more types, more preferably one type or two types.
The propylene polymer (α1) may have at least one structural unit derived from a biomass-derived monomer. Examples of the biomass-derived monomer include biomass-derived propylene, biomass-derived ethylene, and biomass-derived α-olefins having 4 to 20 carbon atoms. The same type of monomer constituting the polymer may be only biomass-derived monomers, only fossil fuel-derived monomers, or both biomass-derived monomers and fossil fuel-derived monomers.

The resin composition (X) of the present invention may contain one type of propylene polymer (α1) or two or more types of propylene polymer (α1). However, from the viewpoint of the resin composition (X) containing the olefin resin (β) and a molded article having an excellent balance between impact resistance and elongation or between impact resistance and strength, and from the viewpoint of the excellent whitening resistance, the resin composition (X) of the present invention preferably contains two or more types of propylene polymer (α1).
In the present invention, the propylene polymer (α1) may be any of products produced by polymerization or copolymerization, commercially available products, and recycled products.

When the propylene polymer (α1) is a copolymer of propylene and one α-olefin other than propylene having 2 to 20 carbon atoms, the propylene polymer (α1) preferably contains more than 50 mol%, more preferably 60 mol% or more, even more preferably 70 mol% or more, particularly preferably 80 mol% or more, particularly preferably 90 mol% or more, and extremely preferably 95 mol% or more of the structural unit (iv) derived from propylene.
On the other hand, the propylene polymer (α1) preferably contains 50 mol% or less, more preferably 40 mol% or less, even more preferably 30 mol% or less, particularly preferably 20 mol% or less, particularly preferably 10 mol% or less, and extremely preferably 5 mol% or less of structural units (v) derived from an α-olefin other than propylene having 2 to 20 carbon atoms (however, the total content of structural units (iv) and structural units (v) is taken as 100 mol%).

Furthermore, when the propylene-based polymer (α1) is a copolymer of propylene and two α-olefins other than propylene, each having 2 to 20 carbon atoms, the propylene-based polymer (α1) may contain 53 mol % or more and less than 95 mol % of the structural unit (iv) derived from propylene.
On the other hand, it may contain more than 2 mol % and not more than 23 mol % of structural units derived from α-olefins (excluding propylene) having a small number of carbon atoms, and may contain more than 3 mol % and not more than 24 mol % of structural units derived from α-olefins (excluding propylene) having a large number of carbon atoms (however, when the propylene-based polymer (α1) is a copolymer of propylene and two or more α-olefins, the content of structural units derived from α-olefins means the total content of structural units derived from two or more α-olefins, and the total content of structural units (iv) and structural units (v) is taken as 100 mol %). The content of the above structural units can be measured by ¹ H-NMR or ¹³ C-NMR.

When the propylene polymer (α1) is a product produced by polymerization or copolymerization, it can be produced by polymerizing or copolymerizing a monomer containing propylene as a main component using a known olefin polymerization catalyst, for example, it can be obtained by polymerizing or copolymerizing using a Ziegler-Natta catalyst or the like.
When the propylene polymer (α1) is a commercially available product, it can be selected from commercially available propylene polymers without any particular limitation. Examples of commercially available propylene polymers (α1) include so-called homopolypropylene resins (resins essentially consisting of propylene homopolymers), random polypropylene resins, and block polypropylene resins. From the viewpoint of the resin composition (X) containing the olefin resin (β) and the molded article having an excellent balance between impact resistance and elongation, or between impact resistance and strength, and having excellent whitening resistance, the propylene polymer (α1) preferably contains a random polypropylene resin.
When the propylene polymer (α1) is a recycled product, recycled plastics containing the propylene polymer (α1) as a main component, or plastic products containing the propylene polymer (α1) as a main component that have been washed, crushed, and pelletized can be used.

A preferred embodiment of the propylene polymer (α1) will be described below.
The propylene polymer (α1) preferably has a melt flow rate (MFR) of 0.01 to 500 g/10 min, as measured in accordance with ASTM D1238 at 230°C under a load of 2.16 kg. The lower limit of the MFR is preferably 0.02 g/10 min, more preferably 0.03 g/10 min, from the viewpoint of increasing fluidity, and the upper limit is preferably 300 g/10 min, more preferably 100 g/10 min, particularly preferably 50 g/10 min, from the viewpoint of increasing the strength of the propylene polymer (α1) itself.

When the main chain of the graft type olefin polymer [R1] is an ethylene-propylene copolymer, the melt flow rate (MFR) of the propylene polymer (α1) is more preferably 0.01 to 100 g/10 min, further preferably 0.01 to 80 g/10 min, particularly preferably 0.01 to 50 g/10 min, particularly preferably 0.01 to 20 g/10 min, further particularly preferably 0.5 to 20 g/10 min, and extremely preferably 0.5 to 10 g/10 min.
When the main chain of the graft olefin polymer [R1] is an ethylene-1-butene copolymer, the melt flow rate (MFR) of the propylene polymer (α1) is more preferably 0.01 to 100 g/10 min, even more preferably 0.01 to 50 g/10 min, particularly preferably 0.01 to 25 g/10 min, and particularly preferably 2.5 to 10 g/10 min.
When the melt flow rate (MFR) of the propylene polymer (α1) satisfies the above range, the resin composition (X) and the molded article of the present invention have an excellent balance between impact resistance and elongation or between impact resistance and strength, excellent whitening resistance, and excellent molding processability, which is preferable.

The propylene polymer (α1) has a weight average molecular weight (Mw) in terms of polystyrene, determined by gel permeation chromatography (GPC), of preferably 80,000 to 900,000, more preferably 100,000 to 700,000, and particularly preferably 150,000 to 700,000.
The terminal structure of the propylene polymer (α1) is usually substantially saturated hydrocarbon, and specifically, the proportion of unsaturated terminals in the propylene polymer (α1) is usually less than 0.1 per 1000 carbon atoms.
The melting point (Tm) of the propylene polymer (α1) measured by differential scanning calorimetry (DSC) is preferably 100 to 170°C, more preferably 120 to 170°C.

[Ethylene-based polymer (α2)]
The resin composition (X) of the present invention may contain an ethylene polymer (α2).
The ethylene polymer (α2) may have at least one structural unit derived from a biomass-derived monomer. Examples of the biomass-derived monomer include biomass-derived ethylene and biomass-derived α-olefins having 3 to 20 carbon atoms. The same type of monomer constituting the polymer may be only biomass-derived monomers, only fossil fuel-derived monomers, or both biomass-derived monomers and fossil fuel-derived monomers.
The ethylene polymer (α2) contained in the resin composition (X) of the present invention may be one type or two or more types.

The resin composition (X) of the present invention contains the ethylene polymer (α2), and thereby a molded article having a good balance between impact resistance and elongation, or a good balance between impact resistance and strength, and excellent whitening resistance can be obtained.
The ethylene-based polymer (α2) may be either an ethylene homopolymer or an ethylene-based copolymer containing more than 50 mol% of structural units derived from ethylene. The ethylene-based polymer (α2) contains preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more of structural units derived from ethylene.

Preferably, the ethylene-based polymer (α2) is a homopolymer of ethylene or a copolymer of ethylene and at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms. From the viewpoint of achieving an excellent balance between impact resistance and elongation, or between impact resistance and strength, and from the viewpoint of achieving excellent whitening resistance, the ethylene-based polymer (α2) preferably comprises a copolymer with at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms, and more preferably is a copolymer with at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms. The copolymer may be a random copolymer or a block copolymer. Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl ... Examples of α-olefins include ethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl-1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene. Among these, the α-olefins propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene are preferred, and the α-olefins 1-butene, 1-pentene, and 1-hexene are more preferred.

The content of the structural unit (vi) derived from ethylene in the ethylene polymer (α2) is 60 to 99 mol%, preferably 65 to 99 mol%, more preferably 70 to 99 mol%, and particularly preferably 80 to 99 mol%.
The content of the structural unit (vii) derived from an α-olefin having 3 to 20 carbon atoms in the ethylene polymer (α2) is 1 to 40 mol %, preferably 1 to 35 mol %, more preferably 1 to 30 mol %, and particularly preferably 1 to 20 mol %.
These contents are based on 100 mol % of the total of structural units derived from ethylene and α-olefins having 3 to 20 carbon atoms.
The content of the above structural units can be measured by ¹ H-NMR or ¹³ C-NMR.
When the content of the structural unit is within the above range, a molded article having an excellent balance between impact resistance and elongation, or between impact resistance and strength, and excellent whitening resistance can be easily obtained.

The ethylene polymer (α2) may be composed of a single polymer selected from the above polymers, or may be composed of a plurality of polymers.
In the present invention, the ethylene polymer (α2) may be any of products produced by polymerization or copolymerization, commercially available products, and recycled products.
When the ethylene polymer (α2) is a product produced by polymerization or copolymerization, it can be produced by polymerizing or copolymerizing a monomer containing ethylene as a main component using a known olefin polymerization catalyst, and can be obtained by polymerizing or copolymerizing using, for example, a Ziegler-Natta catalyst.

When the ethylene polymer (α2) is a commercially available product, it can be selected from commercially available ethylene polymers without any particular limitation. Examples of commercially available ethylene polymers include polyethylene resins such as so-called homopolyethylene resins, ethylene-α-olefin copolymers, and ethylene elastomers.
When the ethylene polymer (α2) is a recycled product, recycled plastics containing an ethylene polymer as a main component, plastic products containing an ethylene polymer as a main component that have been washed, crushed, and pelletized, etc., can be used.

A preferred embodiment of the ethylene polymer (α2) will be described below.
The ethylene polymer (α2) has a density measured at 25°C in accordance with ASTM D1505 (density measured by a density gradient tube method) of preferably 840 kg/ ^m3 or more, more preferably 845 kg/ ^m3 or more, even more preferably 850 kg/m3 or more, particularly preferably 855 kg/ ^m3 or more, and preferably 940 kg/ ^m3 or ^less , more preferably 920 kg/ ^m3 or less, even more preferably 900 kg/m3 or ^less , particularly preferably 890 kg/ ^m3 or less, and extremely preferably 885 kg/ ^m3 or less. That is, it is preferably 840 kg/m ³ to 940 kg/m ³ , more preferably 845 kg/m ³ to 920 kg/m ³ , even more preferably 850 kg/m ³ to 900 kg/m ³ , particularly preferably 855 kg/m ³ to 890 kg/m ³ , and extremely preferably 855 kg/m ³ to 885 kg/m ³ .
When the density is within the above range, a molded article having an excellent balance between impact resistance and elongation, or between impact resistance and strength, and excellent whitening resistance can be easily obtained.

The ethylene polymer (α2) preferably has a melt flow rate (MFR) of 0.01 to 500 g/10 min, as measured in accordance with ASTM D1238 at 190°C under a load of 2.16 kg. The lower limit of the MFR is preferably 0.02 g/10 min, more preferably 0.03 g/10 min, from the viewpoint of increasing the fluidity, and the upper limit is preferably 300 g/10 min, more preferably 100 g/10 min, particularly preferably 50 g/10 min, from the viewpoint of increasing the strength of the ethylene polymer (α2) itself.
When the main chain of the graft olefin polymer [R1] is an ethylene-propylene copolymer, the MFR of the ethylene polymer (α2) is more preferably 0.01 to 5.0 g/10 min, even more preferably 0.01 to 2.0 g/10 min, particularly preferably 0.1 to 1.5 g/10 min, and particularly preferably 0.2 to 1.3 g/10 min, from the viewpoint of achieving a good balance between impact resistance and elongation, or a good balance between impact resistance and strength, and from the viewpoint of achieving a good whitening resistance.
When the main chain of the graft olefin polymer [R1] is an ethylene-1-butene copolymer, the MFR of the propylene polymer (α1) is more preferably 0.5 to 500 g/10 min, even more preferably 0.5 to 100 g/10 min, and particularly preferably 0.6 to 20 g/10 min, from the viewpoints of a good balance between impact resistance and elongation or a good balance between impact resistance and strength, and of a good whitening resistance.

The ethylene polymer (α2) has a weight average molecular weight (Mw) in terms of polystyrene determined by gel permeation chromatography (GPC) of preferably 40,000 to 900,000, more preferably 60,000 to 700,000, and particularly preferably 80,000 to 700,000.
The ethylene polymer (α2) usually has a terminal structure that is substantially saturated hydrocarbon, and specifically, the proportion of unsaturated terminals in the ethylene polymer (α2) is usually less than 0.1 per 1000 carbon atoms.

[Resin composition (X)]
Examples of the resin composition (X) of the present invention include a resin composition containing an olefin resin (β) and a propylene polymer (α1), a resin composition containing an olefin resin (β), a propylene polymer (α1), and an ethylene polymer (α2), and a resin composition containing an olefin resin (β) and an ethylene polymer (α2). Of these, a resin composition containing an olefin resin (β), a propylene polymer (α1), and an ethylene polymer (α2) is preferred.

The resin composition (X) of the present invention more preferably contains the propylene polymer (α1) and the ethylene polymer (α2) in a mass ratio of 1:99 to 99:1. In the resin composition (X) of the present invention containing both the propylene polymer (α1) and the ethylene polymer (α2), the olefin resin (β) is added, so that the propylene polymer (α1) and the ethylene polymer (α2), which are usually poorly compatible, can be homogeneously dispersed.
The olefin resin (β), propylene polymer (α1) and ethylene polymer (α2) contained in the resin composition (X) of the present invention may each be one type or two or more types.
The resin composition (X) of the present invention may contain the olefin resin (β), the propylene polymer (α1), and the ethylene polymer (α2) in any ratio.

In the resin composition (X) of the present invention, the ratio of the total mass of the olefin resin (β) to the total amount of the propylene polymer (α1) and the ethylene polymer (α2), ((β)/((α1)+(α2))), is preferably 0.01 to 0.5.
When the main chain of the graft type olefin polymer [R1] is an ethylene-propylene copolymer, from the viewpoint of a good balance between impact resistance and elongation, or a good balance between impact resistance and strength, and from the viewpoint of a good whitening resistance, the ratio ((β)/((α1)+(α2))) is more preferably 0.02 to 0.23, and even more preferably 0.03 to 0.20.
When the main chain of the graft type olefin polymer [R1] is an ethylene-1-butene copolymer, from the viewpoint of a good balance between impact resistance and elongation, or a good balance between impact resistance and strength, and from the viewpoint of a good whitening resistance, the ratio ((β)/((α1)+(α2))) is more preferably 0.08 to 0.20, even more preferably 0.08 to 0.18, and particularly preferably 0.09 to 0.16.

In the resin composition (X) having the above-mentioned configuration, the propylene-based polymer (α1) and the ethylene-based polymer (α2) can be more uniformly dispersed in the resin composition, and the resin composition (X) is preferred because it has an excellent balance between impact resistance and elongation, or a good balance between impact resistance and strength, and is excellent in whitening resistance.
In the resin composition (X) of the present invention, when the main chain of the graft-type olefin polymer [R1] in the olefin resin (β) is an ethylene-1-butene copolymer, in a preferred embodiment, the melt flow rate (MFR) of the propylene polymer (α1) measured in accordance with ASTM D1238 at 230°C under a load of 2.16 kg is 0.01 to 25 g/10 min, and the density of the ethylene polymer (α2) measured in accordance with ASTM D1505 at 25°C is 850 to 900 kg/ ^m3 .
In a preferred embodiment of the resin composition (X) of the present invention, when the main chain of the graft type olefin polymer [R1] in the olefin resin (β) is an ethylene-1-butene copolymer,
The ratio ((β)/((α1)+(α2))) of the total mass of the olefin resin (β) to the total mass of the propylene polymer (α1) and the ethylene polymer (α2) is 0.08 to 0.20, and the melt flow rate (MFR) of the ethylene polymer (α2) measured in accordance with ASTM D1238 at 190°C under a load of 2.16 kg is 0.5 to 100 g/10 min.

The resin composition (X) of the present invention may contain other components in addition to the propylene polymer (α1), the ethylene polymer (α2), and the olefin resin (β), as long as the object of the present invention is not impaired. Examples of other components include other resins, rubbers, inorganic fillers, and additives. Examples of additives include weather resistance stabilizers, heat resistance stabilizers, antistatic agents, antislip agents, antiblocking agents, antifogging agents, lubricants, pigments, dyes, plasticizers, antioxidants, hydrochloric acid absorbers, antioxidants, and crystal nucleating agents.

