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

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

[0001] 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 a lithium-ion battery, and an electricity storage device.

[0002] 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 the recycling of plastic products has progressed in recent years, there is also a demand for further recycling of used products made from polyolefin resins and discarded plastics.

[0003] Propylene polymers and ethylene polymers are widely used as polyolefin resin materials, but because they are incompatible with each other, even if they are mixed and recycled, they do not disperse uniformly, resulting in poor physical properties and limited applications. Therefore, there has been a need for a method for compatibilizing or compatibilizing propylene polymers and ethylene polymers.

[0004] As methods for compatibilizing or compatibilizing a propylene-based polymer and an ethylene-based polymer, there have been proposed methods such as 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 that is an ethylene-α-olefin copolymer having 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).

[0005] Japanese Patent Publication No. 2016-537449 Japanese Patent Publication No. 2019-116638 Japanese Patent No. 5860043 Japanese Patent No. 6783851 Japanese Patent Publication No. 6-511028 Japanese Patent No. 5466986 Japanese Patent Publication No. 2022-548039 International Publication No. 2023 / 101004

[0006] However, previously reported compatibilizers have room for improvement in the balance between impact resistance and elongation, or the balance between impact resistance and strength. An object of the present invention is to provide a novel olefin-based resin that is useful as a compatibilizer for a propylene-based polymer and an ethylene-based polymer, and to provide uses for the olefin-based resin. Another object of the present invention is to provide a resin composition and molded article, a packaging body for a lithium-ion battery, and an electricity storage device, which 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.

[0007] The present invention relates to, for example, the following [1] to

[29] . [1] An olefin resin (β) containing a graft olefin polymer [R1] having a main chain and a side chain, the olefin resin (β) satisfying all of the following requirements (I) to (IV): (I) the main chain of the graft olefin polymer [R1] is composed of an ethylene-propylene copolymer or an ethylene-1-butene copolymer; (II) the side chain of the graft 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 resin (β) is in the range of 10 to 80 mass%: (i) a propylene homopolymer constituting the side chain of the graft olefin polymer [R1]; (ii) a propylene-ethylene copolymer constituting the side chain of the graft olefin polymer [R1]; (iii) a terminally unsaturated propylene homopolymer not constituting the graft 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.

[0008] [2] The olefin resin (β) according to [1], wherein the main chain of the graft-type olefin polymer [R1] is an ethylene-propylene copolymer, the content of structural units derived from ethylene in the ethylene-propylene copolymer is 70 to 99 mol %, and the content of structural units derived from propylene in the ethylene-propylene copolymer is 1 to 30 mol %.

[0009] [3] The olefin-based resin (β) according to [2], wherein the weight-average molecular weight (Mw) of the ethylene-propylene copolymer constituting the main chain of the graft-type olefin-based 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 content of P of the components (i) to (iv) in the olefin-based resin (β) is 10 to 60 mass%.

[0010] [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) is 0.01 to 30 g / 10 min, as measured at 190°C under a load of 2.16 kg in accordance with ASTM D 1238. [6] The olefin-based resin (β) according to any one of [2] to [5], wherein the ethylene-propylene copolymer has a structural unit content of 75 to 85 mol%, the ethylene-propylene copolymer has a structural unit content of 15 to 25 mol%, and the olefin-based resin (β) has an intrinsic viscosity [η] of 0.9 to 1.25 dL / g, as measured in decalin at 135°C.

[0011] [7] The olefin resin (β) according to [1], wherein the main chain of the graft-type olefin polymer [R1] is an ethylene / 1-butene copolymer, the content of structural units derived from ethylene in the ethylene / 1-butene copolymer is 70 to 90 mol %, the content of structural units derived from 1-butene in the ethylene / 1-butene copolymer is 10 to 30 mol %, and the weight-average molecular weight (Mw) of the ethylene / 1-butene copolymer, calculated as a polyethylene equivalent value by gel permeation chromatography (GPC), is 30,000 to 120,000.

[0012] [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 D 1238. [9] The olefin-based resin (β) according to [7] or [8], wherein the ethylene-1-butene copolymer has a content of structural units derived from ethylene of 78 to 87 mol%, and the ethylene-1-butene copolymer has a content of structural units derived from 1-butene of 13 to 22 mol%.

[0013]

[10] The olefin resin (β) according to any one of [7] to [9], wherein the olefin resin (β) has an intrinsic viscosity [η] of 0.5 to 1.25 dL / g as measured in decalin at 135° C.

[11] The olefin resin (β) according to any one of [1] to

[10] , wherein 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 olefin polymer [R1] is 0 to 20 mol %, and the weight average molecular weight (Mw) of the polymer or copolymer constituting the side chains of the graft olefin polymer [R1], as determined by gel permeation chromatography (GPC) in terms of polypropylene, is in the range of 5,000 to 50,000.

[0014]

[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) 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, 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; (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 represents a hydrogen atom, a hydrocarbon group, a silicon-containing group, or a heteroatom-containing group other than a silicon-containing group; R 1 ~R 4 Two adjacent groups among R may be bonded to each other to form a ring. 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, and 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, and 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 11are not all hydrogen atoms. 13 and R 14 each independently represents an aryl group. 1 represents a carbon atom or a silicon atom. 1 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; 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.

[0015]

[13] A resin composition (X) comprising the olefin resin (β) according to any one of [1] to

[11] , a propylene polymer (α1), and an ethylene polymer (α2).

[14] The resin composition (X) according to

[13] , wherein the main chain of the graft-type olefin polymer [R1] in the olefin resin (β) is an ethylene-propylene copolymer, and the ratio ((β) / ((α1)+(α2))) of the total mass of the olefin resin (β) to the total amount of the propylene polymer (α1) and the ethylene polymer (α2) is 0.02 to 0.23.

[0016]

[15] The resin composition (X) according to

[13] or

[14] , wherein the main chain of the graft olefin polymer [R1] in the olefin resin (β) is an ethylene-propylene copolymer, and 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.

[0017]

[16] The resin composition (X) according to any one of

[13] to

[15] , wherein the main chain of the graft-type olefin polymer [R1] in the olefin resin (β) is an ethylene-propylene copolymer, 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 0.01 to 2.0 g / 10 min.

[17] The resin composition (X) according to

[13] , wherein the main chain of the graft-type olefin polymer [R1] in the olefin resin (β) is an ethylene-1-butene copolymer, and the ratio ((β) / ((α1)+(α2))) of the total mass of the olefin resin (β) to the total amount of the propylene polymer (α1) and the ethylene polymer (α2) is 0.08 to 0.20.

[0018]

[18] The resin composition (X) according to

[13] or

[17] , wherein the main chain of the grafted olefin polymer [R1] in the olefin resin (β) is an ethylene-1-butene copolymer, and 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.

[19] The resin composition (X) according to

[13] ,

[17] or

[18] , wherein the main chain of the grafted olefin polymer [R1] in the olefin resin (β) is an ethylene-1-butene copolymer, 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.