The resin composition (X) of the present invention may be a blend of post-consumer recycled (PIR (post-industrial recycled) and PCR (post-consumer recycled)) resins. For example, PIR and PCR blends may be used to prepare articles alone or in combination with non-recycled (fresh/virgin) polymer resins. The resin composition may be combined with non-recycled plastic resins in ratios of, for example, 1:99 to 99:1 (e.g., 20:80 to 80:20, 40:60 to 60:40, etc.). Post-consumer plastic resins may be formed to form the resin composition (X) for preparing articles.

<Method for producing resin composition (X)>
The method for producing the resin composition (X) is not particularly limited, and it can be prepared, for example, by mixing the olefin resin (β), the propylene polymer (α1), the ethylene polymer (α2), and, if necessary, other optional components in the above-mentioned blending ratios using, for example, a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, a kneader-ruder, etc., or by melt-kneading the mixture, either after mixing or without mixing, using a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, etc. Furthermore, granulation, pulverization, etc. may be carried out as necessary.
When mixing or kneading these components, the components to be blended may be added all at once or in stages.
The melt-kneading method is not particularly limited, and can be carried out using a melt-kneading device such as a commercially available extruder. For example, the temperature of the part of the melt-kneading device where the kneading is carried out is usually 120 to 250°C, preferably 120 to 230°C. The kneading time is usually 0.5 to 30 minutes, particularly preferably 0.5 to 5 minutes.

Olefin resin (β), resin composition (X) containing olefin resin (β) and propylene polymer (α1), resin composition (X) containing olefin resin (β) and ethylene polymer (α2), or resin composition (X) containing olefin resin (β), propylene polymer (α1) and ethylene polymer (α2) are suitable for use in pellets, hot melt adhesives, coatings, and skin materials, and the hot melt adhesives can be used in automotive parts such as interior and exterior automotive parts. Furthermore, molded articles containing resin composition (X) can also be used in films, sheets, and packaging materials, nonwoven fabrics, closures, cap liner materials, foams, and automotive parts such as interior and exterior automotive parts using these.

<Hot melt adhesive>
An example of an application of the olefin resin (β) or the resin composition (X) is a hot melt adhesive. The hot melt adhesive of the present disclosure can be obtained, for example, by melt-mixing the components in a melt dissolving tank such as a heated melt stirring tank, preferably under vacuum or nitrogen gas flow, by rotating a stirring blade, or by melt-mixing the components in sequence using a kneader's twin rotating blades to apply shear under heat, or by melt-mixing using the screws of a single-screw or twin-screw extruder. The temperature is typically adjusted to 120 to 230°C, preferably 150 to 200°C. The bale-shaped or pellet-shaped samples prepared in this manner can be used for various applications.

In the case of a hot melt adhesive, the adherends may be bonded together before the adhesive has cured, or the hot melt adhesive may be reheated and activated before bonding the adherends together. Such a hot melt adhesive may be in the form of a sheet, film, nonwoven fabric, small piece, or rod.
In the hot melt adhesive, the content of the olefin resin (β) is usually 1 to 90 mass%, preferably 3 to 50 mass%, more preferably 5 to 40 mass%, based on the total amount of the adhesive. A content within the above range is preferred from the viewpoint of the balance between the adhesive strength and coatability of the hot melt adhesive.

The hot melt adhesive may optionally contain an amorphous polyalphaolefin (APAO).
The melt viscosity of the APAO is preferably 500 to 200,000 mPa·s/190° C., more preferably 1,000 to 50,000 mPa·s/190° C. A melt viscosity of 500 mPa·s/190° C. or higher provides sufficient cohesive force and improves the adhesive strength of the adhesive, while a melt viscosity of 200,000 mPa·s/190° C. or lower is preferred because it improves workability when applying the hot melt adhesive.
There are various compositions of such APAOs, and examples thereof include homopolymers or copolymers such as atactic polypropylene and atactic polybutene-1, copolymers or terpolymers of propylene, ethylene, butene-1, etc., propylene homopolymers, propylene-butene copolymers, propylene-ethylene copolymers, etc.

The olefin resin (β) has excellent compatibility with APAO and is therefore preferably used.
Specific examples of APAO include RT2730 (product name, manufactured by Rextac Co., Ltd.) (melt viscosity at 190°C: 4,000 mPa·s) and VESTOPLAST 704 (product name, manufactured by Evonik Co., Ltd., melt viscosity (190°C): 3,500 mPa·s).
APAO may be used alone or in combination of two or more types.
When an APAO is used in a hot melt adhesive, its content is usually 1 to 99 mass %, preferably 10 to 90 mass %, and more preferably 20 to 80 mass %, based on the total amount of the adhesive. A content within the above range is preferred from the viewpoint of the balance between the adhesive strength and coatability of the hot melt adhesive.

The hot melt adhesive may optionally contain a tackifier.
Examples of tackifiers include at least one resin selected from natural rosin, modified rosin, polyterpene resin, synthetic petroleum resin, coumarone resin, phenol resin, xylene resin, styrene resin, low-molecular-weight styrene resin, and isoprene resin. Among these, rosin resin, polyterpene resin, and synthetic petroleum resin are preferred, and those having an aliphatic and/or alicyclic structure are more preferred.
Particularly preferred examples of the petroleum resins having an aliphatic and/or alicyclic structure include partially and fully hydrogenated rosin and derivatives thereof in the case of rosin-based resins, homopolymers or copolymers of cyclic terpenes in the case of polyterpene-based resins, and aliphatic petroleum resins, alicyclic petroleum resins, aliphatic-alicyclic copolymer resins, and hydrogenated copolymers of naphtha cracked oil and various terpenes in the case of synthetic petroleum resins.

The tackifier preferably has a softening point of 25 to 160°C. A softening point of 25°C or higher can prevent bleeding onto the surface, while a softening point of 160°C or lower prevents the viscosity at the time of melting from becoming too high, resulting in good processability. Specifically, products under the trade names "Alcon P-70", "Alcon P-90", "Alcon P-100", "Alcon P-115", "Alcon P-125" and "Alcon P-140" (all manufactured by Arakawa Chemical Industries, Ltd.) are preferably used.
The tackifier may be used alone or in combination of two or more kinds.
When a tackifier is used in a hot melt adhesive, the content of the tackifier is usually 1 to 70 mass %, preferably 5 to 50 mass %, and more preferably 10 to 40 mass %, based on the total amount of the adhesive. A content within the above range is preferable because it can impart fluidity and adhesive power without reducing adhesive strength.

The hot melt adhesive may optionally contain a wax.
Examples of waxes include synthetic waxes such as Fischer-Tropsch wax, polyethylene wax, and polypropylene wax, petroleum waxes such as paraffin wax and microcrystalline wax, and natural waxes such as Japan wax, carnauba wax, and beeswax. Polypropylene wax is particularly preferred because the olefin resin (β) has excellent compatibility with polypropylene.
The wax preferably has a Brookfield viscosity (190°C) of 10 to 8000 mPa·s, more preferably 100 to 5000 mPa·s. A Brookfield viscosity within the above range is preferred in terms of cohesive strength and kneading processability.
The wax has a melting point measured by DSC of preferably 80 to 150° C., more preferably 90 to 140° C. A melting point within the above range is preferable in terms of flexibility and kneading processability when using the adhesive.

Examples of commercially available waxes include "Mitsui Hiwax 420P,""Mitsui Hiwax NL100," and "Mitsui Hiwax NP015" (all manufactured by Mitsui Chemicals, Inc.).
The waxes may be used alone or in combination of two or more.
When a wax is used in a hot melt adhesive, the content of the wax is usually 1 to 60 mass %, preferably 1 to 50 mass %, and more preferably 1 to 40 mass %, based on the total amount of the adhesive. A content within the above range is preferable because it can impart fluidity and heat resistance without reducing adhesive strength.

If necessary, at least one additive selected from the group consisting of conventionally known flow modifiers, nucleating agents, antioxidants, heat stabilizers, UV absorbers, light stabilizers, pigments, dyes, antibacterial agents, antifungal agents, antistatic agents, foaming agents, foaming aids, plasticizers such as mineral oil, and fillers can be added to the hot melt adhesive, provided the addition does not impair the objectives of this disclosure.

The application of the hot melt adhesive is not particularly limited as long as the object of the present disclosure can be achieved, but commercially available hot melt applicators are widely used. Examples of types of hot melt applicators include slot coater applicators, roll coater applicators, spiral applicators that can apply in a spiral shape, omega applicators and control seam applicators that can apply in a wave shape, slot spray applicators and curtain spray applicators that can apply in a planar shape, dot applicators that can apply in a dotted shape, and bead applicators that can apply in a linear shape. A particularly preferred application of the hot melt adhesive is bonding cardboard boxes together.
Methods for using the hot melt adhesive of the present disclosure as a hot melt adhesive include molding the resulting hot melt adhesive into a sheet, film, or nonwoven fabric using a screw extruder with a die portion known as a T-die, inflation, calendar, or spinning method, and then fixing it between the adherends to be laminated and heat-bonding it, or by heating and melting the sheet-shaped adhesive on one of the adherends and then pressing it against the other adherend while cooling it. Also available are methods in which the hot melt adhesive of the present disclosure is melted using the screw extruder and then thermally bonded by inserting the adhesive directly between the adherends to be laminated without the above-mentioned molding process, or, if one of the adherends is a thermoplastic plastic, by directly bonding them by co-extrusion or by applying it directly to one of the adherends and then heat-bonding it again.

Hot melt adhesives can be suitably used for bonding substrates made of polyolefin resins or the like together, bonding the substrates to metal materials (e.g., metal plates, metal foils, metal meshes) or other materials (e.g., nonwoven fabrics, woven fabrics, cloth, paper such as cardboard, glass), and bonding the metal materials or the other materials together, among which they are particularly suitable for bonding cardboard to other adherends or cardboard to cardboard.
Examples of the substrate made of the polyolefin resin or the like include single-layer or laminated resin sheets of polyolefin resin (e.g., polyethylene, polypropylene), polyester resin, polycarbonate resin, polyarylate resin, acrylic resin, polyphenylene sulfide resin, polystyrene resin, vinyl resin, vinyl chloride resin, polyimide resin, epoxy resin, etc.

<Coating agent>
The coating agent of the present disclosure is not particularly limited, but examples thereof include a coating agent prepared by dissolving or dispersing an olefin-based resin (β) or a resin composition (X) using the same in an organic solvent. The coating agent contains the olefin-based resin (β) or the resin composition (X).

Examples of organic solvents include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, and decane; alicyclic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane, ethylcyclohexane, and decahydronaphthalene; alcohols such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, and propanediol; ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, isophorone, and acetophenone; cellosolves such as methyl cellosolve and ethyl cellosolve; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, and butyl formate; and halogenated hydrocarbons such as trichloroethylene, dichloroethylene, and chlorobenzene. One or more organic solvents may be used.

The content of the organic solvent in the coating agent is not particularly limited, but may be, for example, 30% by mass or more, 40% by mass or more, 90% by mass or less, or 80% by mass or less.
The coating agent can be used, for example, as an adhesive or heat sealing agent between metals, between polyolefins, between metals and polyolefins, or as an adhesive for PTP (press through pack) packaging, a laminating adhesive, a paint raw material, or a primer raw material. It is particularly suitable when at least one of the adherends is a plastic material, and among plastic materials, it is preferable when the adherend is a polyolefin material, particularly a polybutene-based material or a polypropylene-based material.

<Molded body>
The molded article of the present invention can be obtained by molding the above-mentioned resin composition (X) of the present invention by a known molding method, such as extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calender molding, or foam molding.
The molded article of the present invention is obtained from the resin composition (X) in which the components contained therein are highly dispersed, and therefore has excellent impact resistance and elongation. In the present invention, even when both the propylene-based polymer (α1) and the ethylene-based polymer (α2) are contained, each component is more highly dispersed, and the molded article has excellent impact resistance and elongation compared to when a conventionally known compatibilizer is contained.

The molded article of the present invention can be used in door trim, rear package trim, instrument panels, gaskets, seatback garnishes, column covers, bumpers, fenders, side moldings, wheel covers, mudguards, mirror covers, instrument panels, exterior doors, hoods, spoilers, windscreens, hubcaps, mirror frames, body panels, airbag covers, protective side moldings, shoe soles, shoe midsoles, innersoles, soles, sandals, wire sheaths for automotive wires or electrical wires for equipment, wire insulators, other wire and cable coatings, housings for home appliances, packing, hot plates, Components for home appliances such as rice cookers, pot bodies, and washing machines, containers such as battery containers, packaging films for electronic components, waterproof sheets, flooring materials, ceiling materials, wallpaper, packaging sheets for building materials and parts, flooring mats, floor finishing materials, blinds, pipes, decorative sheets or protective sheets for building materials, home appliances and furniture such as television cabinets, stereo speaker boxes, video cabinets, various types of storage furniture, and modular furniture, housing components such as doors, door frames, window frames, moldings, baseboards, and opening frames, furniture components for kitchens and storage furniture doors, office floor mats, carpet anti-slip pads, low-temperature heat-sealable films, and easy-peel films. films, packaging films, individual packaging materials for medicines, grips, gaskets, multi-layer hoses, infusion bottles, sanitary bottles such as shampoo, cosmetic bottle cases, caps, cap liners, drinking water cap liners, stationery such as writing implements, toys, leisure goods, disposable diapers, disposable underwear, sanitary parts and elastic parts such as sanitary napkins, clothing cases, buckets, washbasins, cooking utensils, various other cases, containers, agricultural films, playground equipment, boat and watercraft parts, garden furniture, roller bottles and culture medium bottles used for cultivation, diaper tabs, sterilization wrap, dustcloths It can be used in bedding, food packaging films, retort packaging materials, retort tableware containers, food packaging trays, beverage cups and bottles, various other bottles, cups, sheets, films, tubes, syringes, syringe barrels, ampoules, petri dishes and other medical devices, medical cases, bandages, intravenous injection bags, liquid storage containers such as pouches and bottles, medical gowns and aprons, surgical drapes, covers for home appliances and residential lighting fixtures, automotive interior lighting covers, LED lamp covers for electrical and electronic components, covers for other display devices, solar cell sealing sheets, battery packaging, and lithium-ion battery packaging.

<Film>
An example of the use of the olefin resin (β) or the resin composition (X) is a film containing either of them.
The film containing the olefin resin (β) or the resin composition (X) using the same may be a stretched film or a non-stretched film, and is preferably a non-stretched film.
The unstretched film is not particularly limited as long as it is an unstretched film, and its shape, size (thickness), etc. may be appropriately selected depending on the desired application. The unstretched film may be a single layer or a multilayer. If it is a multilayer film, at least one layer of the film may contain the olefin-based resin (β) or the resin composition (X). This includes co-extrusion methods using known multilayer film molding methods such as T-die film molding and inflation film molding, as well as methods in which a layer containing the olefin-based resin (β) or the resin composition (X) is laminated on a pre-formed substrate. The substrate is not particularly limited, and may be a metal such as an aluminum plate, a steel plate, or a stainless steel plate, or a thermoplastic resin. When the unstretched film is multilayer, this means that all of the layers are unstretched.

The thickness of the unstretched film (total thickness if multi-layered) is preferably 5 μm or more, more preferably 10 μm or more, and is preferably 150 μm or less, more preferably 100 μm or less.
In this specification, no particular distinction is made between a film and a sheet, but a film generally refers to a membranous body having a thickness of less than 250 μm, and a sheet generally refers to a thin plate-like body having a thickness of 250 μm or more.
The film can be used as, for example, a stretch film, a shrink film, a breathable film, an adhesive film, a film for processing, or the like.

<Sheet>
Examples of applications of the olefin resin (β) or the resin composition (X) include sheets containing either of them.
The sheet is not particularly limited, and its shape, size (thickness), etc. may be appropriately selected depending on the desired application. The sheet may be single-layered or multi-layered. In the case of a multi-layered sheet, at least one layer of the sheet may contain the olefin resin (β) or the resin composition (X).
The thickness of the sheet (total thickness if multi-layered) is preferably 250 to 2000 μm, more preferably 250 to 1500 μm.
Specific uses of the above-mentioned sheet include, for example, packaging sheets for packaging food, liquids, medicines, etc., and containers formed from the sheet (e.g., trays and cups thermoformed from the sheet, and containers formed by folding the sheet).

<Injection molded articles and blow molded articles>
The molded article of the present disclosure may be, for example, an injection molded article. The injection molded article is not particularly limited, and examples of the injection molded article include a molded article produced by injection molding into a desired shape using a conventionally known injection molding apparatus under known conditions.
Injection molded articles can be used in a wide range of applications, such as trim materials for automobile interiors, exterior parts for automobiles, housings for home appliances, containers, tubes, or pipes.

The molded article of the present disclosure may be, for example, a blow molded article. The blow molded article is not particularly limited, and examples of the blow molded article include a molded article produced by blow molding into a desired shape using a conventionally known blow molding device under known conditions.
The blow molded article may be, for example, a multilayer molded article, in which at least one layer of the multilayer molded article contains the olefin resin (β) or the resin composition (X).
Specific applications of injection-molded and blow-molded articles include, for example, food containers, beverage containers, caps, pharmaceutical containers, and various other containers, daily necessities, housings for home appliances, automobile parts, tubes, and pipes. Daily necessities include, for example, clothing cases, buckets, washbasins, stationery such as writing implements, containers, toys, cooking utensils, and various other cases.

<Sealant film>
An example of the molded article is a sealant film.
The sealant film has at least one layer (hereinafter also referred to as "layer (X)") formed from a resin composition (X). The sealant film may be a single layer or a multilayer having two or more layers. In this case, the resin composition (X) is preferably a resin composition (X) containing an olefin resin (β) and a propylene polymer (α1), or a resin composition (X) containing an olefin resin (β), a propylene polymer (α1), and an ethylene polymer (α2).
The sealant film may have two or more layers (X). The sealant film may have the layer (X) and a layer (another layer) other than the layer (X). The sealant film may have two or more of the other layers.

In this specification, no particular distinction is made between a film and a sheet, but a film generally refers to a membranous body having a thickness of less than 250 μm, and a sheet generally refers to a thin plate-like body having a thickness of 250 μm or more.
The shape, size, thickness, etc. of the sealant film may be appropriately selected depending on the desired application. The sealant film may be either a stretched film or a non-stretched film, but is preferably a non-stretched film. When the non-stretched film is a multilayer film, "non-stretched" means that none of the layers are stretched.
The non-stretched film is not particularly limited as long as it is a film that has not been stretched, and the shape, size, thickness, etc. may be appropriately selected depending on the desired application. The non-stretched film may be a single layer or a multilayer film having two or more layers. When the non-stretched film is a multilayer film, at least one of the layers may be layer (X). That is, the non-stretched film may be a single layer or multilayer film consisting of only layer (X), or may be a laminate having layer (X) and a substrate. Specific examples of the substrate will be described later.

The thickness of the sealant film or unstretched film (the total thickness of each layer if the film is multilayered) is preferably 5 μm or more, more preferably 10 μm or more, even more preferably 20 μm or more, and is preferably 150 μm or less, more preferably 130 μm or less, even more preferably 100 μm or less, for example, 5 to 150 μm.
Specific applications of the sealant film or non-stretched film include, for example, packaging films for packaging food, liquids, medicines, electronic components, etc., and packaging materials obtained therefrom.

The above-mentioned sealant film or non-stretched film can be produced, for example, using at least resin composition (X) using a conventionally known single-layer or multi-layer film molding machine. The method for producing the non-stretched film is not particularly limited as long as it does not impair the objectives of the present disclosure. Non-stretched films include films obtained by co-extrusion using known multi-layer film molding methods such as T-die film molding and inflation film molding, and films obtained by laminating layer (X) onto a pre-formed substrate. The non-stretched film may be obtained, for example, by a manufacturing method including a step of bonding a single-layer or multi-layer film containing at least one layer (X) (e.g., a single-layer or multi-layer film consisting only of layer (X)) to a substrate by any method selected from the group consisting of melt extrusion lamination, thermal lamination, and dry lamination.

<Laminate>
An example of the molded article is a laminate.
The laminate includes a substrate and a layer (layer (X)) formed from a resin composition (X). In this case, the resin composition (X) is preferably a resin composition (X) containing a propylene polymer (α1) or a resin composition (X) containing an olefin resin (β), a propylene polymer (α1), and an ethylene polymer (α2).
In one embodiment, the laminate includes a substrate and the sealant film. The laminate is formed by laminating, for example, a substrate and a sealant film.

Examples of the substrate include resin films, metal foils, paper, and vapor-deposited films. Examples of the resin constituting the resin film include thermoplastic resins, specifically polyolefin resins (e.g., polyethylene, polypropylene), polystyrene resins, polyester resins (e.g., polyethylene terephthalate (PET)), polyamide resins, polyimide resins, polycarbonate resins, polyarylate resins, acrylic resins, polyphenylene sulfide resins, vinyl resins, vinyl chloride resins, and epoxy resins. The resin film may be a single layer or a multilayer of two or more layers. The resin film may be a stretched film or a non-stretched film. Examples of the metal foil include aluminum foil, steel foil, and stainless steel foil, with aluminum foil being preferred.
The substrate is preferably at least one selected from the group consisting of polyolefin film, polystyrene film, polyester film, polyamide film, laminated film of polyolefin film and gas barrier resin film, metal foil such as aluminum foil, paper, and vapor-deposited film.

The above laminate can be produced, for example, using a conventionally known single-layer or multi-layer film molding machine. The above laminate can be produced, for example, by a manufacturing method including a step of bonding a substrate and the above sealant film by any method selected from the group consisting of melt extrusion lamination, thermal lamination, and dry lamination. The above laminate can be produced, for example, by a manufacturing method including a step of bonding a substrate and a single-layer or multi-layer film consisting only of layer (X) by any method selected from the group consisting of melt extrusion lamination, thermal lamination, and dry lamination.

The laminate itself may be used as a sealant film. In this case, the substrate is preferably a resin film, more preferably a non-stretched film. That is, the sealant film may be a single-layer or multi-layer film consisting of only the layer (X), or may be a laminate having the layer (X) and the substrate.
The sealant film and the laminate have excellent resistance to whitening when stretched, and good heat resistance and tensile strength. Therefore, by taking advantage of the properties of the sealant film, they can be suitably used as packaging for a variety of items, such as daily necessities, food (food packaging materials), liquids, pharmaceuticals, electronic components, and construction materials.

The sealant film or laminate may be included in an electricity storage device such as a lithium ion battery or a lithium ion capacitor. The sealant film or laminate can be suitably used, for example, as packaging for lithium ion batteries. From another perspective, the present disclosure can also be said to provide an electricity storage device containing resin composition (X). Examples of such electricity storage devices include electricity storage devices containing the sealant film or laminate, and specific examples thereof include packaging for lithium ion batteries containing the sealant film or laminate.

<Lithium-ion battery>
The sealant film or the laminate can be suitably used as a packaging material for lithium ion batteries.
A lithium-ion battery typically includes a positive electrode, a negative electrode, a separator between the positive and negative electrodes, and a nonaqueous electrolyte. The positive electrode typically includes a positive electrode current collector made of a metal or carbon material, and a positive electrode active material capable of absorbing and releasing lithium, such as a composite oxide of lithium and a transition metal. The negative electrode typically includes a negative electrode current collector made of a carbon material, and a negative electrode active material capable of absorbing and releasing lithium ions, such as metallic lithium, a lithium-containing alloy, or a metal or alloy capable of alloying with lithium. The nonaqueous electrolyte includes a lithium salt as an electrolyte and a nonaqueous solvent. In a lithium-ion battery, the positive electrode, negative electrode, and separator are impregnated with the nonaqueous electrolyte. Details of the nonaqueous solvent will be described later in the section "Nonaqueous Solvent."

In many cases, lithium-ion batteries have packaging (lithium-ion battery packaging) around their periphery. The positive electrode, negative electrode, separator, and non-aqueous electrolyte are enclosed inside the packaging. Typically, a positive electrode terminal and a negative electrode terminal are connected to the positive electrode and negative electrode, respectively. Part of the positive electrode terminal and part of the negative electrode terminal are exposed to the outside of the packaging.

The case where the sealant film or the laminate is used as a package will be described below. A lithium ion battery is obtained by sandwiching a positive electrode, a negative electrode, or the like between a pair of sealant films or a pair of laminates, and heat-sealing the peripheral edges of the pair of sealant films or the pair of laminates in a manner such that a portion of the positive electrode terminal and a portion of the negative electrode terminal are exposed to the outside of the pair of sealant films or the pair of laminates. When the laminate is used as a package, the laminate may have a substrate made of a metal such as aluminum foil.
Lithium ion batteries using the lithium ion battery packaging can be used in, for example, portable electronic devices, personal computers, robots, drones, automobiles, aircraft, wearable devices, and energy storage systems (ESS) for home use or renewable energy power generation.

<Non-aqueous solvent>
A non-aqueous electrolyte for a lithium ion battery generally contains a non-aqueous solvent.
As the non-aqueous solvent, various known ones can be appropriately selected. As the non-aqueous solvent, it is preferable to use at least one selected from the group consisting of cyclic aprotic solvents and chain aprotic solvents. When aiming to improve the flash point of the solvent in order to improve the safety of the battery, it is preferable to use a cyclic aprotic solvent as the non-aqueous solvent.

(cyclic aprotic solvents)
Examples of cyclic aprotic solvents include cyclic carbonates, cyclic carboxylic acid esters, cyclic sulfones, and cyclic ethers.
The cyclic aprotic solvent may be used alone or in combination of two or more.
The content of the cyclic aprotic solvent in the nonaqueous solvent is preferably 10 to 100% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 80% by mass. By adjusting the content to such a ratio, for example, the conductivity of the electrolyte, which is related to the charge/discharge characteristics of the battery, can be increased.

Examples of cyclic carbonates include ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, and 2,3-pentylene carbonate. Among these, ethylene carbonate and propylene carbonate, which have high dielectric constants, are preferred. For batteries that use graphite as the negative electrode active material, ethylene carbonate is more preferred. Two or more cyclic carbonates may be used in combination.

Examples of cyclic carboxylic acid esters include γ-butyrolactone, δ-valerolactone, and alkyl-substituted derivatives such as methyl-γ-butyrolactone, ethyl-γ-butyrolactone, and ethyl-δ-valerolactone.
Cyclic carboxylic acid esters have low vapor pressure, low viscosity, and high dielectric constant, and can reduce the viscosity of the electrolyte without lowering the flash point and the degree of dissociation of the electrolyte. Therefore, cyclic carboxylic acid esters have the characteristic of being able to increase the conductivity of the electrolyte, which is an indicator of the charge/discharge characteristics of the battery, without increasing the flammability of the electrolyte. Therefore, when aiming to increase the flash point of the solvent, it is preferable to use a cyclic carboxylic acid ester as the cyclic aprotic solvent. γ-Butyrolactone is most preferable.

The cyclic carboxylic acid ester is preferably used in combination with other cyclic aprotic solvents and/or chain aprotic solvents, for example, a mixture (combination) of a cyclic carboxylic acid ester with a cyclic carbonate and/or a chain carbonate.
Examples of combinations of cyclic carboxylic acid esters and cyclic carbonates and/or chain carbonates include γ-butyrolactone and ethylene carbonate, γ-butyrolactone, ethylene carbonate and dimethyl carbonate, γ-butyrolactone, ethylene carbonate and methyl ethyl carbonate, γ-butyrolactone, ethylene carbonate and diethyl carbonate, γ-butyrolactone and propylene carbonate, γ-butyrolactone, propylene carbonate and dimethyl carbonate, and γ-butyrolactone, propylene carbonate and methyl ethyl carbonate. carbonate, γ-butyrolactone, propylene carbonate, and diethyl carbonate, γ-butyrolactone, ethylene carbonate, and propylene carbonate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and dimethyl carbonate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and methyl ethyl carbonate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and diethyl carbonate, γ-butyrolactone, ethylene carbonate, dimethyl carbonate, and methyl ethyl carbonate, γ-butyrolactone γ-butyrolactone, ethylene carbonate, dimethyl carbonate, and diethyl carbonate, γ-butyrolactone, ethylene carbonate, methyl ethyl carbonate, and diethyl carbonate, γ-butyrolactone, ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, and diethyl carbonate, γ-butyrolactone, ethylene carbonate, propylene carbonate, dimethyl carbonate, and methyl ethyl carbonate, γ-butyrolactone, ethylene carbonate, propylene carbonate, dimethyl carbonate, and diethyl carbonate, γ-butyrolactone, Examples include ethylene carbonate, propylene carbonate, methyl ethyl carbonate, and diethyl carbonate, γ-butyrolactone, ethylene carbonate, propylene carbonate, dimethyl carbonate, methyl ethyl carbonate, and diethyl carbonate, γ-butyrolactone and sulfolane, γ-butyrolactone, ethylene carbonate, and sulfolane, γ-butyrolactone, propylene carbonate, and sulfolane, γ-butyrolactone, ethylene carbonate, propylene carbonate, and sulfolane, and γ-butyrolactone, sulfolane, and dimethyl carbonate.

Examples of cyclic sulfones include sulfolane, 2-methyl sulfolane, 3-methyl sulfolane, dimethyl sulfone, diethyl sulfone, dipropyl sulfone, methyl ethyl sulfone, and methyl propyl sulfone.
An example of the cyclic ether is dioxolane.

(chain aprotic solvent)
Examples of the chain aprotic solvent include chain carbonates, chain carboxylic acid esters, chain ethers, and chain phosphate esters.
The chain aprotic solvent may be used alone or in combination of two or more.
The content of the chain aprotic solvent in the non-aqueous solvent is preferably 10 to 100% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 80% by mass.

Examples of chain carbonate include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, ethyl propyl carbonate, dipropyl carbonate, methyl butyl carbonate, ethyl butyl carbonate, dibutyl carbonate, methyl pentyl carbonate, ethyl pentyl carbonate, dipentyl carbonate, methyl heptyl carbonate, ethyl heptyl carbonate, diheptyl carbonate, methyl hexyl carbonate, ethyl hexyl carbonate, dihexyl carbonate, methyl octyl carbonate, ethyl octyl carbonate, dioctyl carbonate and methyl trifluoroethyl carbonate.Two or more chain carbonates can be mixed and used.
An example of the chain carboxylic acid ester is methyl pivalate.
An example of the chain ether is dimethoxyethane.
An example of the chain phosphate ester is trimethyl phosphate.

(Solvent Combination)
The nonaqueous electrolyte solution may contain only one type of nonaqueous solvent, or two or more types of nonaqueous solvents.
One or more cyclic aprotic solvents may be used alone, one or more chain aprotic solvents may be used alone, or a mixture of a cyclic aprotic solvent and a chain aprotic solvent may be used. When it is particularly intended to improve the load characteristics and low-temperature characteristics of the battery, it is preferable to use a combination of a cyclic aprotic solvent and a chain aprotic solvent as the non-aqueous solvent.
From the viewpoint of electrochemical stability of the electrolyte, it is most preferable to use a cyclic carbonate as the cyclic aprotic solvent and a chain carbonate as the chain aprotic solvent. The combination of a cyclic carboxylic acid ester with a cyclic carbonate and/or a chain carbonate can also increase the conductivity of the electrolyte, which is related to the charge/discharge characteristics of the battery.

Combinations of cyclic carbonates and chain carbonates include, for example, ethylene carbonate and dimethyl carbonate, ethylene carbonate and methyl ethyl carbonate, ethylene carbonate and diethyl carbonate, propylene carbonate and dimethyl carbonate, propylene carbonate and methyl ethyl carbonate, propylene carbonate and diethyl carbonate, ethylene carbonate, propylene carbonate and methyl ethyl carbonate, ethylene carbonate, propylene carbonate and diethyl carbonate, ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate, ethylene carbonate and dimethyl carbonate Examples include ethylene carbonate, methyl ethyl carbonate, and diethyl carbonate, ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, and diethyl carbonate, ethylene carbonate, propylene carbonate, dimethyl carbonate, and methyl ethyl carbonate, ethylene carbonate, propylene carbonate, dimethyl carbonate, and diethyl carbonate, ethylene carbonate, propylene carbonate, methyl ethyl carbonate, and diethyl carbonate, and ethylene carbonate, propylene carbonate, dimethyl carbonate, methyl ethyl carbonate, and diethyl carbonate.

The mixing ratio of the cyclic carbonate to the chain carbonate (cyclic carbonate:chain carbonate), expressed as a mass ratio, is preferably 5:95 to 80:20, and more preferably 10:90 to 70:30. By using such a mixing ratio, it is possible to suppress an increase in the viscosity of the electrolyte and increase the degree of dissociation of the electrolyte, thereby increasing the conductivity of the electrolyte, which is related to the charge/discharge characteristics of the battery, and further increasing the solubility of the electrolyte. This results in an electrolyte with excellent electrical conductivity at room temperature or low temperatures, which improves the load characteristics of the battery at room temperature to low temperatures.