[0019]

[20] The main chain of the graft-type olefin polymer [R1] in the olefin resin (β) is an ethylene-1-butene copolymer, and the density of the ethylene polymer (α2) measured at 25°C in accordance with ASTM D1505 is 850 to 900 kg / m ３

[21] The resin composition (X) according to any one of

[13] and

[17] to

[19] , wherein 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, and the density of the ethylene polymer (α2) measured in accordance with ASTM D1505 at 25°C is 850 to 900 kg / m ３ The resin composition (X) according to any one of

[13] and

[17] to

[20] .

[0020]

[22] The resin composition (X) according to any one of

[13] and

[17] to

[21] , wherein the main chain of the graft olefin polymer [R1] in the olefin resin (β) is an ethylene-1-butene copolymer, 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 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.

[0021]

[23] Resin composition (X) according to any one of

[13] to

[22] , wherein 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 %, and the weight average molecular weight (Mw) of the polymer or copolymer constituting the side chains of the graft type olefin polymer [R1], determined as a polypropylene equivalent value by gel permeation chromatography (GPC), is in the range of 5,000 to 50,000.

[0022]

[24] The olefin resin (β) according to any one of [1] to

[11] , which is used as a packaging material for lithium ion batteries.

[25] The resin composition (X) according to any one of

[13] to

[23] , which is used as a packaging material for lithium ion batteries.

[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] .

[0023]

[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 packaging body for a lithium ion battery according to

[27] .

[0024] According to the present invention, it is possible to provide a novel olefin-based resin useful as a compatibilizer for a propylene-based polymer and an ethylene-based polymer, and to provide uses of the olefin-based resin. Furthermore, it is possible to provide a resin composition and a molded article, a packaging body for a lithium-ion battery, and an electricity storage device, which 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.

[0025] 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.

[0026] 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 ​​written before and after "to" as the lower and upper limits. A numerical range "A to B" indicates A or more and B or less. In this specification, when the units of the numerical values ​​written before and after "to" that indicate a numerical range are the same, the unit of the numerical value written before "to" may be omitted. For example, "851 kg / m ３ ~900 kg / m ３ " to "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 total amount of the multiple substances present in the resin composition is referred to unless otherwise specified. In this specification, 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 contain one type or two or more types. In the notation of groups (atomic groups) in this specification, notations that do not indicate substituted or unsubstituted include both unsubstituted and substituted groups. In this specification, the term "layer" includes cases where, when the region where the layer is present is observed, the layer is formed throughout the entire region, as well as cases where the layer is formed only in a portion of the region. In this specification, room temperature means 23°C. In this specification, the term "mainly containing" means that the content of the target substance exceeds 50% by mass.

[0027] <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 content P of the following components (i) to (iv) in the olefin 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 not constituting the graft type olefin polymer [R1]; (iv) a terminally unsaturated propylene-ethylene copolymer not constituting 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.

[0028] In the present invention, the term "grafted olefin polymer" refers to a polymer in which one or more side chains of the grafted olefin polymer [R1] are bonded to the main chain of the grafted olefin polymer [R1]. The grafted olefin polymer [R1] of the present invention has a structure in which side chains of the grafted olefin polymer [R1] composed of a propylene homopolymer or a propylene-ethylene copolymer are chemically bonded to the main chain of the grafted olefin polymer [R1] composed of an ethylene-propylene copolymer or an ethylene-1-butene copolymer. Therefore, the olefin resin (β) containing the grafted olefin polymer [R1] has high compatibility with both the propylene polymer (α1) and the ethylene polymer (α2) described below. In the grafted 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 chains usually satisfy the relationship "number average molecular weight of the main chain > number average molecular weight of the side chain." Therefore, whether the chain in the graft type olefin polymer [R1] is a main chain or a side chain can be determined by measuring the number average molecular weight (Mn).

[0029] 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. 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) have an excellent balance between impact resistance and elongation, or between impact resistance and strength, 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. 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 providing a resin composition (X) containing the olefin resin (β) and a molded article with even better whitening resistance, 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 are as follows: １ H-NMR or １３ It can be measured by C-NMR.

[0030] (II): The side chain of the graft type olefin polymer [R1] is composed of a propylene homopolymer or a propylene-ethylene copolymer. From the viewpoint that the olefin resin (β) exhibits excellent compatibility with the propylene polymer (α1) described below and that the resin composition (X) containing the olefin resin (β) and the molded article thereof exhibit excellent whitening resistance, the side chain of the graft type 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. 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 %, even 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 %. １ H-NMR or １３ It can be measured by C-NMR.

[0031] The main chain and side chains of the graft 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 usually 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 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.

[0032] 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.

[0033] The weight average molecular weight (Mw) of the polymer or copolymer (propylene homopolymer or propylene-ethylene copolymer) constituting the side chain of the graft olefin polymer [R1], as determined by gel permeation chromatography (GPC) in terms of polypropylene, 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 particularly preferably 15,000 to 30,000, from the viewpoint of excellent compatibility of the olefin resin (β) with the propylene polymer (α1) described later and of excellent whitening resistance of the resin composition (X) and molded article containing the olefin resin (β).

[0034] Furthermore, the graft olefin polymer [R1] 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 preferably 5,000 to 150,000, more preferably 6,000 to 110,000, and even more preferably 6,000 to 70,000.

[0035] When one or more, preferably two or more, 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 above-mentioned preferred ranges, the olefin-based resin (β) containing it exhibits 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) exhibit an excellent balance between impact resistance and elongation or between impact resistance and strength, and also exhibit excellent whitening resistance.

[0036] The olefin resin (β) of the present invention contains the graft-type olefin polymer [R1] and satisfies both of the following requirements (III) and (IV).

[0037] (III): The total content of P of the following components (i) to (iv) in the olefin resin (β) is 10 to 80% by 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]; and (iv) a terminally unsaturated propylene-ethylene copolymer not constituting the graft type olefin polymer [R1].

[0038] The content of P (the sum of the above components (i) to (iv)) in this olefin 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 the olefin resin (β) having excellent compatibility with both the propylene polymer (α1) and the ethylene polymer (α2) described below, the viewpoint of the resin composition (X) and the molded article containing the olefin resin (β) having an excellent balance between impact resistance and elongation or an excellent balance between impact resistance and strength, and the viewpoint of excellent whitening resistance.

[0039] The olefin resin (β) of the present invention may be composed solely of the graft olefin polymer [R1], or may contain components other than the graft olefin polymer [R1], such as a propylene homopolymer or a propylene-ethylene copolymer that is an unreacted product or by-product during the synthesis of the graft olefin polymer [R1] and does not constitute the graft olefin polymer [R1], as part of the above P. Therefore, the above (i) to (iv) constituting P are usually components derived from terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer that serves as a raw material for the side chain of the graft olefin polymer [R1], the above (iii) is usually 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 above (iv) is usually 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 the olefin resin (β) is produced by the method for producing the olefin resin (β) described below, P, which is the sum of the above (i) to (iv), is the sum of components derived from the side chain raw materials.