A lithium ion battery contains a nonaqueous electrolyte solution containing the nonaqueous solvent. For this reason, the packaging (lithium ion battery packaging) constituting the lithium ion battery is preferably resistant to leaching into the nonaqueous solvent and swelling caused by the nonaqueous solvent, and is preferably able to maintain a certain level of mechanical strength even when exposed to contact with the nonaqueous solvent. The sealant film and laminate, which have a layer (layer (X)) formed from resin composition (X), have excellent whitening resistance and, for example, are resistant to leaching into the nonaqueous solvent and swelling caused by the nonaqueous solvent, and are able to maintain a certain level of mechanical strength even when exposed to contact with the nonaqueous solvent. Therefore, the sealant film and laminate can be suitably used as packaging for lithium ion batteries.

The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples as long as it does not depart from the gist of the invention.
<Measurement and evaluation methods>
In the following examples and comparative examples, the physical properties were measured or evaluated by the following methods.

[Weight average molecular weight (Mw)]
The weight-average molecular weight (Mw) of the polymer sample was measured using a gel permeation chromatograph (HLC-8321 GPC/HT model, manufactured by Tosoh Corporation) with two TSKgel GMH ₆ -HT columns and two TSKgel GMH ₆ -HTL columns (both columns with an inner diameter of 7.5 mm and a length of 300 mm) connected in series. The mobile phase medium was o-dichlorobenzene to which 0.025% by mass of BHT (Fujifilm Wako Pure Chemical Industries) was added as an antioxidant. Measurements were performed at a sample concentration of 0.15% (W/V), a flow rate of 1.0 ml/min, and 140°C. Standard polystyrenes manufactured by Tosoh Corporation were used for molecular weights of 590 to 20,600,000. The obtained chromatogram was analyzed using Empower3 data processing software manufactured by Waters, with a calibration curve prepared using a standard polystyrene sample, according to a known method, to calculate the weight average molecular weight (Mw).

[Melting point (Tm) and heat of fusion (ΔH)]
The melting point (Tm) and heat of fusion (ΔH) of the olefin resin (β) described below were determined by DSC measurement under the following conditions.
Using a differential scanning calorimeter (SII DSC220), approximately 5.0 mg of sample was heated from 30°C to 200°C at a heating rate of 10°C/min under a nitrogen atmosphere and held at that temperature for 10 minutes. The sample was then cooled to -100°C at a cooling rate of 10°C/min, held at that temperature for 5 minutes, and then heated to 200°C at a heating rate of 10°C/min. The endothermic peak observed during this second heating was taken as the melting peak, and the temperature at which the melting peak appeared was determined as the melting point (Tm). In Tables 1-1 to 1-3 described below, if there were two melting peaks, the temperatures of both melting points (Tm) are listed. The heat of fusion (ΔH) was also determined by calculating the area of the melting peak. If the melting peak was multimodal, the area of the entire melting peak was calculated.

[Glass transition temperature (Tg)]
The glass transition temperature (Tg) of the olefin resin (β) described below was determined by DSC measurement under the same conditions as the melting point (Tm). The glass transition temperature (Tg) is detected as the DSC curve bending due to a change in specific heat during the second heating, causing the baseline to shift in parallel. The temperature at the intersection of the tangent to the baseline lower than this bending and the tangent to the point where the slope of the bending portion is maximum was taken as the glass transition temperature (Tg).

[Composition of each monomer component]
For the main chain of the olefin-based resin (β) described below, the repeating units derived from each monomer of ethylene and propylene or 1-butene copolymer were calculated from a calibration curve based on the correlation between the ethylene composition ratio (mol %) and the melting point (Tm) (°C). The calibration curve was prepared by carrying out polymerization in the same manner as in the examples described below, except that no terminally unsaturated polypropylene was added. Furthermore, by varying the feed ratio of continuously fed ethylene to propylene or 1-butene, multiple ethylene-propylene copolymers or ethylene-1-butene copolymers with different propylene or 1-butene composition ratios were obtained. The propylene or 1-butene composition ratios of the obtained ethylene-propylene copolymers or ethylene-1-butene copolymers were measured by the following nuclear magnetic resonance spectroscopy analysis, and a calibration curve was prepared. For the side chain of the olefin-based resin (β) described below, the analytical values of the terminally unsaturated propylene polymer and terminally unsaturated propylene-ethylene copolymer obtained in step (A) of the examples described below were used as is.
(Nuclear magnetic resonance spectroscopy: measurement conditions)
Apparatus: JEOL ECX400P nuclear magnetic resonance spectrometer, measurement nuclei: ¹ H (400 MHz); ¹³ C (125 MHz), measurement mode: single pulse, pulse width: 45° (5.25 μsec), number of points: 32 k, measurement range: 20 ppm (−4 to 16 ppm), repetition time: 7.0 sec, number of accumulations: 64, measurement solvent: orthodichlorobenzene-d ₄ , sample concentration: ca. 20 mg/0.6 mL, measurement temperature: 120°C, window function: exponential (BF: 0.12 Hz), chemical shift reference: orthodichlorobenzene (7.1 ppm).
The proportions of ethylene and propylene in the ethylene-propylene copolymer that is the main chain of the graft-type olefin polymer [R1] in the olefin-based resin (β), or the proportions of ethylene and 1-butene in the ethylene-1-butene copolymer that is the main chain of the graft-type olefin-based polymer [R1] in the olefin-based resin (β), were measured and quantified by measuring the peak intensity derived from ethylene and the peak intensity (integral value) derived from propylene or 1-butene obtained from 125 MHz ^13C -NMR (JEOL ECX400P).

[Terminal vinyl ratio]
The terminal vinyl ratio of terminally unsaturated polypropylene and terminally unsaturated propylene-ethylene copolymer was measured by quantifying the terminal vinyl ratio as the amount of vinyl groups in the total amount of terminal unsaturation from the intensity ratio of peaks derived from unsaturated bonds obtained from ⁴⁰⁰ MHz 1 H-NMR (JEOL ECX400P).

[Proportion of P (total content of components (i) to (iv) above) in olefin-based resin (β)]
(Method 1: Calculate from the amount of ingredients)
The proportion of the component P derived from the terminally unsaturated polypropylene and the terminally unsaturated propylene-ethylene copolymer in the olefin resin (β) described below (the proportion of the total P content of the components (i) to (iv) above) was calculated from the difference between the charged amount of the terminally unsaturated polypropylene or the terminally unsaturated propylene-ethylene copolymer and the amount of the obtained olefin resin (β).
(Method 2: Calculation by analyzing olefin resin (β))
The proportion of component P derived from terminally unsaturated polypropylene and terminally unsaturated propylene-ethylene copolymer in the olefin resin (β) described below was calculated by analyzing the olefin resin (β). Specifically, the proportion (mass%) of P, which is the total of components derived from terminally unsaturated polypropylene and terminally unsaturated propylene-ethylene copolymer, was calculated from a calibration curve based on the correlation between the heat of fusion (ΔH) (J/g) of the melting point (Tm) (°C) and the proportion (mass%) of P calculated from the above-mentioned charged amount.
The calibration curve was prepared as follows. First, polymerization was carried out in the same manner as in the Examples described below, while varying the amounts of terminally unsaturated polypropylene and terminally unsaturated propylene-ethylene copolymer charged, to obtain a plurality of olefin resins having different P proportions (% by mass). Next, polymerization was carried out in the same manner for a plurality of main chain ethylene compositions, to obtain a plurality of olefin resins having different main chain ethylene composition proportions and different P proportions (% by mass). Furthermore, a calibration curve was prepared using the heat of fusion (ΔH) (J/g) of the melting points (Tm) of these olefin resins and the P proportion (% by mass) calculated from the charged amounts.
The P content in the olefin resin (β-1) produced in Example 1A described later was 46.1% by mass by Method 1 (calculated from the charged amount) and 46.3% by mass by Method 2 (analysis result using the created calibration curve), which were equivalent. The P content in the olefin resin (β-2) produced in Example 2A described later was 31.6% by mass by Method 1 (calculated from the charged amount) and 31.5% by mass by Method 2, which were equivalent.
In the following examples (see Tables 1-1 to 1-3), values calculated by Method 1 are shown.

[Confirmation of Graft-Type Olefin Polymer [R1]]
By peak separation of the chromatogram obtained by gel permeation chromatography, it was confirmed that the terminally unsaturated polypropylene and the terminally unsaturated propylene-ethylene copolymer had been consumed, and that the graft olefin polymer [R1] had been produced.

[Intrinsic viscosity [η]]
The intrinsic viscosity [η] of the olefin resin (β) described below was measured at 135° C. in a decalin solvent using an Ubbelohde viscometer as a measuring device.
Approximately 20 mg of copolymer was dissolved in 25 mL of decalin, and then the specific viscosity ηsp was measured using an Ubbelohde viscometer in an oil bath at 135 ° C. After diluting the decalin solution with 5 mL of decalin, the specific viscosity ηsp was measured in the same manner as above. This dilution operation was repeated two more times, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was calculated as the limiting viscosity [η] (unit: dl / g) (see the formula below).
[η]=lim(ηsp/C) (C→0)

[Melt flow rate (MFR)]
The melt flow rate (MFR) of the olefin resin (β) described below was measured in accordance with ASTM D1238E under conditions of 190° C. and a load of 2.16 kg.
[density]
The strand resin flowed out in the above-mentioned measurement of melt flow rate (MFR) was used to measure density at 23° C. by the density gradient tube method in accordance with JIS K7112.

<Reagents>
[reagent]
Toluene used was purified using an organic solvent purification apparatus manufactured by GlassContour, Inc. Xylene was first-grade xylene manufactured by Junsei Chemical Co., Ltd., which was passed through a 500 mL alumina column.
The alumina column used was E. Merck's activated alumina 90 (neutral, activity level I) dried for at least 4 hours at 150° C. The aluminoxane toluene solution used was a 20% by mass methylaluminoxane/toluene solution manufactured by Nippon Alkyla Aluminum Co., Ltd., diluted with toluene (1.0 M).
Triisobutylaluminum manufactured by Tosoh Finechem Co., Ltd. was diluted with toluene (1.0 M) for use. Triphenylcarbenium tetrakis(pentafluorophenyl)borate manufactured by Asahi Glass Co., Ltd. was dissolved in toluene at 4.0 mmol/L for use.
Dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride used as the polymerization catalyst for compound [A] and the bridged metallocene compound represented by the following formula (B-1), used as the polymerization catalyst for compound [B], were synthesized according to known methods.

[Example 1A]
Step (A): Production of Terminally Unsaturated Polypropylene (M-1) 1.5 L of toluene was placed in a 2 L glass reactor that had been thoroughly purged with nitrogen, and the temperature was then raised to 87°C. While stirring the interior of the polymerization vessel at 600 rpm, propylene was continuously fed at 240.0 L/hr to saturate the liquid and gas phases. While propylene was still being continuously fed, 7.5 mL (7.5 mmol) of a toluene solution (1.0 mol/L) of methylaluminoxane (also referred to as MAO) was added, followed by 4.0 mL (0.012 mmol) of a toluene solution (0.0030 mol/L) of dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride. Polymerization was carried out at 87°C for 30 minutes under atmospheric pressure. The polymerization was terminated by adding a small amount of isobutanol. The resulting polymerization reaction solution was added to 5 L of methanol containing a small amount of hydrochloric acid, and a polymer was precipitated. The precipitate was washed with methanol and then dried under reduced pressure at 80°C for 10 hours to obtain 108.3 g of a propylene polymer (terminally unsaturated polypropylene (M-1)). The resulting terminally unsaturated polypropylene (M-1) had a polypropylene-equivalent Mw of 22,907, an Mw/Mn of 1.88, and a one-terminal vinyl percentage of 72% as measured by ^1H -NMR.

Step (B): Production of Olefin Resin (β-1) 10.0 g of terminally unsaturated polypropylene (M-1) and 500 mL of xylene were placed in a 1 L glass reactor that had been thoroughly purged with nitrogen, and the temperature was then raised to 100° C. to dissolve the terminally unsaturated polypropylene (M-1). While stirring the inside of the polymerization vessel at 600 rpm, ethylene and propylene were continuously fed thereto at 99.0 L/hr and 15.6 L/hr, respectively, to saturate the liquid phase and gas phase. While continuously supplying ethylene and propylene, 3.0 mL (3.0 mmol) of a toluene solution (1.0 mol/L) of triisobutylaluminum (also referred to as iBu ₃ Al), 1.5 mL (0.0030 mmol) of a toluene solution (0.0020 mol/L) of the bridged metallocene compound (B-1), and then 3.75 mL (0.015 mmol) of a toluene solution (4.0 mmol/L) of triphenylcarbenium tetrakis(pentafluorophenyl)borate (also referred to as Ph ₃ CB(C ₆ F ₅ ) ₄ ) were added, and polymerization was carried out at 100°C for 30 minutes under atmospheric pressure. The polymerization was terminated by adding a small amount of isobutanol. The resulting polymerization reaction solution was added to 1.5 L of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitate was washed with methanol and then dried under reduced pressure at 130°C for 10 hours to obtain 21.7 g of olefin resin (β-1). Gel permeation chromatography confirmed that the terminally unsaturated polypropylene had been consumed, confirming that a graft-type olefin polymer [R1-1] had been produced. The analytical results of the olefin resin (β-1) are shown in Table 1-1.

[Example 2A]
In step (B) of Example 1A, the amount of terminally unsaturated polypropylene (M-1) added was changed to 7.0 g, the toluene solution of the bridged metallocene compound (B-1) (0.0020 mol/L) was changed to 2.5 mL (0.0050 mmol), and the amount of toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl)borate (4.0 mmol/L) added was changed to 6.25 mL (0.025 mmol). The same procedure as in Example 1A was carried out to obtain 22.2 g of olefin resin (β-2). Gel permeation chromatography confirmed that the terminally unsaturated polypropylene had been consumed, confirming the formation of a graft-type olefin polymer [R1-2]. The analytical results of the obtained olefin resin (β-2) are shown in Table 1-1.

[Example 3A]
The same procedure as in Example 1A was carried out, except that in step (B) of Example 1A, the amount of terminally unsaturated polypropylene (M-1) added was changed to 9.5 g and the supply rate of propylene was changed to 7.2 L/hr, to obtain 21.4 g of an olefin resin (β-3). It was confirmed by gel permeation chromatography that the terminally unsaturated polypropylene had been consumed, and that a graft-type olefin polymer [R1-3] had been produced. The analytical results of the obtained olefin resin (β-3) are shown in Table 1-1.

[Example 4A]
The same procedure as in Example 2A was carried out, except that in step (B) of Example 2A, the propylene supply rate was changed to 7.2 L/hr, to obtain 22.6 g of an olefin resin (β-4). It was confirmed by gel permeation chromatography that the terminally unsaturated polypropylene had been consumed, and that a graft-type olefin polymer [R1-4] had been produced. The analytical results of the obtained olefin resin (β-4) are shown in Table 1-1.

[Example 5A]
In step (B) of Example 1A, the amount of terminally unsaturated polypropylene (M-1) added was changed to 8.0 g, the propylene feed rate was changed to 24.0 L/hr, the amount of triisobutylaluminum in a toluene solution (1.0 mol/L) was changed to 2.3 mL (2.3 mmol), the amount of the bridged metallocene compound (B-1) in a toluene solution (0.0020 mol/L) was changed to 1.0 mL (0.0020 mmol), and the amount of triphenylcarbenium tetrakis(pentafluorophenyl)borate in a toluene solution (4.0 mmol/L) was changed to 2.5 mL (0.010 mmol). The same procedure as in Example 1A was carried out, yielding 17.1 g of an olefin resin (β-5). Gel permeation chromatography confirmed that the terminally unsaturated polypropylene had been consumed, confirming the formation of a graft-type olefin polymer [R1-5]. The analytical results of the resulting olefin resin (β-5) are shown in Table 1-1.

[Example 6A]
In step (B) of Example 5A, the amount of terminally unsaturated polypropylene (M-1) added was changed to 6.0 g, the toluene solution of the bridged metallocene compound (B-1) (0.0020 mol/L) was changed to 2.0 mL (0.0040 mmol), and the toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl)borate (4.0 mmol/L) was changed to 5.0 mL (0.020 mmol). The same procedure as in Example 5A was carried out to obtain 20.9 g of an olefin-based resin (β-6). Gel permeation chromatography confirmed that the terminally unsaturated polypropylene had been consumed, and it was confirmed that a graft-type olefin-based polymer [R1-6] had been produced. The analytical results of the obtained olefin-based resin (β-6) are shown in Table 1-1.