[0040] 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 is 100% by mass of the olefin resin (β). Therefore, when the olefin resin (β) is produced by the method for producing the olefin resin (β) 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 P content calculated from the difference between the amount of the olefin resin (β) and the amount of the side chain raw material and the P content calculated by analyzing the olefin resin (β) are very similar values ​​according to the inventors' findings, so either method may be used to determine the P content. 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.

[0041] (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 viewpoints 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 between impact resistance and strength, excellent blushing resistance, and excellent resin composition and molding processability. Here, when the main chain of the graft-type olefin polymer [R1] is an ethylene-propylene copolymer, the intrinsic 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.

[0042] 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 −30 to 165° C., and even more preferably 0 to 165° C.

[0043] 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). Since the olefin-based resin (β) contains a graft-type olefin-based polymer [R1], it 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-based polymer [R1] constituting the olefin-based resin (β), and the higher Tm is due to the side chain of the graft-type olefin-based polymer [R1] constituting the olefin-based resin (β). When the Tm is within the above range, the resin composition (X) and molded article containing the olefin-based resin (β) have excellent compatibility with both the propylene-based polymer (α1) and the ethylene-based polymer (α2) described below. The resin composition (X) and molded article containing the olefin-based resin (β) have an excellent balance between impact resistance and elongation, or between impact resistance and strength, and also have excellent 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.

[0044] The olefin resin (β) of the present invention preferably has a melt flow rate (MFR) of 0.01 to 100 g / 10 min, as measured at 190°C under a load of 2.16 kg in accordance with ASTM D 1238. 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. Furthermore, 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, this can be achieved by 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 during polymerization of 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.

[0045] The olefin resin (β) of the present invention preferably has a glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) of −75 to −40° C. 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, and are therefore preferable in terms of excellent molding processability.

[0046] The olefin resin (β) of the present invention preferably has a density measured at 23°C in accordance with JIS K7112 (density measured by a density gradient tube method) of 850 to 950 kg / m ３ and more preferably 850 to 925 kg / m ３ and more preferably 860 to 900 kg / m ３The 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 resin (β) satisfies such a range, the resin composition (X) and molded article containing the olefin resin (β) are preferred because they have an excellent balance between impact resistance and elongation or a balance between impact resistance and strength and excellent whitening resistance.

[0047] The olefin resin (β) of the present invention contains ethylene-derived structural units in an amount of preferably 10 to 92% by mass, more preferably 15 to 86% by mass, even more preferably 20 to 80% by mass, and particularly preferably 20 to 70% by mass, when the total content of structural units derived from ethylene, structural units derived from propylene or 1-butene, and structural units other than the structural units derived from ethylene and the structural units derived from propylene or 1-butene (other structural units) in the olefin resin (β) containing the graft olefin polymer [R1] is taken as 100% by mass, from the viewpoint of compatibility with the propylene polymer (α1) and the ethylene polymer (α2) described below.

[0048] The presence of the graft type olefin polymer [R1] in the 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 graft type olefin polymer [R1] in the olefin resin (β) with peak separation by GPC. For example, by performing peak separation from a molecular weight distribution curve measured using GPC, the constituent ratio of each portion can be determined, and the formation of the graft type olefin polymer [R1] can be confirmed from this. In addition, various analytical techniques can be used to confirm this, and the means of confirmation are not particularly limited.

[0049] 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 as 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 as 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 preferably a copolymer in which the content of structural units derived from ethylene in the ethylene-propylene copolymer that is the main chain of the graft type olefin polymer [R1] is 1 to 30 mol %, and more preferably the content of structural units derived from ethylene in the ethylene-propylene copolymer that is the main chain of the graft type olefin polymer [R1] is 75 to 85 mol %, and the content of structural units derived from propylene in the ethylene-propylene copolymer that is the main chain of the graft type olefin polymer [R1] is 15 to 25 mol %, and the intrinsic viscosity [η] of the olefin resin (β) measured in decalin at 135°C is 0.9 to 1.25 dL / g.

[0050] 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 constitutes 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 constitutes 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.

[0051] <Method for Producing Olefin 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 to produce a terminally unsaturated polypropylene, or a step of copolymerizing propylene and ethylene to produce a terminally unsaturated propylene-ethylene copolymer, in the presence of an olefin polymerization catalyst containing a transition metal compound [A] of Group 4 of the periodic table that contains a ligand having a dimethylsilylbisindenyl skeleton. 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]:

[0052]

[0053] (In formula [B], R 1 , R 2 , R 3 , R 4 , R 5 , R 8 , R 9 and R 12 each independently represents a hydrogen atom, a hydrocarbon group, a silicon-containing group, or a heteroatom-containing group other than a silicon-containing group; R 1 ~R 4 Two adjacent groups among R may be bonded to each other to form a ring. 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, and 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, and R 6 and R 7 may be bonded to each other to form a ring, and R 10 and R 11may 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. 13 and R 14 each independently represents an aryl group. 1 represents a carbon atom or a silicon atom. 1 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; 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.

[0054] Steps (A) and (B) will be described in order below. [Step (A)] Step (A) is a step for producing a terminally unsaturated polypropylene or a terminally unsaturated propylene-ethylene copolymer, which serves as a raw material for the side chains 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.

[0055] [Transition Metal Compound [A]] In step (A), an olefin polymerization catalyst containing 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]) is used. 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 the catalyst component (C) described below.

[0056] 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.

[0057] 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 a zirconocene, an olefin resin (β) containing a desired graft-type olefin polymer [R1] can be efficiently produced.

[0058] More specifically, suitable compounds include dimethylsilylbis{1-(2-n-propyl-4-(9-phenanthryl)indenyl)}zirconium dichloride, dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride, and dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl. The transition metal compounds [A] described above may be used singly or in combination of two or more.

[0059] [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.

[0060] [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 preferred step is one 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.

[0061] 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), which will be described later.

[0062] 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 normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of a batch system, a semi-continuous system, and a continuous system. The reaction time in step (A) (average residence time when polymerization is carried out in a continuous system) 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.

[0063] In the polymerization or copolymerization in step (A), it is preferable to supply propylene alone or propylene and ethylene in proportions such that the propylene amount is 80 to 100 mol % and the ethylene amount is 0 to 20 mol %. 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.

[0064] The molecular weight of the terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer obtained in step (A) can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. It can also be adjusted by using the catalyst component (C) described below, such as triisobutylaluminum, methylaluminoxane, or diethylzinc. When hydrogen is added, the amount is preferably 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 under hydrogen-free conditions.

[0065] 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 all unsaturated carbon-carbon bonds) of usually 40% or more, preferably 50%, and more preferably 60% or more. The terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer produced in step (A) has a terminal vinyl group ratio of usually 0.1 to 15, and preferably 0.4 to 15, per 1,000 carbon atoms.

[0066] If 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 1,000 carbon atoms are low, the amount of terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer (specifically, a propylene homopolymer or a propylene-ethylene copolymer having a vinyl group at one end) introduced into the main chain in the subsequent step (B) will be low, and the amount of grafted olefin polymer [R1] produced will be low, and the desired effect may not be obtained.

[0067] The terminal vinyl ratio (the ratio of the number of vinyl groups to the total number of unsaturated carbon-carbon bonds) and the ratio of terminal vinyl groups per 1,000 carbon atoms are: １ It can be calculated by a conventional method based on polymer structural analysis by H-NMR measurement.

[0068] [Step (B)] Step (B) is a step of copolymerizing the terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer produced in step (A) above 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.

[0069] [Bridged Metallocene Compound] The bridged metallocene compound used in step (B) is a compound represented by the following general formula [B].

[0070]

[0071] In formula [B], R 1 , R 2 , R 3 , R 4 , R 5 , R 8 , R 9 and R 12 each independently represents a hydrogen atom, a hydrocarbon group, a silicon-containing group, or a heteroatom-containing group other than a silicon-containing group; R 1 ~R 4 Two adjacent groups among these may be bonded to each other to form a ring.

[0072] The hydrocarbon group is preferably a hydrocarbon group having 1 to 20 carbon atoms, and specific examples thereof include an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group or a substituted aryl group 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 oxygen-containing groups such as methoxy, ethoxy, and phenoxy groups; nitrogen-containing groups such as nitro, cyano, N-methylamino, N,N-dimethylamino, and N-phenylamino groups; boron-containing groups such as boranetriyl and diboranyl groups; and sulfur-containing groups such as sulfonyl and sulfenyl groups.

[0073] The hydrogen atoms of the hydrocarbon groups may be substituted with halogen atoms, and examples thereof include trifluoromethyl groups, trifluoromethylphenyl groups, pentafluorophenyl groups, and chlorophenyl groups.

[0074] Examples of silicon-containing groups include silyl groups, siloxy groups, hydrocarbon-substituted silyl groups, and hydrocarbon-substituted siloxy groups, such as 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.

[0075] R 6 and R 11 are the same atom or group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, and a heteroatom-containing group other than a silicon-containing group, and R 7 and R 10 are the same atom or group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, and a heteroatom-containing group other than a silicon-containing group, and 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. 6 , R 7 , R 10 and R 11 are not all hydrogen atoms.

[0076] R 13 and R 14 each independently represents an aryl group. 1 represents a zirconium atom or a hafnium atom. 1 represents a carbon atom or a silicon atom.

[0077] 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; 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.

[0078] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and preferably a chlorine atom. Examples of the hydrocarbon group include a hydrocarbon group having 1 to 10 carbon atoms, and specific examples thereof 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, and preferably a methyl group, an ethyl group, or a benzyl group.

[0079] 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 the neutral conjugated or non-conjugated diene 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, s-cis- or s-trans-η 4 -1,4-bis(trimethylsilyl)-1,3-butadiene and the like.

[0080] Specific examples of the anionic ligand 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.

[0081] Specific examples of neutral ligands capable of coordinating with lone electron pairs include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, and ethers such as tetrahydrofuran, diethyl ether, dioxane, and 1,2-dimethoxyethane.

[0082] The substituent R in the above formula [B] 1 ~R 4 The cyclopentadienyl group having R 1 ~R 4 an unsubstituted cyclopentadienyl group in which R is a hydrogen atom; 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, or a 3-cyclohexylcyclopentadienyl group; Examples of 3-,5-disubstituted 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 (R 1 ~R 4 is a hydrogen atom).

[0083] Substituent R in formula [B] 5 ~R 12 The fluorenyl group having R 5 ~R 12is a hydrogen atom; 2-position mono-substituted fluorenyl groups such as a 2-methylfluorenyl group, a 2-t-butylfluorenyl group, and a 2-phenylfluorenyl group; 4-position mono-substituted fluorenyl groups such as a 4-methylfluorenyl group, a 4-t-butylfluorenyl group, and a 4-phenylfluorenyl group; 2-position di-substituted fluorenyl groups such as a 2,7-di-t-butylfluorenyl group and a 3,6-di-t-butylfluorenyl group; 2-position tetra-substituted fluorenyl groups such as a 2,7-dimethyl-3,6-di-t-butylfluorenyl group and a 2,7-diphenyl-3,6-di-t-butylfluorenyl group; and 2-position tetra-substituted fluorenyl groups such as a 2,7-dimethyl-3,6-di-t-butylfluorenyl group and a 2,7-diphenyl-3,6-di-t-butylfluorenyl group. 6 and R 7 are bonded to each other to form a ring, and R 10 and R 11 and 2-, 3-, 6-, and 7-tetrasubstituted fluorenyl groups in which the groups are bonded to each other to form a ring, but are not limited thereto.

[0084]

[0085]

[0086] In formulas [VI] and [V-II], R 5 , R 8 , R 9 , R 12 is the same as defined in the above general formula [B], and R a , R b , R c , R d , R e , R f , R g and R h are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and 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 formula [VI], R x and R y are each independently a hydrocarbon group having 1 to 3 carbon atoms which may have an unsaturated bond, and R x is R aor R c may form a double bond together with the carbon to which R is attached, y is R e or R g may form a double bond together with the carbon to which R is attached, x and R y and are preferably saturated or unsaturated hydrocarbon groups having 1 or 2 carbon atoms.

[0087] Specific examples of the group represented by the general formula [V-I] or [V-II] include an octamethyloctahydrodibenzofluorenyl group represented by the formula [V-III], a tetramethyldodecahydrodibenzofluorenyl group represented by the formula [V-IV], an octamethyltetrahydrodicyclopentafluorenyl group represented by the formula [V-V], a hexamethyldihydrodicyclopentafluorenyl group represented by the formula [V-VI], and a b,h-dibenzofluorenyl group represented by the formula [V-VII].

[0088]

[0089]

[0090]

[0091]

[0092]

[0093] These bridged metallocene compounds containing a fluorenyl group and represented by the above general formula [B] are all excellent in copolymerization ability with non-conjugated polyenes. 1 When Y is a silicon atom, transition metal compounds having 2-substituted fluorenyl groups at the 2 and 7 positions, 3-substituted fluorenyl groups at the 3 and 6 positions, 2-substituted fluorenyl groups at the 2, 3, 6 and 7 positions, and 2-substituted fluorenyl groups at the 2, 3, 6 and 7 positions represented by the above general formula [VI] are particularly preferred. 5 From R 12 Particularly preferred are metallocene compounds having an unsubstituted fluorenyl group in which R is a hydrogen atom, a 3- and 6-disubstituted fluorenyl group, a 2-, 3-, 6- and 7-tetrasubstituted fluorenyl group, and a 2-, 3-, 6- and 7-tetrasubstituted fluorenyl group represented by the above general formula [VI].