[Example 7A]
In step (B) of Example 1A, the amount of terminally unsaturated polypropylene (M-1) added was changed to 7.0 g, the ethylene supply rate to 90.0 L/hr, the propylene supply rate to 30.0 L/hr, the amount of triisobutylaluminum in a toluene solution (1.0 mol/L) to 2.0 mL (2.0 mmol), the amount of the bridged metallocene compound (B-1) in a toluene solution (0.0020 mol/L) to 2.0 mL (0.0040 mmol), and the amount of triphenylcarbenium tetrakis(pentafluorophenyl)borate in a toluene solution (4.0 mmol/L) to 5.0 mL (0.020 mmol) were changed. The same procedure as in Example 1A was carried out to obtain 11.6 g of an olefin resin (β-7). It was confirmed by gel permeation chromatography that the terminally unsaturated polypropylene had been consumed, and it was confirmed that a graft-type olefin polymer [R1-7] had been produced. The analytical results of the obtained olefin resin (β-7) are shown in Table 1-1.

[Example 8A]
In step (B) of Example 7A, the amount of terminally unsaturated polypropylene (M-1) added was changed to 4.5 g, the toluene solution (0.0020 mol/L) of the bridged metallocene compound (B-1) was changed to 3.0 mL (0.0060 mmol), and the toluene solution (4.0 mmol/L) of triphenylcarbenium tetrakis(pentafluorophenyl)borate was changed to 7.5 mL (0.030 mmol). The same procedure as in Example 7A was carried out to obtain 14.4 g of an olefin-based resin (β-8). Gel permeation chromatography confirmed that the terminally unsaturated polypropylene had been consumed, and it was confirmed that a graft-type olefin-based polymer [R1-8] had been produced. The analytical results of the obtained olefin-based resin (β-8) are shown in Table 1-1.

[Example 9A]
The same operation as in Example 1A was carried out, except that in step (B) of Example 1A, the feed rate of ethylene was changed to 120.0 L/hr, the feed rate of propylene to 18.0 L/hr, the amount of a toluene solution of triisobutylaluminum (1.0 mol/L) was changed to 2.5 mL (2.5 mmol), and the polymerization temperature was changed to 96°C, to obtain 23.1 g of an olefin resin (β-9). Gel permeation chromatography confirmed that the terminally unsaturated polypropylene had been consumed, and that a graft-type olefin polymer [R1-9] had been produced. The analytical results of the obtained olefin resin (β-9) are shown in Table 1-1.

[Example 10A]
In step (B) of Example 9A, the amount of terminally unsaturated polypropylene (M-1) added was changed to 9.0 g, the propylene feed rate was changed to 7.2 L/hr, the toluene solution of triisobutylaluminum (1.0 mol/L) was changed to 3.0 mL (3.0 mmol), the toluene solution of the bridged metallocene compound (B-1) (0.0020 mol/L) was changed to 1.0 mL (0.0020 mmol), and the toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl)borate (4.0 mmol/L) was changed to 2.5 mL (0.010 mmol). The same procedure as in Example 9A was carried out, yielding 20.1 g of an olefin-based resin (β-10). Gel permeation chromatography confirmed that the terminally unsaturated polypropylene had been consumed, confirming the formation of a graft-type olefin-based polymer [R1-10]. The analytical results of the resulting olefin-based resin (β-10) are shown in Table 1-1.

[Example 11A]
Step (A): Production of Terminally Unsaturated Polypropylene (M-1) Terminally unsaturated polypropylene (M-1) was synthesized in the same manner as in Step (A) of Example 1A.
Step (B): Production of Olefin Resin (β-11) 7.5 g of terminally unsaturated polypropylene (M-1) and 500 mL of xylene were placed in a 1 L glass reactor that had been thoroughly purged with nitrogen, and the temperature was then raised to 103° C. to dissolve the terminally unsaturated polypropylene (M-1). While stirring the inside of the polymerization vessel at 600 rpm, ethylene, propylene, and hydrogen were continuously fed thereto at rates of 120.0 L/hr, 19.2 L/hr, and 6.0 L/hr, respectively, to saturate the liquid phase and gas phase. While continuously supplying ethylene, propylene, and hydrogen, 3.0 mL (3.0 mmol) of a toluene solution of triisobutylaluminum (1.0 mol/L), 2.5 mL (0.0050 mmol) of a toluene solution of the above-mentioned bridged metallocene compound (B-1) (0.0020 mol/L), and then 6.25 mL (0.025 mmol) of a toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl)borate (4.0 mmol/L) were added, and polymerization was carried out at normal pressure and 103°C for 30 minutes. The polymerization was terminated by adding a small amount of isobutanol. The resulting polymerization reaction solution was added to 1.5 L of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitate was washed with methanol and then dried under reduced pressure at 130°C for 10 hours, yielding 15.1 g of olefin resin (β-11). It was confirmed by gel permeation chromatography that the terminally unsaturated polypropylene had been consumed, and that a graft-type olefin polymer [R1-11] had been produced. The analytical results of the olefin resin (β-11) are shown in Table 1-1.

[Example 12A]
The same procedure as in Example 2A was carried out, except that the amount of terminally unsaturated polypropylene (M-1) added in step (B) of Example 2A was changed to 3.0 g, to obtain 18.2 g of an olefin resin (β-12). It was confirmed by gel permeation chromatography that the terminally unsaturated polypropylene had been consumed, and that a graft-type olefin polymer [R1-12] had been produced. The analytical results of the obtained olefin resin (β-12) are shown in Table 1-1.

[Example 13A]
In step (B) of Example 12A, the amount of terminally unsaturated polypropylene (M-1) added was changed to 14.0 g, the toluene solution (0.0010 mol/L) of the bridged metallocene compound (B-1) was changed to 2.0 mL (0.0020 mmol), and the toluene solution (4.0 mmol/L) of triphenylcarbenium tetrakis(pentafluorophenyl)borate was changed to 2.5 mL (0.010 mmol). The same procedure as in Example 12A was carried out to obtain 19.9 g of an olefin-based resin (β-13). Gel permeation chromatography confirmed that the terminally unsaturated polypropylene had been consumed, and it was confirmed that a graft-type olefin-based polymer [R1-13] had been produced. The analytical results of the obtained olefin-based resin (β-13) are shown in Table 1-1.

[Example 14A]
Step (A): Production of Terminally Unsaturated Polypropylene (M-2) 1.5 L of toluene was placed in a 2 L glass reactor that had been thoroughly purged with nitrogen, and the temperature was then raised to 100°C. While stirring the interior of the polymerization vessel at 600 rpm, propylene was continuously fed at 180.0 L/hr to saturate the liquid and gas phases. While propylene was still being continuously fed, 8.0 mL (8.0 mmol) of a toluene solution (1.0 mol/L) of methylaluminoxane (also referred to as MAO) was added, followed by 8.0 mL (0.032 mmol) of a toluene solution (0.0040 mol/L) of dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride, and polymerization was carried out at 100°C for 15 minutes under atmospheric pressure. The polymerization was terminated by adding a small amount of isobutanol. The obtained polymerization reaction solution was added to 5 L of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitate was washed with methanol and then dried under reduced pressure at 80°C for 10 hours to obtain 88.4 g of a propylene polymer (terminally unsaturated polypropylene (M-2)). The obtained terminally unsaturated polypropylene (M-2) had a polypropylene-equivalent Mw of 12,297, an Mw/Mn of 2.11, and a one-terminal vinyl ratio of 80% as measured by ^1H -NMR.

Step (B): Production of Olefin Resin (β-14) 6.5 g of terminally unsaturated polypropylene (M-2) and 500 mL of xylene were placed in a 1 L glass reactor that had been thoroughly purged with nitrogen, and the temperature was then raised to 100° C. to dissolve the terminally unsaturated polypropylene (M-2). While stirring the inside of the polymerization vessel at 600 rpm, ethylene and propylene were continuously fed thereto at 99.0 L/hr and 15.6 L/hr, respectively, to saturate the liquid phase and gas phase. While continuously supplying ethylene and propylene, 3.0 mL (3.0 mmol) of a toluene solution (1.0 mol/L) of triisobutylaluminum (also referred to as iBu ₃ Al), 1.5 mL (0.0015 mmol) of a toluene solution (0.0010 mol/L) of the bridged metallocene compound (B-1), and then 1.88 mL (0.0752 mmol) of a toluene solution (4.0 mmol/L) of triphenylcarbenium tetrakis(pentafluorophenyl)borate (also referred to as Ph ₃ CB(C ₆ F ₅ ) ₄ ) were added, and polymerization was carried out at 100°C for 30 minutes under atmospheric pressure. The polymerization was terminated by adding a small amount of isobutanol. The resulting polymerization reaction solution was added to 1.5 L of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitate was washed with methanol and then dried under reduced pressure at 130°C for 10 hours to obtain 12.1 g of an olefin resin (β-14). Gel permeation chromatography confirmed that the terminally unsaturated polypropylene had been consumed, confirming that a graft-type olefin polymer [R1-14] had been produced. The analytical results of the olefin resin (β-14) are shown in Table 1-1.

[Example 15A]
In step (B) of Example 14A, the amount of terminally unsaturated polypropylene (M-2) added was changed to 4.5 g, the toluene solution (0.0020 mol/L) of the bridged metallocene compound (B-1) was changed to 1.0 mL (0.0020 mmol), and the toluene solution (4.0 mmol/L) of triphenylcarbenium tetrakis(pentafluorophenyl)borate was changed to 2.5 mL (0.010 mmol). The same procedure as in Example 14A was carried out to obtain 13.1 g of an olefin-based resin (β-15). Gel permeation chromatography confirmed that the terminally unsaturated polypropylene had been consumed, and it was confirmed that a graft-type olefin-based polymer [R1-15] had been produced. The analytical results of the obtained olefin-based resin (β-15) are shown in Table 1-1.

[Example 16A]
Step (A): Production of Terminally Unsaturated Polypropylene (M-3) 2 L of toluene and 4.0 mL (4.0 mmol) of a toluene solution of methylaluminoxane (also referred to as MAO) (1.0 mol/L) were charged into a 4 L stainless steel autoclave that had been thoroughly purged with nitrogen. The temperature was raised to 90°C while stirring the interior of the polymerization vessel at 600 rpm, and the autoclave was closed after reaching that temperature. Next, the propylene partial pressure was increased to 0.30 MPaG. 5.0 mL of toluene and 2.0 mL (0.002 mmol) of a toluene solution of dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride (0.0010 mol/L) were injected into the vessel to initiate polymerization. The pressure was maintained while continuously supplying propylene gas, and polymerization was carried out at 90°C for 20 minutes, after which 5 mL of methanol was injected to terminate the polymerization. The obtained polymerization reaction solution was added to 5 L of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitate was washed with methanol and then dried under reduced pressure at 80°C for 10 hours to obtain 63.8 g of a propylene polymer (terminally unsaturated polypropylene (M-3)). The obtained terminally unsaturated polypropylene (M-3) had a polypropylene-equivalent Mw of 49,332, an Mw/Mn of 1.99, and a one-terminal vinyl ratio of 74% as measured by ¹ H-NMR.

Step (B): Production of Olefin Resin (β-16) The same procedure as in Example 14A was carried out, except that in step (B) of Example 14A, the terminally unsaturated polypropylene (M-2) was changed to (M-3), to obtain 12.5 g of Olefin Resin (β-16). Gel permeation chromatography confirmed that the terminally unsaturated polypropylene had been consumed, and that a graft-type olefin polymer [R1-16] had been produced. The analytical results of the obtained Olefin Resin (β-16) are shown in Table 1-1.

[Example 17A]
The same procedure as in Example 15A was carried out, except that in step (B) of Example 15A, the terminally unsaturated polypropylene (M-2) was replaced with 4.0 g of (M-3), to obtain 12.1 g of an olefin resin (β-17). It was confirmed by gel permeation chromatography that the terminally unsaturated polypropylene had been consumed, and that a graft-type olefin polymer [R1-17] had been produced. The analytical results of the obtained olefin resin (β-17) are shown in Table 1-1.

[Example 18A]
Step (A): Production of Terminally Unsaturated Propylene-Ethylene Copolymer (M-4) 250 mL of toluene was placed in a 500 mL glass reactor that had been thoroughly purged with nitrogen, and the temperature was then raised to 90°C. Ethylene and propylene were continuously fed into the reactor at 15.0 L/hr and 120.0 L/hr, respectively, while stirring the interior of the polymerization reactor at 600 rpm, saturating the liquid and gas phases. While ethylene and propylene were still being continuously fed, 0.5 mL (0.5 mmol) of a toluene solution (1.0 mol/L) of methylaluminoxane (also referred to as MAO) was added, followed by 1.0 mL (0.001 mmol) of a toluene solution (0.0010 mol/L) of dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride. Polymerization was carried out at normal pressure for 15 minutes at 90°C. The polymerization was terminated by adding a small amount of isobutanol. The resulting polymerization reaction solution was added to 1 L of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitate was washed with methanol and then dried under reduced pressure at 80°C for 10 hours to obtain 8.3 g of a terminally unsaturated propylene-ethylene copolymer (M-4). The resulting terminally unsaturated propylene-ethylene copolymer (M-4) had a polypropylene-equivalent Mw of 20,735 and an Mw/Mn of 1.91, a one-terminal vinyl ratio of 69% as measured by ^1H -NMR, and a propylene composition of 88.7 mol% based on a calibration curve showing the correlation between the ethylene composition ratio (mol%) and the melting point (Tm) (°C).

Step (B): Production of Olefin Resin (β-18) The same procedure as in Example 15A was carried out, except that in step (B) of Example 15A, the terminally unsaturated polypropylene (M-2) was replaced with 3.5 g of terminally unsaturated propylene-ethylene copolymer (M-4), to obtain 11.8 g of olefin resin (β-18). Gel permeation chromatography confirmed that the terminally unsaturated propylene-ethylene copolymer had been consumed, confirming that a graft-type olefin polymer [R1-18] had been produced. The analytical results of the obtained olefin resin (β-18) are shown in Table 1-2.

[Example 19A]
In step (B) of Example 1A, the amount of terminally unsaturated polypropylene (M-1) added was changed to 12.5 g, the ethylene supply rate was changed to 102.0 L/hr, the propylene supply rate was changed to 14.4 L/hr, the hydrogen supply rate was changed to 1.44 L/hr, the toluene solution of the bridged metallocene compound (B-1) (0.0020 mol/L) was changed to 4.0 mL (0.0080 mmol), and the toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl)borate (4.20 mmol/L) was changed to 8.0 mL (0.032 mmol). The same procedure as in Example 1A was carried out, yielding 25.6 g of an olefin-based resin (β-19). Gel permeation chromatography confirmed that the terminally unsaturated polypropylene had been consumed, confirming the formation of a graft-type olefin-based polymer [R1-19]. The analytical results of the resulting olefin-based resin (β-19) are shown in Table 1-2.

[Example 20A]
The same procedure as in Example 1A was carried out, except that in step (B) of Example 1A, the amount of terminally unsaturated polypropylene (M-1) added was changed to 8.5 g, the propylene feed rate was changed to 19.2 L/hr, the amount of triisobutylaluminum in a toluene solution (1.0 mol/L) was changed to 3.5 mL (3.5 mmol), and the amount of triphenylcarbenium tetrakis(pentafluorophenyl)borate in a toluene solution (4.0 mmol/L) was changed to 3.0 mL (0.012 mmol), to obtain 16.6 g of an olefin-based resin (β-20). Gel permeation chromatography confirmed that the terminally unsaturated polypropylene had been consumed, and that a graft-type olefin-based polymer [R1-20] had been produced. The analytical results of the obtained olefin-based resin (β-20) are shown in Table 1-2.

[Example 21A]
In step (B) of Example 20A, the amount of terminally unsaturated polypropylene (M-1) added was changed to 7.0 g, the toluene solution (0.0020 mol/L) of the bridged metallocene compound (B-1) was changed to 2.5 mL (0.0050 mmol), and the toluene solution (4.0 mmol/L) of triphenylcarbenium tetrakis(pentafluorophenyl)borate was changed to 5.0 mL (0.020 mmol). The same procedure as in Example 20A was carried out, yielding 20.5 g of an olefin-based resin (β-21). Gel permeation chromatography confirmed that the terminally unsaturated polypropylene had been consumed, and confirmed that a graft-type olefin-based polymer [R1-21] had been produced. The analytical results of the resulting olefin-based resin (β-21) are shown in Table 1-2.