[0094] In the present invention, in the bridged metallocene compound represented by the above general formula [B], Y 1 is a silicon atom, and R 5 From R 12 When all of the atoms up to R are hydrogen atoms, 13 and R 14 is 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; Y 1 is a silicon atom, and R 6 and R 11 and are both t-butyl groups, and R 5 , R 7 , R 8 , R 9 , R 10 , R 12 is not a t-butyl group, R 13 and R 14 is selected from groups other than a benzyl group and a silicon-substituted phenyl group; Y 1 is a carbon atom, and R 5 From R 12 When all are hydrogen atoms, R 13 , R 14 is 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; Y 1 is a carbon atom, and R 6 and R 11 is a common group selected from a t-butyl group, a methyl group, or a phenyl group, and R 5 , R 7 , R 8 , R 9 , R 10 and R 12 When R is a group or atom different from 13 , R 14 is 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; Y 1 is a carbon atom, and R 6is a dimethylamino group, a methoxy group, or a methyl group, and R 5 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 But, R 6 When R is a group or atom different from 13 , R 14 is selected from groups other than a methyl group and a phenyl group; Y 1 is a carbon atom, and R is a fluorenyl group. 5 ~R 12 is b,h-dibenzofluorenyl or a,i-dibenzofluorenyl, R 13 , R 14 is preferably selected from groups other than a methyl group and a phenyl group.

[0095] 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 above general formula [B], when Y is a silicon atom, include 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)(octamethyl diphenylsilylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, diphenylsilylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, diphenylsilylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, diphenylsilylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride,

[0096] 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)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride di(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, di(p-tolyl)silylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, di(p-tolyl)silylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride, di(m-tolyl)silylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di( 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(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, di(m-tolyl)silylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride, etc.

[0097] 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,

[0098] 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(cyclopentadienyl)(2, 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-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,

[0099] 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,

[0100] 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)(octyl) 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,

[0101] 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)di 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 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-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,

[0102] 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,

[0103] 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 di(2-naphthyl)methylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride, and the like.

[0104] In addition, as the bridged metallocene compound represented by the general formula [B], in the above specific examples, M in the general formula [B] 1 Examples of such a material include those in which the zirconium atoms are replaced by hafnium atoms.

[0105] 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.

[0106] The bridged metallocene compounds may be used singly or in combination of two or more.

[0107] The bridged metallocene compound represented by the formula [B] used in step (B) is not particularly limited and can be produced by any method, such as those described in J. Organomet. Chem., 63,509 (1996), WO2005 / 100410, WO2006 / 123759, WO01 / 27124, JP-A-2004-168744, JP-A-2004-175759, and JP-A-2000-212194.

[0108] [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.

[0109] [Step (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 in the presence of the polymerization catalyst described above, or a step of copolymerizing the terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer produced in step (A) with ethylene and 1-butene. The polymerization mode of step (B) is not particularly limited, but it can be preferably 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 to use an aliphatic hydrocarbon or aromatic hydrocarbon as the polymerization solvent, and to copolymerize ethylene and propylene, or ethylene and 1-butene, with the terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer produced in step (A) in the presence of an olefin polymerization catalyst containing a bridged metallocene compound represented by general formula [B] above, thereby obtaining a polymerization reaction solution containing a graft olefin polymer [R1].

[0110] In step (B), the terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer produced in step (A) is usually fed in the form of a solution or a slurry to the reactor in step (B). The feeding method is not particularly limited, and the polymerization reaction liquid obtained in step (A) may be continuously fed to the reactor of 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).

[0111] Examples of polymerization solvents 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. The polymerization solvent for step (B) may be the same as or different from the polymerization solvent for step (A). The polymerization temperature for step (B) is typically in the range of 50°C to 200°C, preferably 80°C to 200°C, and more preferably 90°C to 200°C.

[0112] The polymerization pressure in step (B) is usually normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out by any of batch, semi-continuous, and continuous methods. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions. Among these, it is preferable in the present invention to employ a method in which the monomers are continuously supplied to a reactor to carry out copolymerization.

[0113] The reaction time in step (B) (average residence time when the copolymerization 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.

[0114] The polymer concentration in step (B) during steady-state operation is, for example, 0.5 to 40% by mass, preferably 1 to 35% by mass, and is preferably 1.5 to 35% by mass from the viewpoints of viscosity limitations in polymerization capacity, the load in a post-treatment step (solvent removal), and productivity.

[0115] 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), the copolymerization is preferably carried out under conditions such that the weight average molecular weight (Mw) of the ethylene-propylene polymer portion or the ethylene-1-butene polymer portion that will form the main chain of the resulting graft-type olefin polymer [R1], as determined by gel permeation chromatography (GPC) in terms of polyethylene, is in the range of 30,000 to 200,000.

[0116] 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. Furthermore, 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 amount is suitably about 0.001 to 100 NL per kg of olefin.

[0117] [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 catalyst component (C). 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 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.

[0118] The catalyst component (C) is one or more compounds selected from (C1) organometallic compounds, (C2) organoaluminum oxy-compounds, and (C3) compounds that react with the transition metal compounds contained in the olefin polymerization catalyst to form ion pairs. Compounds (C1) to (C3) will be explained below in order.

[0119] ((C1) Organometallic Compound) Specific examples of the (C1) organometallic compound 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 (C1) organometallic compound does not include the (C2) organoaluminum oxy compound described below.

[0120] R a p Al (OR b ) q H r Y s ...(C1-a) In the above 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.

[0121] M3 AlR c 4...(C1-b) In the above general formula (C1-b), M 3 represents Li, Na or K, and R c represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.

[0122] 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; M 4 is Mg, Zn or Cd.

[0123] Examples of the organoaluminum compound represented by the general formula (C1-a) include compounds represented by the following general formulas (C-1a-1) to (C-1a-4). a p 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,

[0124] R a p 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; a p 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 that satisfies 2≦p<3,

[0125] Ra 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, and s is a number that satisfies 0≦s<3, and p+q+s=3.

[0126] More specific examples of the organoaluminum compound belonging to the 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, tri-tert-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-CH) x Al y (C5H 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; R a 2.5 Al (OR b ) 0.5 Partially alkoxylated alkylaluminum having an average composition represented by the formula: a and R bmay 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.

[0127] 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.

[0128] The compounds belonging to the general formula (C1-b) include LiAl(C2H5)4, LiAl(C7H 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.

[0129] In addition, as the organometallic compound (C1), methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, butylmagnesium chloride, etc. can also be used.

[0130] Furthermore, compounds that form the 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) described above can be used alone 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 typically 0.01 to 100,000, preferably 0.05 to 50,000.

[0131] ((C2) Organoaluminum oxy compound) The (C2) organoaluminum oxy compound 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-2-78687. Specific examples of the (C2) organoaluminum oxy compound 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.

[0132] (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 steam is directly applied to 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.

[0133] The aluminoxane may contain a small amount of an organometallic component. Alternatively, the solvent or unreacted organoaluminum compound may be removed by distillation from the recovered aluminoxane solution, and the resulting aluminoxane may then be redissolved in a solvent or suspended in a poor solvent for the aluminoxane. Specific examples of organoaluminum compounds used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the general formula (C1-a) above. Among these, trialkylaluminums and tricycloalkylaluminums are preferred, with trimethylaluminum being particularly preferred. The organoaluminum compounds described above may be used singly or in combination of two or more.