[Example 22A]
In step (B) of Example 1A, the amount of terminally unsaturated polypropylene (M-1) added was changed to 12.5 g, the propylene feed rate was changed to 26.4 L/hr, the toluene solution of the bridged metallocene compound (B-1) (0.0020 mol/L) was changed to 2.5 mL (0.0050 mmol), and the toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl)borate (4.0 mmol/L) was changed to 5.0 mL (0.020 mmol). The same procedure as in Example 1A was carried out to obtain 22.2 g of an olefin-based resin (β-22). Gel permeation chromatography confirmed that the terminally unsaturated polypropylene had been consumed, confirming the formation of a graft-type olefin-based polymer [R1-22]. The analytical results of the obtained olefin-based resin (β-22) are shown in Table 1-2.

[Example 23A]
Step (A): Production of Terminally Unsaturated Polypropylene (M-1) Terminally unsaturated polypropylene (M-1) was synthesized in the same manner as in Step (A) of Example 1A.
Step (B): Production of Olefin Resin (β-23) 13.0 g of terminally unsaturated polypropylene (M-1) and 500 mL of xylene were placed in a 1 L glass reactor that had been thoroughly purged with nitrogen, and the temperature was then raised to 100° C. to dissolve the terminally unsaturated polypropylene (M-1). While stirring the inside of the polymerization reactor at 600 rpm, ethylene, 1-butene, and hydrogen were continuously fed thereto at rates of 99.0 L/hr, 10.8 L/hr, and 1.44 L/hr, respectively, to saturate the liquid phase and gas phase. While continuously supplying ethylene, 1-butene, and hydrogen, 3.1 mL (3.1 mmol) of a toluene solution of triisobutylaluminum (1.0 mol/L), 3.5 mL (0.0070 mmol) of a toluene solution of the above-mentioned bridged metallocene compound (B-1) (0.0020 mol/L), and then 7.0 mL (0.028 mmol) of a toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl)borate (4.0 mmol/L) were added, and polymerization was carried out at 100°C for 30 minutes under atmospheric pressure. The polymerization was terminated by adding a small amount of isobutanol. The resulting polymerization reaction solution was added to 1.5 L of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitate was washed with methanol and then dried under reduced pressure at 130°C for 10 hours, yielding 28.3 g of olefin resin (β-23). It was confirmed by gel permeation chromatography that the terminally unsaturated polypropylene had been consumed, and that a graft-type olefin polymer [R1-23] had been produced. The analytical results of the olefin resin (β-23) are shown in Table 1-3.

[Example 24A]
The same procedure as in Example 23A was carried out, except that the amount of terminally unsaturated polypropylene (M-1) added in step (B) of Example 23A was changed to 5.5 g, to obtain 19.7 g of an olefin resin (β-24). It was confirmed by gel permeation chromatography that the terminally unsaturated polypropylene had been consumed, and that a graft-type olefin polymer [R1-24] had been produced. The analytical results of the obtained olefin resin (β-24) are shown in Table 1-3.

[Example 25A]
Step (A): Production of Terminally Unsaturated Polypropylene (M-1) Terminally unsaturated polypropylene (M-1) was synthesized in the same manner as in Step (A) of Example 1A.
Step (B): Production of Olefin Resin (β-25) 12.0 g of terminally unsaturated polypropylene (M-1) and 500 mL of xylene were placed in a 1 L glass reactor that had been thoroughly purged with nitrogen, and the temperature was then raised to 103° C. to dissolve the terminally unsaturated polypropylene (M-1). While stirring the inside of the polymerization vessel at 600 rpm, ethylene and 1-butene were continuously fed thereto at 99.0 L/hr and 18.0 L/hr, respectively, to saturate the liquid phase and gas phase. While continuously supplying ethylene and 1-butene, 3.5 mL (3.5 mmol) of a toluene solution of triisobutylaluminum (1.0 mol/L), 2.5 mL (0.0050 mmol) of a toluene solution of the above-mentioned bridged metallocene compound (B-1) (0.0020 mol/L), and then 5.0 mL (0.020 mmol) of a toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl)borate (4.0 mmol/L) were added, and polymerization was carried out at atmospheric pressure and 103°C for 30 minutes. The polymerization was terminated by adding a small amount of isobutanol. The resulting polymerization reaction solution was added to 1.5 L of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitate was washed with methanol and then dried under reduced pressure at 130°C for 10 hours, yielding 24.5 g of an olefin resin (β-25). It was confirmed by gel permeation chromatography that the terminally unsaturated polypropylene had been consumed, and that a graft-type olefin polymer [R1-25] had been produced. The analytical results of the olefin resin (β-25) are shown in Table 1-3.

[Example 26A]
The same procedure as in Example 25A was carried out, except that the amount of terminally unsaturated polypropylene (M-1) added in step (B) of Example 25A was changed to 6.0 g, to obtain 19.5 g of an olefin resin (β-26). It was confirmed by gel permeation chromatography that the terminally unsaturated polypropylene had been consumed, and that a graft-type olefin polymer [R1-26] had been produced. The analytical results of the obtained olefin resin (β-26) are shown in Table 1-3.

[Example 27A]
The same procedure as in Example 23A was carried out, except that in step (B) of Example 23A, the amount of terminally unsaturated polypropylene (M-1) added was changed to 14.0 g, the feed rate of 1-butene to 22.8 L/hr, the feed rate of hydrogen to 0.60 L/hr, the amount of triisobutylaluminum in toluene (1.0 mol/L) to 2.5 mL (2.5 mmol), the amount of the toluene solution of the bridged metallocene compound (B-1) (0.0020 mol/L) to 2.5 mL (0.0050 mmol), and the amount of triphenylcarbenium tetrakis(pentafluorophenyl)borate in toluene (4.0 mmol/L) to 5.0 mL (0.020 mmol), to obtain 26.9 g of olefin resin (β-27). It was confirmed by gel permeation chromatography that the terminally unsaturated polypropylene had been consumed, and that a graft-type olefin polymer [R1-27] had been produced. The analytical results of the obtained olefin resin (β-27) are shown in Table 1-3.

[Comparative Example 1A]
The same procedure as in Example 1A was carried out except that the terminally unsaturated polypropylene (M-1) was not added in step (B) of Example 1A, thereby obtaining 14.2 g of an olefin resin (β'-1). The analytical results of the obtained olefin resin (β'-1) are shown in Table 1-2.
[Comparative example 2A]
The same procedure as in step (A) of Example 1A was carried out to obtain 108.3 g of an olefin resin (β'-2). The analytical results of the obtained olefin resin (β'-2) are shown in Table 1-2.

[Comparative example 3A]
The same procedure as in Example 19A was carried out except that the terminally unsaturated polypropylene (M-1) was not added in step (B) of Example 19A, thereby obtaining 12.8 g of an olefin resin (β'-9). The analytical results of the obtained olefin resin (β'-9) are shown in Table 1-2.
[Comparative example 4A]
The same procedure as in Example 21A was carried out except that the terminally unsaturated polypropylene (M-1) was not added in step (B) of Example 21A, thereby obtaining 16.7 g of an olefin resin (β'-10). The analytical results of the obtained olefin resin (β'-10) are shown in Table 1-2.
[Comparative example 5A]
The same procedure as in Example 22A was carried out except that the terminally unsaturated polypropylene (M-1) was not added in step (B) of Example 22A, thereby obtaining 17.4 g of an olefin resin (β'-11). The analytical results of the obtained olefin resin (β'-11) are shown in Table 1-2.

[Comparative Example 6A]
Step (A): Production of Terminally Unsaturated Polypropylene (M-1) Terminally unsaturated polypropylene (M-1) was synthesized in the same manner as in Step (A) of Example 1A.
Step (B): Production of Olefin Resin (β'-3) 6.5 g of terminally unsaturated polypropylene (M-1) and 500 mL of xylene were placed in a 1 L glass reactor that had been thoroughly purged with nitrogen, and the temperature was then raised to 100°C to dissolve the terminally unsaturated polypropylene (M-1). While stirring the inside of the polymerization reactor at 600 rpm, ethylene and hydrogen were continuously fed thereto at 99.0 L/hr and 4.1 L/hr, respectively, to saturate the liquid phase and gas phase. While continuously supplying ethylene and hydrogen, 2.0 mL (2.0 mmol) of a toluene solution of triisobutylaluminum (1.0 mol/L), 2.0 mL (0.0040 mmol) of a toluene solution of the bridged metallocene compound (B-1) (0.0020 mol/L), and then 4.0 mL (0.016 mmol) of a toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl)borate (4.0 mmol/L) were added, and polymerization was carried out at normal pressure and 100°C for 30 minutes. The polymerization was terminated by adding a small amount of isobutanol. The resulting polymerization reaction solution was added to 1.5 L of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitate was washed with methanol and then dried under reduced pressure at 130°C for 10 hours, yielding 14.0 g of olefin resin (β'-3). It was confirmed by gel permeation chromatography that the terminally unsaturated polypropylene had been consumed, and that a graft-type olefin polymer [R1-28] had been produced. The analytical results of the olefin resin (β'-3) are shown in Table 1-2.

[Comparative Example 7A]
In step (B) of Comparative Example 6A, the amount of terminally unsaturated polypropylene (M-1) added was changed to 4.0 g, the toluene solution (0.0020 mol/L) of the bridged metallocene compound (B-1) was changed to 2.5 mL (0.0050 mmol), and the toluene solution (4.0 mmol/L) of triphenylcarbenium tetrakis(pentafluorophenyl)borate was changed to 5.0 mL (0.020 mmol). The same procedure as in Comparative Example 6A was carried out to obtain 12.4 g of an olefin resin (β'-4). Gel permeation chromatography confirmed that the terminally unsaturated polypropylene had been consumed, and it was confirmed that a graft-type olefin polymer [R1-29] had been produced. The analytical results of the obtained olefin resin (β'-4) are shown in Table 1-2.

[Example 28A]
Step (A): Production of Terminally Unsaturated Polypropylene (M-1) Terminally unsaturated polypropylene (M-1) was synthesized in the same manner as in Step (A) of Example 1A.
Step (B): Production of Olefin Resin (β'-5) 6.0 g of terminally unsaturated polypropylene (M-1) and 500 mL of xylene were placed in a 1 L glass reactor that had been thoroughly purged with nitrogen, and the temperature was then raised to 96°C to dissolve the terminally unsaturated polypropylene (M-1). While stirring the inside of the polymerization vessel at 600 rpm, ethylene and propylene were continuously fed thereto at 81.0 L/hr and 42.0 L/hr, respectively, to saturate the liquid phase and gas phase. While continuously supplying ethylene and propylene, 2.0 mL (2.0 mmol) of a toluene solution of triisobutylaluminum (1.0 mol/L), 1.0 mL (0.0020 mmol) of a toluene solution of the above-mentioned bridged metallocene compound (B-1) (0.0020 mol/L), and then 2.0 mL (0.008 mmol) of a toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl)borate (4.0 mmol/L) were added, and polymerization was carried out at normal pressure and 96°C for 30 minutes. The polymerization was terminated by adding a small amount of isobutanol. The resulting polymerization reaction solution was added to 1.5 L of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitate was washed with methanol and then dried under reduced pressure at 130°C for 10 hours, yielding 12.5 g of olefin resin (β'-5). It was confirmed by gel permeation chromatography that the terminally unsaturated polypropylene had been consumed, and that a graft-type olefin polymer [R1-30] had been produced. The analytical results of the olefin resin (β'-5) are shown in Table 1-2.

[Example 29A]
In step (B) of Example 28A, the amount of terminally unsaturated polypropylene (M-1) added was changed to 4.0 g, the toluene solution (0.0020 mol/L) of the bridged metallocene compound (B-1) was changed to 1.5 mL (0.0030 mmol), and the toluene solution (4.0 mmol/L) of triphenylcarbenium tetrakis(pentafluorophenyl)borate was changed to 3.0 mL (0.012 mmol). The same procedure as in Example 29A was carried out, yielding 11.7 g of olefin-based resin (β'-6). Gel permeation chromatography confirmed that the terminally unsaturated polypropylene had been consumed, and confirmed that a graft-type olefin-based polymer [R1-31] had been produced. The analytical results of the obtained olefin-based resin (β'-6) are shown in Table 1-2.

[Comparative Example 8A]
Step (A): Production of Terminally Unsaturated Polypropylene (M-1) Terminally unsaturated polypropylene (M-1) was synthesized in the same manner as in Step (A) of Example 1A.
Step (B): Production of Olefin Resin (β'-7) 5.0 g of terminally unsaturated polypropylene (M-1) and 500 mL of xylene were placed in a 1 L glass reactor that had been thoroughly purged with nitrogen, and the temperature was then raised to 105°C to dissolve the terminally unsaturated polypropylene (M-1). While stirring the inside of the polymerization reactor at 600 rpm, ethylene, propylene, and hydrogen were continuously fed into the reactor at rates of 120.0 L/hr, 20.4 L/hr, and 18.0 L/hr, respectively, to saturate the liquid phase and gas phase. While continuously supplying ethylene, propylene, and hydrogen, 3.5 mL (3.5 mmol) of a toluene solution of triisobutylaluminum (1.0 mol/L), 3.5 mL (0.0070 mmol) of a toluene solution of the above-mentioned bridged metallocene compound (B-1) (0.0020 mol/L), and then 7.0 mL (0.028 mmol) of a toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl)borate (4.0 mmol/L) were added, and polymerization was carried out at 105°C for 30 minutes under atmospheric pressure. The polymerization was terminated by adding a small amount of isobutanol. The resulting polymerization reaction solution was added to 1.5 L of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitate was washed with methanol and then dried under reduced pressure at 130°C for 10 hours, yielding 10.0 g of olefin resin (β'-7). It was confirmed by gel permeation chromatography that the terminally unsaturated polypropylene had been consumed, and that a graft-type olefin polymer [R1-32] had been produced. The analytical results of the olefin resin (β'-7) are shown in Table 1-2.

[Comparative Example 9A]
In step (B) of Comparative Example 8A, the amount of terminally unsaturated polypropylene (M-1) added was changed to 3.0 g, the toluene solution of the bridged metallocene compound (B-1) (0.0020 mol/L) was changed to 5.0 mL (0.010 mmol), and the toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl)borate (4.0 mmol/L) was changed to 10.0 mL (0.040 mmol). The same procedure as in Comparative Example 8A was carried out to obtain 9.0 g of an olefin resin (β'-8). Gel permeation chromatography confirmed that the terminally unsaturated polypropylene had been consumed, and it was confirmed that a graft-type olefin polymer [R1-33] had been produced. The analytical results of the obtained olefin resin (β'-8) are shown in Table 1-2.

[Comparative Example 10A]
The same procedure as in Example 23A was carried out except that the terminally unsaturated polypropylene (M-1) was not added in step (B) of Example 23A, thereby obtaining 21.7 g of an olefin resin (β'-12). The analytical results of the obtained olefin resin (β'-12) are shown in Table 1-3.
[Comparative Example 11A]
The same procedure as in Example 25A was carried out except that the terminally unsaturated polypropylene (M-1) was not added in step (B) of Example 25A, thereby obtaining 13.5 g of an olefin resin (β'-13). The analytical results of the obtained olefin resin (β'-13) are shown in Table 1-3.
[Comparative Example 12A]
The same procedure as in Example 27A was carried out except that the terminally unsaturated polypropylene (M-1) was not added in step (B) of Example 27A, thereby obtaining 14.5 g of an olefin resin (β'-14). The analytical results of the obtained olefin resin (β'-14) are shown in Table 1-3.

[Examples 1B to 20B, Examples 1C to 18C, Reference Examples 1B and 1C, Comparative Examples 1B to 7B, and Comparative Examples 1C to 3C]
Preparation of Resin Composition (X) The raw materials shown in Tables 2-1, 2-2, 3-1, and 3-2 were placed in a Laboplastomill manufactured by Toyo Seiki Seisaku-sho, Ltd. in the blending ratios (parts by mass) shown in Tables 2-1, 2-2, 3-1, and 3-2, and melt-kneaded at 200°C and 60 rpm for about 5 minutes to prepare a resin composition.
The following propylene polymer (α1) and ethylene polymer (α2) used as raw materials were used.
[Propylene polymer (α1-1)]
Homopropylene (manufactured by Prime Polymer Co., Ltd., trade name: Prime Polypro F113G, MFR (230°C, 2.16 kg load) = 3.0 g/10 min)
[Ethylene polymer (α2-1)]
Metallocene linear low-density polyethylene (manufactured by Prime Polymer Co., Ltd., trade name: Evolue SP2540, MFR (190°C, 2.16 kg load) = 3.8 g/10 min)
The physical properties of each of the resulting resin compositions were measured or evaluated by the following test methods, and the results are shown in Table 2-1, Table 2-2, Table 3-1, or Table 3-2.