[0134] Examples of solvents that can be used in preparing 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 chlorides and bromides, of the above aromatic hydrocarbons, aliphatic hydrocarbons, 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.

[0135] The benzene-insoluble organoaluminum oxy-compound used in the present invention is preferably one in which the solubility of the Al component in benzene at 60°C is usually 10% or less, preferably 5% or less, and particularly preferably 2% or less, calculated as Al atoms, i.e., it is insoluble or sparingly soluble in benzene. The organoaluminum oxy-compound (C2) used in the present invention also includes boron-containing organoaluminum oxy-compounds represented by the following general formula (III):

[0136] (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.

[0137] 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. 19 -B(OH)2...(IV) (In general formula (IV), R 19 is R in the above general formula (III). 17 It represents the same group as

[0138] Specific examples of alkylboronic acids represented by general formula (IV) above 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.

[0139] Specific examples of the organoaluminum compound to be reacted with such alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the above general formula (C1-a).

[0140] As the organoaluminum compound, trialkylaluminum and tricycloalkylaluminum are preferred, with trimethylaluminum, triethylaluminum, and triisobutylaluminum being particularly preferred. These may be used alone or in combination of two or more. It is preferred that the olefin polymerization catalyst contains (C2) an organoaluminum oxy compound, since this will result in high polymerization activity for olefin compounds.

[0141] The organoaluminum oxy compounds (C2) described above may be used singly or in combination of two or more. The organoaluminum oxy compounds (C2) are used in an amount such that the molar ratio (C2 / M) of the 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.

[0142] (C3) Compound that Reacts with Transition Metal Compound to Form an Ion Pair) (C3) Compound that reacts with a transition metal compound to form an ion pair is a compound that reacts with a transition metal compound contained in the olefin polymerization catalyst to form an ion pair. The transition metal compound contained in the 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).

[0143] Examples of the compound (C3) used in the present invention that reacts with a transition metal compound to form an ion pair (hereinafter referred to as "ionizing ionic compound") 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 U.S. Pat. No. 5,321,106. Further examples include heteropoly compounds and isopoly compounds.

[0144] Specific examples of the Lewis acid include compounds represented by BR3 (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. Examples of the ionic compound include compounds represented by the following general formula (V):

[0145] (In general formula (V), R 20 Is H +, a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, or a ferrocenium cation having a transition metal; R 21 ~R 24 may be the same or different and are organic groups, preferably aryl groups or substituted aryl groups.

[0146] Specific examples of the carbonium cation include tri-substituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

[0147] 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.

[0148] Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation. 20 As the cation, a carbonium cation and an ammonium cation are preferred, and a triphenylcarbonium cation, an N,N-dimethylanilinium cation, and an N,N-diethylanilinium cation are particularly preferred.

[0149] Further, examples of the ionic compound include trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

[0150] Specific examples of the trialkyl-substituted ammonium salt 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.

[0151] Specific examples of the N,N-dialkylanilinium salts include N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, N,N,2,4,6-pentamethylanilinium tetra(phenyl)boron, etc. Specific examples of the dialkylammonium salts include di(1-propyl)ammonium tetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron, etc.

[0152] Further examples of the ionic compound 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):

[0153] (In formula (VI), Et represents an ethyl group.)

[0154] (In formula (VII), Et represents an ethyl group.)

[0155] Specific examples of borane compounds, which are examples of 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).

[0156] 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-dicarboxundecaborate)chromate (III), tri(n-butyl)ammonium bis(tribromooctahydride-7,8-dicarboxundecaborate)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), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboudecaborate)nickelate (IV);

[0157] Heteropoly compounds, which are examples of ionized ionic compounds, are compounds that contain the atom selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten.Specifically, can include, but are not limited to, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolibdic acid, phosphomolybdic acid, titaniummolybdic 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 the salts of these acids. Examples of the salts include salts of the above acids with metals of 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.

[0158] 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 ion 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. 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.

[0159] The above-mentioned ionizing ionic compounds ((C3) compounds that react with the transition metal compound contained in the olefin polymerization catalyst 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.

[0160] [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 object of the present invention. 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 suitable 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. Among these, 1-butene, 1-pentene, 1-hexene, and 1-octene are preferred. Ethylene, propylene, 1-butene, and α-olefins having 3 to 20 carbon atoms may be derived from naphtha-derived raw materials, bionaphtha-derived raw materials, or a combination of naphtha-derived raw materials and bionaphtha-derived raw materials. Furthermore, the α-olefins may contain one or more chemically recycled raw materials.

[0161] [Other Steps] In addition to the above-described steps (A) and (B), the method for producing the olefin resin (β) of the present invention may, if necessary, include a step of recovering the polymer produced in step (A) or (B), or in 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.

[0162] <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.

[0163] [Propylene-Based Polymer (α1)] The resin composition (X) of the present invention can contain a propylene-based polymer (α1). Examples of the propylene-based 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 α-olefin may be a random copolymer (random polypropylene) or a block copolymer (block polypropylene).

[0164] Specific examples of the α-olefin 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 α-olefins include ethylene, 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, can be preferably used.

[0165] The α-olefin other than propylene having 2 to 20 carbon atoms may be one type alone or two or more types. From the viewpoint of achieving excellent whitening resistance in the resin composition (X) containing the olefin resin (β) and the molded article, the α-olefin other than propylene having 2 to 20 carbon atoms is 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 biomass-derived monomers 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.

[0166] The propylene polymer (α1) contained in the resin composition (X) of the present invention may be one type or two or more types, but 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 from the viewpoint of excellent whitening resistance, the propylene polymer (α1) contained in the resin composition (X) of the present invention is preferably two or more types. In the present invention, the propylene polymer (α1) may be any of a product produced by polymerization or copolymerization, a commercially available product, and a recycled product.

[0167] 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 at least 60 mol%, even more preferably at least 70 mol%, particularly preferably at least 80 mol%, particularly preferably at least 90 mol%, and extremely preferably at least 95 mol% of structural units (iv) derived from propylene. On the other hand, the propylene polymer (α1) preferably contains no more than 50 mol%, more preferably no more than 40 mol%, even more preferably no more than 30 mol%, particularly preferably no more than 20 mol%, particularly preferably no more than 10 mol%, and extremely preferably no more than 5 mol% of structural units (v) derived from an α-olefin other than propylene having 2 to 20 carbon atoms. (However, the total content of the structural units (iv) and (v) is taken as 100 mol%).)