[Tensile test]
The resin composition was heated for 6 minutes using a hydraulic hot press molding machine set at 200°C, and then molded for 2 minutes under a pressure of 10 MPa. Thereafter, the resin composition was cooled at 20°C under a pressure of 10 MPa for 2 minutes to produce a sheet having a thickness of 2 mm.
After 72 hours had passed at room temperature from molding, the produced sheet was subjected to a tensile test in accordance with JIS K7162 under the following conditions to determine the tensile elongation.
<Measurement conditions>
Test piece: JIS K7162-5A dumbbell 5 mm (width) x 2 mm (thickness) x 75 mm (length)
Pulling speed: 50 mm/min. Distance between grippers: 50 mm
Distance between gauge lines: 20mm
Temperature: 23℃

[Transmission electron microscope observation]
The prepared resin composition was heated for 6 minutes using a hydraulic hot press molding machine set at 200°C, and then molded for 2 minutes under a pressure of 10 MPa. Thereafter, the resin composition was cooled at 20°C under a pressure of 10 MPa for 2 minutes to produce a sheet having a thickness of 3 mm.
The obtained compact was cut into small pieces of 0.5 mm square and stained with ruthenic acid (RuO ₄ ). The small pieces obtained were then cut into ultrathin sections with a thickness of approximately 100 nm using an ultramicrotome equipped with a diamond knife. Carbon was vapor-deposited onto these ultrathin sections, and the phase structure was observed using a transmission electron microscope (Hitachi High-Tech H-7650).

[Izod impact strength]
The resin composition was heated for 6 minutes using a hydraulic hot press molding machine set at 200°C, and then molded for 2 minutes under a pressure of 10 MPa. Thereafter, the resin composition was cooled at 20°C under a pressure of 10 MPa for 2 minutes to produce a sheet having a thickness of 3 mm.
After 72 hours at room temperature from molding, the Izod impact strength of the prepared sheet was measured under the following conditions in accordance with ASTM D256. In addition, the fracture morphology after the test at 23°C or -30°C was visually confirmed.
<Test conditions>
Hammer capacity: 3.92J
Missing angle: 149.0 degrees Notch is machined Temperature: 23°C or -30°C

[Rate of change in impact resistance]
The rate of change in Izod impact strength at a test temperature of 23°C was calculated using the following formula.
Rate of change (%) = (Izod impact strength - Izod impact strength of Reference Example) × 100 / Izod impact strength of Reference Example For the Izod impact strength of Reference Examples in the above formula, the Izod impact strength of Reference Example 1B was used in Examples 1B to 20B and Comparative Examples 1B to 7B, and the Izod impact strength of Reference Example 1C was used in Examples 1C to 18C and Comparative Examples 1C to 3C. It was determined that the larger the rate of change (%), the better the Izod impact strength.

[Change in tensile elongation]
The rate of change in tensile elongation was calculated using the following formula.
Change rate (%) = (tensile elongation - tensile elongation of Reference Example) × 100 / tensile elongation of Reference Example For the tensile elongation of Reference Example in the above formula, the tensile elongation of Reference Example 1B was used for Examples 1B to 20B and Comparative Examples 1B to 7B, and the tensile elongation of Reference Example 1C was used for Examples 1C to 18C and Comparative Examples 1C to 3C. Note that it was determined that the larger the value of the change rate (%), the better the tensile elongation.

[Balance of impact resistance and elongation]
The resin composition is required to have high impact resistance and high elongation.
As an index showing these balances, the values of balance index (1) according to the following formula were calculated for Examples 1B to 20B, Reference Example 1B, and Comparative Examples 1B to 7B, and the values of balance index (2) according to the following formula were calculated for Examples 1C to 18C, 1C, and Comparative Examples 1C to 3C, to evaluate the balance between impact resistance and elongation of the resin composition.
Balance index (1) (10 ⁴ J/m %) = Izod impact strength (J/m) × tensile elongation (%) × 10 ⁻⁴
Balance index (2) (10 ⁴ ·J/m·%) = (((Izod impact strength (23°C) (J/m)) ² + (Izod impact strength (-30°C) (J/m)) ² ) / 2) ^1/2 × tensile elongation (%) × 10 ⁻⁴

In the above formula of balance index (1), "Izod impact strength" is the Izod impact strength measured at a test temperature of 23°C by the above method.
In the above formula of balance index (2), "Izod impact strength (23°C)" is the Izod impact strength at a test temperature of 23°C, and "Izod impact strength (-30°C)" is the Izod impact strength at a test temperature of -30°C.
The larger the values of the balance index (1) and the balance index (2), the better the balance between impact resistance and elongation of the resin composition or the like can be evaluated.

As shown in Tables 2-1, 2-2, 3-1 and 3-2, the resin compositions of the examples had higher Izod impact strength and tensile elongation at 23°C than the resin compositions of the comparative examples, and were found to have excellent room temperature impact resistance and elongation.
Furthermore, as shown in Tables 3-1 and 3-2, the resin compositions of the Examples had higher Izod impact strength at -30°C than the resin compositions of the Comparative Examples, demonstrating excellent low-temperature impact resistance. Specifically, the Izod impact strength and tensile elongation of Examples 1B to 20B and Examples 1C to 18C were higher than those of Comparative Examples 1B to 7B and Comparative Examples 1C to 3C. This confirmed that the independent presence of an ethylene-propylene copolymer and a terminally unsaturated polypropylene alone did not improve impact resistance and elongation, but that the inclusion of the graft olefin polymer [R1] improved impact resistance and elongation. Furthermore, Comparative Examples 4B and 5B demonstrated that when the ethylene content of the main chain of the graft olefin polymer [R1] was as high as 100 mol%, elongation was achieved but impact resistance was poor, whereas the resin compositions of the Examples achieved both impact resistance and elongation. Furthermore, Comparative Examples 6B and 7B show that when the molecular weight of the olefin resin (β) is too low, both impact resistance and elongation are poor, while the resin compositions of the Examples achieve both impact resistance and elongation.

The phase structures of the resin compositions obtained in Example 1B, Reference Example 1B, Comparative Example 1B, Example 1C, Reference Example 1C, and Comparative Example 1C were observed with a transmission electron microscope, and the results are shown in Figures 1, 2, 3, 4, 5, and 6, respectively. Figures 1, 2, and 3 show phase-separated structures consisting of a sea phase formed by the propylene-based resin component and an island phase formed by the ethylene-based resin component. In Example 1B, the dispersed particle size of the phase formed by the ethylene-based resin component is smaller and more dispersed than in Reference Example 1B and Comparative Example 1B. In Figures 4, 5, and 6, the phase-separated structures consisting of a sea phase formed by the ethylene-based resin component and an island phase formed by the propylene-based resin component are smaller and more dispersed than in Reference Example 1C and Comparative Example 1C. These results confirm that the presence of the graft olefin polymer [R1-1] improves compatibility and improves the impact resistance and elongation of the resin compositions.

[Examples 1D to 7D and Comparative Examples 1D to 6D]
Preparation of Resin Compositions The raw materials listed in Table 4 were placed in a Laboplastomill manufactured by Toyo Seiki Seisaku-sho, Ltd. in the compounding ratios (parts by mass) listed in Table 4, and melt-kneaded at 200°C and 60 rpm for approximately 5 minutes to prepare resin compositions.
The raw material olefin resins (β-20) to (β-23), (β-25) to (β-27) (β'-2), and (β'-10) to (β'-14) were obtained in the above Examples 20A to 23A, Examples 25A to 27A, Comparative Example 2A, Comparative Example 4A to 5A, and Comparative Example 10A to 12A, respectively.
The following raw materials, propylene polymer (α1-2), propylene polymer (α1-3) and ethylene polymer (α2-2), were used.
[Propylene polymer (α1-2)]
Random polypropylene (MFR (230°C, 2.16 kg load, based on ASTM D1238): 7 g/10 min, melting point: 140°C, propylene content: 95 mol%, ethylene content: 1 mol%, 1-butene content: 4 mol%)
[Propylene polymer (α1-3)]
Propylene polymer (α1-3) prepared according to the method for Propylene polymer 1 described in the Examples section of JP-A No. 2024-116045 (MFR (230°C, 2.16 kg load, in accordance with ASTM D1238): 6 g/10 min)
[Ethylene polymer (α2-2)]
Ethylene-propylene copolymer (melting point: 44°C, density: 869 kg/m ³ , ethylene content: 81 mol %, propylene content: 19 mol %, MFR (190°C, 2.16 kg load) = 0.6 g/10 min)

Measurement of Physical Properties of Molded Articles Physical properties of molded articles of the prepared resin compositions were measured by the following methods. The results are shown in Table 4.
[Whitening resistance]
The resin composition was heated for 6 minutes using a hydraulic hot press molding machine set at 200°C, and then molded for 2 minutes under a pressure of 10 MPa. Thereafter, the resin composition was cooled at 20°C under a pressure of 10 MPa for 2 minutes to produce a sheet having a thickness of 0.5 mm.
After 7 days or more had passed since molding at room temperature, size 2 dumbbells as specified in JIS K6251 were made from the sheet. The hue of the dumbbells before stretching (L value (before stretching)) and the hue after stretching the dumbbells by 15 mm at 23°C and a tensile speed of 50 mm/min (L value (after stretching)) were measured using a spectrophotometer (CM-3700A, manufactured by Konica Minolta, Inc.). The hue change (ΔL) was calculated based on the following formula. A smaller ΔL value indicates better whitening resistance of the polymer composition.
ΔL = L value (after stretching) - L value (before stretching)

[Tensile test]
The resin composition was heated for 6 minutes using a hydraulic hot press molding machine set at 200°C, and then molded for 2 minutes under a pressure of 10 MPa. Thereafter, the resin composition was cooled at 20°C under a pressure of 10 MPa for 2 minutes to produce a sheet having a thickness of 2 mm.
After 72 hours had passed at room temperature from molding, the produced sheet was subjected to a tensile test under the following conditions in accordance with JIS K7162, from which the elastic modulus and breaking stress were determined.
<Measurement conditions>
Test piece: JIS K7162-5A dumbbell 5 mm (width) x 2 mm (thickness) x 75 mm (length)
Pulling speed: 50 mm/min. Distance between grippers: 50 mm
Distance between gauge lines: 20mm
Temperature: 23℃

[High-speed surface impact test]
The resin composition was heated for 6 minutes using a hydraulic hot press molding machine set at 200°C, and then molded for 2 minutes under a pressure of 10 MPa. Thereafter, the resin composition was cooled at 20°C under a pressure of 10 MPa for 2 minutes to produce a sheet having a thickness of 0.5 mm.
After 72 hours at room temperature from molding, the produced sheet was subjected to a high-speed surface impact test in accordance with JIS K7211-2 under the following conditions, from which the puncture point energy was determined.
<Measurement conditions>
Striker diameter: 20mmΦ
Support stand diameter: 40mmΦ
Test speed: 4.4 m/s
Temperature: -20℃

[Balance between impact resistance and stress]
The resin composition is required to have high impact resistance and high stress.
As an index showing the balance between these, in Examples 1D to 7D and Comparative Examples 1D to 6D, the value of balance index (3) was calculated by the following formula to evaluate the balance between impact resistance and stress of the resin composition.
Balance index (3) [10 J MPa] = puncture point energy (J) × fracture stress (MPa) × ¹⁰
The larger the balance index (3) value, the better the balance between impact resistance and stress can be evaluated.

[Balance of whitening resistance, elastic modulus, impact resistance and stress]
The resin composition is required to have high whitening resistance, high elastic modulus, high impact resistance, and high stress.
As an index showing these balances, in Examples 1D to 7D and Comparative Examples 1D to 6D, the value of balance index (4) was calculated using the following formula, and the balance of whitening resistance, elastic modulus, impact resistance, and stress of the resin composition was evaluated.
Balance index (4) [10 ³ ·J·MPa ² ] = puncture point energy (J) × fracture stress (MPa) × elastic modulus (MPa) / color change (ΔL) (-) × 10 ⁻³
The larger the value of the balance index (4), the better the balance of whitening resistance, elastic modulus, impact resistance and stress can be evaluated.

As shown in Table 4, the resin compositions of the Examples had smaller ΔL values and were superior in whitening resistance than the resin compositions of the Comparative Examples. Furthermore, as shown in Table 4, the resin compositions of the Examples had a higher balance of elastic modulus/puncture point energy and a higher balance of breaking stress/puncture point energy than the resin compositions of the Comparative Examples, and were also superior in the balance of impact resistance and strength. Specifically, Examples 1D to 7D had smaller ΔL values and a higher balance of elastic modulus/puncture point energy and a higher balance of breaking stress/puncture point energy than Comparative Examples 1D to 6D. It was confirmed that the mere presence of an ethylene-propylene copolymer and a terminally unsaturated polypropylene independently did not have the effect of improving the balance between whitening resistance, impact resistance, and strength, but that the inclusion of the graft-type olefin polymer [R1] improved the balance between whitening resistance, impact resistance, and strength.

[Reference Example 1E, Examples 1E to 14E, and Comparative Examples 1E to 7E]
Preparation of Resin Compositions The raw materials shown in Tables 5-1 and 5-2 were placed in a Laboplastomill manufactured by Toyo Seiki Seisaku-sho, Ltd. in the blending ratios (parts by mass) shown in Tables 5-1 and 5-2, and melt-kneaded at 200°C and 60 rpm for about 5 minutes to prepare resin compositions.
The raw material olefin resins (β-19) to (β-26), (β'-2), (β'-9) to (β'-13) were obtained in the above Examples 19A to 26A, Comparative Examples 2A to 5A, and Comparative Examples 10A to 11A, respectively.
The following propylene polymers (α1-4) and ethylene polymers (α2-3) used as raw materials were as follows:
[Propylene polymer (α1-4)]
Block polypropylene (MFR (230°C, 2.16 kg load, in accordance with ASTM D1238): MFR: 3.5 g/10 min, density: 900 kg/m ³ , amorphous viscosity η: 2.8 dL/g, propylene:ethylene (molar ratio) 81.1:18.9)
[Ethylene polymer (α2-3)]
Ethylene-1-butene copolymer (MFR (190°C, 2.16 kg load) = 1.2 g/10 min, density 885 kg/m ³ )

Measurement of physical properties of molded articles The physical properties of molded articles of the prepared resin compositions were measured by the following methods. The results are shown in Tables 5-1 and 5-2.
[Tensile test]
The resin composition was heated for 6 minutes using a hydraulic hot press molding machine set at 200°C, and then molded for 2 minutes under a pressure of 10 MPa. Thereafter, the resin composition was cooled at 20°C under a pressure of 10 MPa for 2 minutes to produce a sheet having a thickness of 2 mm.
After 72 hours had passed at room temperature from molding, the produced sheet was subjected to a tensile test under the following conditions in accordance with JIS K7162, from which the elastic modulus and tensile elongation were determined.
<Measurement conditions>
Test piece: JIS K7162-5A dumbbell 5 mm (width) x 2 mm (thickness) x 75 mm (length)
Pulling speed: 50 mm/min. Distance between grippers: 50 mm
Distance between gauge lines: 20mm

[High-speed surface impact test]
The resin composition was heated for 6 minutes using a hydraulic hot press molding machine set at 200°C, and then molded for 2 minutes under a pressure of 10 MPa. Thereafter, the resin composition was cooled at 20°C under a pressure of 10 MPa for 2 minutes to produce a sheet having a thickness of 0.5 mm.
After 72 hours at room temperature from molding, the produced sheet was subjected to a high-speed surface impact test in accordance with JIS K7211-2 under the following conditions, from which the puncture point energy was determined.
<Measurement conditions>
Striker diameter: 20mmΦ
Support stand diameter: 40mmΦ
Test speed: 4.4 m/s
Temperature: -20℃

[Change in tensile elongation]
In Table 5-1, the rate of change in tensile elongation was calculated using the following formula.
Change rate (%)=(tensile elongation-tensile elongation of Reference Example 1E)×100/tensile elongation of Reference Example 1E It was determined that the larger the change rate (%), the better the tensile elongation.
[Change in tensile modulus]
In Table 5-1, the rate of change in tensile modulus was calculated using the following formula.
Change rate (%) = (tensile modulus of elasticity - tensile modulus of elasticity of Reference Example 1E) x 100 / tensile modulus of elasticity of Reference Example 1E

[Rate of change in fracture stress]
In Table 5-1, the rate of change in breaking stress was calculated using the following formula.
Rate of change (%)=(breaking stress-breaking stress of Reference Example 1E)×100/breaking stress of Reference Example 1E It was determined that the greater the value of rate of change (%), the better the breaking stress.
[Puncture point energy change rate]
In Table 5-1, the rate of change of the puncture point energy was calculated using the following formula.
Change rate (%)=(puncture point energy−puncture point energy of Reference Example 1E)×100/puncture point energy of Reference Example 1E It was determined that the larger the change rate (%), the better the puncture point energy.