[0168] Furthermore, when the propylene polymer (α1) is a copolymer of propylene and two α-olefins other than propylene having 2 to 20 carbon atoms, the propylene polymer (α1) may contain 53 mol% or more and less than 95 mol% of structural units (iv) derived from propylene. On the other hand, the propylene polymer (α1) may contain more than 2 mol% and 23 mol% or less of structural units derived from α-olefins having a smaller number of carbon atoms (excluding propylene), and may contain more than 3 mol% and 24 mol% or less of structural units derived from α-olefins having a larger number of carbon atoms (excluding propylene). (However, when the propylene 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 sum of the contents of structural units (iv) and structural units (v) is taken as 100 mol%). The content of the above structural units is １ H-NMR or １３ It can be measured by C-NMR.

[0169] 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, a Ziegler-Natta catalyst. When the propylene polymer (α1) is a commercially available product, commercially available propylene polymers can be used 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 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.

[0170] A preferred embodiment of the propylene polymer (α1) is described below. The propylene polymer (α1) preferably has a melt flow rate (MFR) of 0.01 to 500 g / 10 min, as measured at 230°C under a load of 2.16 kg in accordance with ASTM D1238. 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.

[0171] 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 such a range, the resin composition (X) and molded article of the present invention are preferred because they have an excellent balance between impact resistance and elongation or between impact resistance and strength, excellent whitening resistance, and excellent moldability.

[0172] The polystyrene-equivalent weight average molecular weight (Mw) of the propylene polymer (α1) determined by gel permeation chromatography (GPC) is 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 1,000 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.

[0173] [Ethylene-Based Polymer (α2)] The resin composition (X) of the present invention may contain an ethylene-based polymer (α2). The ethylene-based 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 may contain both biomass-derived monomers and fossil fuel-derived monomers. The ethylene-based polymer (α2) contained in the resin composition (X) of the present invention may be one type or two or more types.

[0174] The resin composition (X) of the present invention contains an ethylene polymer (α2), which allows the production of a molded article having an excellent balance between impact resistance and elongation, or between impact resistance and strength, and excellent whitening resistance. The ethylene polymer (α2) may be either an ethylene homopolymer or an ethylene copolymer containing more than 50 mol% of structural units derived from ethylene. The ethylene polymer (α2) preferably contains 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more of structural units derived from ethylene.

[0175] Preferably, the ethylene 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 polymer (α2) preferably contains 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, 1-dodecene, etc. Among these, α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene can be preferably used, and α-olefins such as 1-butene, 1-pentene, and 1-hexene can be more preferably used.

[0176] 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 the structural units derived from ethylene and the α-olefin having 3 to 20 carbon atoms. The content of the above structural units is １ H-NMR or １３ 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.

[0177] 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 a product produced by polymerization or copolymerization, a commercially available product, and a recycled product. 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, for example, it can be obtained by polymerizing or copolymerizing using a Ziegler-Natta catalyst or the like.

[0178] When the ethylene polymer (α2) is a commercially available product, commercially available ethylene polymers can be used 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 the main component, plastic products containing an ethylene polymer as the main component that have been washed, crushed, and pelletized, and the like can be used.

[0179] A preferred embodiment of the ethylene polymer (α2) will be described below. The ethylene polymer (α2) preferably has a density measured at 25° C. in accordance with ASTM D1505 (density measured by a density gradient tube method) of 840 kg / m ３ More preferably, 845 kg / m ３ More preferably, 850 kg / m ３ More preferably, it is 855 kg / m or more. ３ or more, preferably 940 kg / m ３ or less, more preferably 920 kg / m ３ More preferably, 900 kg / m or less ３ Particularly preferably 890 kg / m or less ３ Below 885 kg / m, very preferably ３ That is, preferably, 840 kg / m or less. ３ ~940 kg / m ３ and more preferably 845 kg / m ３ ~920 kg / m ３ and more preferably 850 kg / m ３ ~900 kg / m ３ and particularly preferably 855 kg / m ３ ~890 kg / m ３ and very preferably 855 kg / m ３ ~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.

[0180] 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.

[0181] 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 1,000 carbon atoms.

[0182] [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.

[0183] 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 propylene polymer (α1) and the ethylene polymer (α2), which are usually poorly compatible, can be homogeneously dispersed by adding the olefin resin (β). 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), propylene polymer (α1), and ethylene polymer (α2) in any ratio.

[0184] In the resin composition (X) of the present invention, the ratio ((β) / ((α1)+(α2))) of the total mass of the olefin resin (β) to the total amount of the propylene polymer (α1) and the ethylene polymer (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 achieving an excellent balance between impact resistance and elongation or an excellent balance between impact resistance and strength, and from the viewpoint of achieving excellent 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.

[0185] In the resin composition (X) having the above-mentioned configuration, the propylene polymer (α1) and the ethylene polymer (α2) can be more uniformly dispersed, and the resin composition (X) is preferable because it has an excellent balance between impact resistance and elongation, or a balance between impact resistance and strength, and excellent whitening resistance. In addition, 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 melt flow rate (MFR) of the propylene polymer (α1) measured at 230°C under a load of 2.16 kg in accordance with ASTM D1238 is 0.01 to 25 g / 10 min, and the density of the ethylene polymer (α2) measured at 25°C in accordance with ASTM D1505 is 850 to 900 kg / m ３In 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 amount 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.

[0186] 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 the other components include other resins, rubbers, inorganic fillers, and additives. Examples of the 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.

[0187] The resin composition (X) of the present invention may be a blend of post-consumer recycled (PIR (post-industrial recycled), PCR (post-consumer recycled)) resins. For example, PIR, 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.

[0188] <Method for Producing Resin Composition (X)> The method for producing the resin composition (X) is not particularly limited. For example, the resin composition (X) can be prepared by mixing the olefin resin (β), the propylene polymer (α1), the ethylene polymer (α2), and, if necessary, other optional components in the above-described blending ratio using, for example, a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, a kneader / ruder, or the like, or by melt-kneading the components after or without mixing using a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, or the like. Furthermore, granulation, pulverization, or the like may be performed as necessary. When mixing or kneading, 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 performed using a melt-kneading device such as a commercially available extruder. For example, the temperature of the kneading section of the melt-kneading device is typically 120 to 250°C, preferably 120 to 230°C. The kneading time is typically 0.5 to 30 minutes, particularly preferably 0.5 to 5 minutes.

[0189] The resin composition (X) containing the olefin resin (β), the olefin resin (β) and the propylene polymer (α1), the resin composition (X) containing the olefin resin (β) and the ethylene polymer (α2), or the resin composition (X) containing the olefin resin (β), the propylene polymer (α1), and the ethylene polymer (α2) is suitable for use in pellets, hot melt adhesives, coating agents, and skin materials, and the hot melt adhesives can be used in automobile parts such as automobile interior and exterior parts. Furthermore, molded articles containing the resin composition (X) can also be used in automobile parts such as films, sheets, packaging materials using them, nonwoven fabrics, closures, cap liner materials, foams, and automobile interior and exterior parts.

[0190] <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 sequence in a melt dissolving tank such as a heated melt stirring tank, preferably under vacuum or nitrogen gas flow, by rotating a stirring blade; by melt-mixing by applying shear under heat using the twin rotating blades of a kneader; 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.