[Balance between impact resistance and stress]
The resin composition is required to have high impact resistance and high stress.
As an index showing these balances, in Reference Example 1E, Examples 1E to 14E, and Comparative Examples 1E to 7E, the value of the balance index (5) according to the following formula was calculated to evaluate the balance between impact resistance and stress of the resin composition.
Balance index (5) [10 ² J MPa] = puncture point energy (J) × fracture stress (MPa) × ¹⁰
The larger the value of the balance index (5), the better the balance between impact resistance and stress can be evaluated.

[Balance of elongation, flexibility, impact resistance and stress]
The resin composition is required to have high elongation, high flexibility, high impact resistance, and high stress.
As an index showing these balances, in Reference Example 1E, Examples 1E to 14E, and Comparative Examples 1E to 7E, the value of the balance index (6) according to the following formula was calculated, and the flexibility, impact resistance, and stress balance of the resin composition were evaluated.
Balance index (6) [% J] = tensile elongation (%) × puncture point energy (J) × fracture stress (MPa) / elastic modulus (MPa)
The larger the value of the balance index (6), the better the balance of elongation, flexibility, impact resistance and stress can be evaluated.

As shown in Tables 5-1 and 5-2, the resin compositions of the Examples had higher elastic modulus/puncture point energy balances, fracture stress/puncture point energy balances, and elongation/puncture point energy balances than the resin compositions of the Comparative Examples, and were found to have excellent balances in impact resistance, strength, and elongation. Specifically, Examples 1E to 14E had higher elastic modulus/puncture point energy balances, fracture stress/puncture point energy balances, and elongation/puncture point energy balances than Comparative Examples 1E to 7E. It was confirmed that the independent presence of the ethylene-propylene copolymer and terminally unsaturated polypropylene alone did not have the effect of improving the balance of impact resistance, strength, and elongation, but that the inclusion of the graft-type olefin polymer [R1] improved the balance of impact resistance, strength, and elongation.

[Examples 1F to 4F, Comparative Examples 1F to 2F]
Preparation of Resin Compositions The raw materials listed in Table 6 were placed in a Laboplastomill manufactured by Toyo Seiki Seisaku-sho, Ltd. in the compounding ratios (parts by mass) listed in Table 6, and melt-kneaded at 200°C and 60 rpm for approximately 5 minutes to prepare resin compositions.
The raw material olefin resins (β-20) and (β-25) were those obtained in the above Examples 20A and 25A, respectively.
The following propylene polymers (α1-5) and ethylene polymers (α2-4) used as raw materials were as follows:
[Propylene polymer (α1-5)]
Block polypropylene (melting point: 162°C, MFR (230°C, 2.16 kg load): 54 g/10 min), density: 900 kg/m ³ )
[Ethylene polymer (α2-4)]
Ethylene-1-butene copolymer (MFR (190°C, 2.16 kg load) = 0.6 g/10 min, density 861 kg/m ³ )

Measurement of physical properties of molded articles The physical properties of molded articles of the prepared resin compositions were measured by the following methods. The results are shown in Table 6.
[Izod impact strength]
The resin composition was heated for 6 minutes using a hydraulic hot press molding machine set at 200°C, and then molded for 2 minutes under a pressure of 10 MPa. Thereafter, the resin composition was cooled at 20°C under a pressure of 10 MPa for 2 minutes to produce a sheet having a thickness of 3 mm.
After 72 hours at room temperature from molding, the Izod impact strength of the prepared sheet was measured four times in accordance with ASTM D256 under the following conditions. The fracture morphology after the four tests was also visually confirmed.
<Test conditions>
Hammer capacity: 3.92J
Missing angle: 149.0 degrees The notch is machined Temperature: -40°C

[Bending test]
The resin composition was heated for 6 minutes using a hydraulic hot press molding machine set at 200°C, and then molded for 2 minutes under a pressure of 10 MPa. Thereafter, the resin composition was cooled at 20°C under a pressure of 10 MPa for 2 minutes to produce a sheet having a thickness of 3 mm.
After 72 hours had passed at room temperature from molding, a bending test was carried out on the produced sheet in accordance with ASTM D-790 under the following conditions to measure the bending modulus (MPa).
<Test conditions>
Span: 48 mm
Test speed: 5 mm/min Temperature: 23°C

[Tensile test]
The resin composition was heated for 6 minutes using a hydraulic hot press molding machine set at 200°C, and then molded for 2 minutes under a pressure of 10 MPa. Thereafter, the resin composition was cooled at 20°C under a pressure of 10 MPa for 2 minutes to produce a sheet having a thickness of 2 mm.
After 72 hours had passed at room temperature from molding, the produced sheet was subjected to a tensile test under the following conditions in accordance with JIS K7162, from which the elastic modulus and tensile elongation were determined.
<Measurement conditions>
Test piece: JIS K7162-5A dumbbell 5 mm (width) x 2 mm (thickness) x 75 mm (length)
Pulling speed: 50 mm/min. Distance between grippers: 50 mm
Distance between gauge lines: 20mm

[Balance of impact resistance and elongation]
The resin composition is required to have high impact resistance and high elongation.
As an index showing these balances, in Examples 1F to 4F and Comparative Examples 1F to 2F, the value of balance index (7) was calculated by the following formula to evaluate the balance between impact resistance and elongation of the resin composition.
Balance index (7) [10 ⁴ J/m %] = average value of four Izod impact strengths (J/m) × tensile elongation (%) × 10 ⁻⁴
The larger the value of the balance index (7), the better the balance between impact resistance and elongation can be evaluated.

[Balance of elongation, flexibility, impact resistance and stress]
The resin composition is required to have high elongation, high flexibility, high impact resistance, and high stress.
As an index showing these balances, in Examples 1F to 4F and Comparative Examples 1F to 2F, the value of the balance index (8) was calculated using the following formula, and the balance of elongation, flexibility, impact resistance, and stress of the resin composition was evaluated.
Balance index (8) [10 ³ J/m %] = Izod impact strength (J/m) × tensile elongation (%) × breaking stress (MPa) / flexural modulus (MPa) × 10 ⁻³
The larger the value of the balance index (8), the better the balance of elongation, flexibility, impact resistance and stress can be evaluated.

As shown in Table 6, the resin compositions of the examples had a high balance between flexural modulus and Izod impact strength measured at −40° C., a high balance between flexural modulus and stress at break, and a high balance between flexural modulus and elongation, and were found to have an excellent balance between low-temperature impact resistance, strength, and elongation.

Claims (28)

An olefin resin (β) containing a graft-type olefin polymer [R1] having a main chain and a side chain,
Meet all of the following requirements (I) to (IV):
Olefin resin (β):
(I) The main chain of the graft-type olefin polymer [R1] is composed of an ethylene-propylene copolymer or an ethylene-1-butene copolymer;
(II) The side chain of the graft type olefin polymer [R1] is composed of a propylene homopolymer or a propylene-ethylene copolymer;
(III) The total content of P of the following components (i) to (iv) in the olefin-based resin (β) is in the range of 10 to 80 mass%:
(i) a propylene homopolymer constituting the side chain of the graft-type olefin polymer [R1];
(ii) a propylene-ethylene copolymer constituting the side chain of the graft-type olefin polymer [R1];
(iii) a terminally unsaturated propylene homopolymer that does not constitute the graft-type olefin polymer [R1];
(iv) a terminally unsaturated propylene-ethylene copolymer that does not constitute the graft-type olefin polymer [R1];
(IV) The intrinsic viscosity [η] of the olefin resin (β) measured in decalin at 135° C. is 0.5 to 5.0 dL/g. the main chain of the graft-type olefin polymer [R1] is an ethylene-propylene copolymer,
the ethylene-propylene copolymer has a structural unit content derived from ethylene of 70 to 99 mol %;
the content of structural units derived from propylene in the ethylene-propylene copolymer is 1 to 30 mol%;
The olefin-based resin (β) according to claim 1. the weight-average molecular weight (Mw) of the ethylene-propylene copolymer constituting the main chain of the graft olefin polymer [R1], determined as a polyethylene-equivalent value by gel permeation chromatography (GPC), is 50,000 to 250,000;
The olefin-based resin (β) according to claim 2. the total P content of the components (i) to (iv) in the olefin-based resin (β) is 10 to 60 mass%;
The olefin-based resin (β) according to claim 2. the melt flow rate (MFR) of the olefin resin (β) measured in accordance with ASTM D1238 at 190°C under a load of 2.16 kg is 0.01 to 30 g/10 min;
The olefin-based resin (β) according to claim 2. the ethylene-propylene copolymer has a structural unit content of 75 to 85 mol % derived from ethylene;
the ethylene-propylene copolymer has a structural unit content derived from propylene of 15 to 25 mol %,
The intrinsic viscosity [η] of the olefin resin (β) measured in decalin at 135°C is 0.9 to 1.25 dL/g.
The olefin-based resin (β) according to claim 2. the main chain of the graft type olefin polymer [R1] is an ethylene-1-butene copolymer,
the ethylene-1-butene copolymer has a structural unit content of 70 to 90 mol % derived from ethylene;
the ethylene/1-butene copolymer has a content of structural units derived from 1-butene of 10 to 30 mol %,
the ethylene/1-butene copolymer has a weight average molecular weight (Mw) of 30,000 to 120,000, as determined by gel permeation chromatography (GPC) in terms of polyethylene;
The olefin-based resin (β) according to claim 1. the melt flow rate (MFR) of the olefin resin (β) measured in accordance with ASTM D1238 at 190°C under a load of 2.16 kg is 2.5 to 30 g/10 min;
The olefin-based resin (β) according to claim 7. the ethylene-1-butene copolymer has a structural unit content of 78 to 87 mol % derived from ethylene;
the ethylene/1-butene copolymer has a content of structural units derived from 1-butene of 13 to 22 mol%;
The olefin-based resin (β) according to claim 7. The intrinsic viscosity [η] of the olefin resin (β) measured in decalin at 135°C is 0.5 to 1.25 dL/g.
The olefin-based resin (β) according to claim 7. the content of structural units derived from propylene in the side chains of the graft-type olefin polymer [R1] is 80 to 100 mol %,
the content of structural units derived from ethylene in the side chains of the graft type olefin polymer [R1] is 0 to 20 mol %,
the weight-average molecular weight (Mw) of the polymer or copolymer constituting the side chain of the grafted olefin polymer [R1], determined by gel permeation chromatography (GPC) in terms of polypropylene, is in the range of 5,000 to 50,000;
The olefin-based resin (β) according to any one of claims 1 to 10. A method for producing the olefin resin (β) according to any one of claims 1 to 10, comprising the following steps (A) and (B):
(A) In the presence of an olefin polymerization catalyst containing a transition metal compound [A] of Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton,
a step of polymerizing propylene to produce a terminally unsaturated polypropylene, or a step of copolymerizing propylene and ethylene to produce a terminally unsaturated propylene-ethylene copolymer;
(B) in the presence of an olefin polymerization catalyst containing a bridged metallocene compound represented by the following general formula [B]:
A step of copolymerizing the terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer produced in step (A) with ethylene and propylene, or a step of copolymerizing the terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer produced in step (A) with ethylene and 1-butene.
(In formula [B], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a heteroatom-containing group other than a silicon-containing group, and any two adjacent groups among R ¹ to R ⁴ may be bonded to each other to form a ring. R ⁶ and R ¹¹ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group, R ⁷ and R ¹⁰ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group, R ⁶ and R ⁷ may be bonded to each other to form a ring, and R ¹⁰ and R ¹¹ may be bonded to each other to form a ring; provided that R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms. R ¹³ and R ¹⁴ each independently represent an aryl group. ^Y1 represents a carbon atom or a silicon atom. ^M1 represents a zirconium atom or a hafnium atom. Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or non-conjugated diene having 4 to 10 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair, and j represents an integer of 1 to 4, and when j is an integer of 2 or greater, multiple Qs may be the same or different. The olefin-based resin (β) according to any one of claims 1 to 10,
a propylene polymer (α1);
and an ethylene polymer (α2),
Resin composition (X). the main chain of the graft-type olefin-based polymer [R1] in the olefin-based resin (β) is an ethylene-propylene copolymer,
a ratio ((β)/((α1)+(α2))) of the total mass of the olefin resin (β) to the total mass of the propylene polymer (α1) and the ethylene polymer (α2) is 0.02 to 0.23;
The resin composition (X) according to claim 13. the main chain of the graft-type olefin-based polymer [R1] in the olefin-based resin (β) is an ethylene-propylene copolymer,
the melt flow rate (MFR) of the propylene polymer (α1) measured in accordance with ASTM D1238 at 230°C under a load of 2.16 kg is 0.01 to 20 g/10 min;
The resin composition (X) according to claim 13. the main chain of the graft-type olefin-based polymer [R1] in the olefin-based resin (β) is an ethylene-propylene copolymer,
the melt flow rate (MFR) of the ethylene polymer (α2) is 0.01 to 2.0 g/10 min, as measured at 190°C under a load of 2.16 kg in accordance with ASTM D1238;
The resin composition (X) according to claim 13. the main chain of the graft-type olefin-based polymer [R1] in the olefin-based resin (β) is an ethylene-1-butene copolymer,
a ratio ((β)/((α1)+(α2))) of the total mass of the olefin resin (β) to the total mass of the propylene polymer (α1) and the ethylene polymer (α2) is 0.08 to 0.20;
The resin composition (X) according to claim 13. the main chain of the graft-type olefin-based polymer [R1] in the olefin-based resin (β) is an ethylene-1-butene copolymer,
the melt flow rate (MFR) of the propylene polymer (α1) measured in accordance with ASTM D1238 at 230°C under a load of 2.16 kg is 0.01 to 25 g/10 min;
The resin composition (X) according to claim 13. the main chain of the graft-type olefin-based polymer [R1] in the olefin-based resin (β) is an ethylene-1-butene copolymer,
the melt flow rate (MFR) of the ethylene polymer (α2) measured in accordance with ASTM D1238 at 190°C under a load of 2.16 kg is 0.5 to 100 g/10 min;
The resin composition (X) according to claim 13. the main chain of the graft-type olefin-based polymer [R1] in the olefin-based resin (β) is an ethylene-1-butene copolymer,
The density of the ethylene polymer (α2) measured at 25°C in accordance with ASTM D1505 is 850 to 900 kg/ ^m3 .
The resin composition (X) according to claim 13. the main chain of the graft-type olefin-based polymer [R1] in the olefin-based resin (β) is an ethylene-1-butene copolymer,
the melt flow rate (MFR) of the propylene polymer (α1) measured in accordance with ASTM D1238 at 230°C under a load of 2.16 kg is 0.01 to 25 g/10 min;
the density of the ethylene polymer (α2) measured at 25°C in accordance with ASTM D1505 is 850 to 900 kg/ ^m3 ;
The resin composition (X) according to claim 13. the main chain of the graft-type olefin-based polymer [R1] in the olefin-based resin (β) is an ethylene-1-butene copolymer,
a ratio ((β)/((α1)+(α2))) of the total mass of the olefin resin (β) to the total mass of the propylene polymer (α1) and the ethylene polymer (α2) is 0.08 to 0.20;
the melt flow rate (MFR) of the ethylene polymer (α2) measured in accordance with ASTM D1238 at 190°C under a load of 2.16 kg is 0.5 to 100 g/10 min;
The resin composition (X) according to claim 13. the content of structural units derived from propylene in the side chains of the graft-type olefin polymer [R1] is 80 to 100 mol %,
the content of structural units derived from ethylene in the side chains of the graft type olefin polymer [R1] is 0 to 20 mol %,
the weight-average molecular weight (Mw) of the polymer or copolymer constituting the side chain of the grafted olefin polymer [R1], determined by gel permeation chromatography (GPC) in terms of polypropylene, is in the range of 5,000 to 50,000;
The resin composition (X) according to any one of claims 13 to 22. Lithium-ion battery packaging applications
The olefin-based resin (β) according to any one of claims 1 to 10. Lithium-ion battery packaging applications
The resin composition (X) according to any one of claims 13 to 22. The olefin resin (β) according to any one of claims 1 to 10, or the resin composition (X) according to any one of claims 13 to 22,
Molded body. The olefin resin (β) according to any one of claims 1 to 10, or the resin composition (X) according to any one of claims 13 to 22,
Packaging for lithium-ion batteries. The lithium ion battery packaging according to claim 27,
Energy storage device.