[0191] In the case of hot melt adhesives, the adherends may be bonded together before the adhesive cures, or the cured hot melt adhesive may be reheated to activate it and then bonded together. Examples of the shape of such cured hot melt adhesives themselves include sheets, films, nonwoven fabrics, small pieces, and rods. In hot melt adhesives, the content of the olefin resin (β) is typically 1 to 90% by mass, preferably 3 to 50% by mass, and more preferably 5 to 40% by mass, based on the total amount of 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.

[0192] 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 strength and improves the adhesive strength of the adhesive. On the other hand, 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 APAO compositions, but examples 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, and propylene-ethylene copolymers.

[0193] The olefin resin (β) has excellent compatibility with APAO and is therefore preferably used. Specific examples of APAO include RT2730 (product name, manufactured by Rextaq 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). APAOs may be used alone or in combination of two or more. When an APAO is used in a hot melt adhesive, its content is usually 1 to 99% by mass, preferably 10 to 90% by mass, and more preferably 20 to 80% by 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.

[0194] The hot melt adhesive may contain a tackifier as needed. Examples of tackifiers include at least one resin selected from natural rosin, modified rosin, polyterpene resin, synthetic petroleum resin, coumarone resin, phenolic 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, with those having an aliphatic and / or alicyclic structure being even more preferred. Particularly preferred petroleum resins having an aliphatic and / or alicyclic structure include partially and fully hydrogenated rosin and their derivatives in the case of rosin resins, homopolymers or copolymers of cyclic terpenes in the case of polyterpene 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.

[0195] A tackifier having a softening point of 25 to 160°C is preferred. A softening point of 25°C or higher can prevent bleeding to the surface, while a softening point of 160°C or lower prevents excessively high viscosity during melting, 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. One tackifier may be used alone, or two or more tackifiers may be used in combination. When a tackifier is used in a hot melt adhesive, its content is typically 1 to 70% by mass, preferably 5 to 50% by mass, and more preferably 10 to 40% by mass, based on the total amount of the adhesive. A content within the above range is preferred because it can impart fluidity and adhesive strength without reducing adhesive strength.

[0196] The hot melt adhesive may contain wax as needed. 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. Because the olefin resin (β) has excellent compatibility with polypropylene, polypropylene wax is particularly preferred. The wax preferably has a B-type viscosity (190°C) of 10 to 8,000 mPa·s, more preferably 100 to 5,000 mPa·s. A B-type viscosity within the above range is preferable in terms of cohesion and kneading processability. The wax preferably has a melting point, as measured by DSC, of ​​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.

[0197] Examples of commercially available waxes include those sold under the trade name "Mitsui Hiwax 420P," "Mitsui Hiwax NL100," and "Mitsui Hiwax NP015" (all manufactured by Mitsui Chemicals, Inc.). A single wax may be used, or two or more waxes may be used in combination. When a wax is used in a hot melt adhesive, its content is typically 1 to 60% by mass, preferably 1 to 50% by mass, and more preferably 1 to 40% by mass, based on the total amount of the adhesive. A content within the above range is preferred because it can impart fluidity and heat resistance without reducing adhesive strength.

[0198] If necessary, at least one additive selected from conventionally known flow modifiers, nucleating agents, antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, pigments, dyes, antibacterial agents, antifungal agents, antistatic agents, foaming agents, foaming assistants, plasticizers such as mineral oil, and fillers can be added to the hot melt adhesive, within a range that does not impair the objectives of the present disclosure.

[0199] The application of the hot melt adhesive is not particularly limited as long as the objectives of the present disclosure can be achieved, but commercially available hot melt applicators are widely used. Examples of hot melt applicators include slot coater applicators, roll coater applicators, spiral applicators that can apply in a spiral pattern, omega applicators and control seam applicators that can apply in a wave pattern, slot spray applicators and curtain spray applicators that can apply in a planar pattern, dot applicators that can apply in a dot pattern, and bead applicators that can apply in a linear pattern. A particularly preferred application of hot melt adhesives is the bonding of cardboard boxes. 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, such as a T-die method, inflation method, calendar method, or spinning method, and then fixing it between the adherends to be laminated and heat-bonded. Alternatively, a sheet-shaped adhesive is heated and melted on one adherend, and then pressure-bonded to the other adherend while cooling. Alternatively, the hot melt adhesive of the present disclosure may be melted in the above-described screw extruder, and the adhesive may be inserted directly between the adherends to be laminated to effect thermal bonding without the above-described molding process. Alternatively, when one of the adherends is a thermoplastic plastic, the adhesive may be directly bonded by co-extrusion, or the adhesive may be applied directly to one of the adherends and then heat-bonded again.

[0200] Hot melt adhesives can be used to bond substrates made of polyolefin resins or the like, to bond 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), or to bond the metal materials or the other materials to each other. They are particularly suitable for bonding cardboard to other adherends, or cardboard to cardboard. Examples of substrates made of polyolefin resins or the like include single-layer or laminated resin sheets made of polyolefin resins (e.g., polyethylene, polypropylene), polyester resins, polycarbonate resins, polyarylate resins, acrylic resins, polyphenylene sulfide resins, polystyrene resins, vinyl resins, vinyl chloride resins, polyimide resins, epoxy resins, and the like.

[0201] <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).

[0202] 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.

[0203] 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, or 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, or 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, polyolefin materials, particularly polybutene-based materials and polypropylene-based materials, are preferred.

[0204] <Molded Article> The molded article of the present invention can be obtained by molding the resin composition (X) of the present invention described above using a known molding method. For example, it can be obtained by a known thermoforming method such as extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calendar molding, or foam molding. The molded article of the present invention is obtained from a 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 a propylene-based polymer (α1) and an 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.

[0205] The molded article of the present invention can be used for door trim, rear package trim, instrument panel, gasket, seat back garnish, column cover, bumper, fender, side molding, wheel cover, mudguard, mirror cover, instrument panel, exterior door, hood, spoiler, windscreen, hub cap, mirror frame, body panel, air bag cover, protective side molding, shoe sole, shoe midsole, inner sole, sole, sandal, wire sheath for automobile or electrical wire for equipment, wire insulator, other wire / cable covering, hand of household appliance, etc. Housings, packing, hot plates, rice cookers, pot bodies, washing machines and other home appliance components, containers such as battery containers, electronic component packaging films, waterproof sheets, flooring materials, ceiling materials, wallpaper, building material component packaging sheets, flooring mats, floor finishing materials, blinds, pipes, decorative sheets or building material protection sheets, home appliances and furniture products such as television cabinets, stereo speaker boxes, video cabinets, various types of storage furniture, unit furniture, etc., housing components such as doors, door frames, window frames, moldings, baseboards, opening frames, etc., furniture components such as kitchen and storage furniture doors, office floor mats, car PET anti-slip pads, low-temperature heat sealable film, easy-peel film, packaging film, individual packaging materials for medicines, grips, gaskets, multi-layer hoses, infusion bottles, sanitary bottles for shampoo etc., cosmetic bottles and cases, caps, cap liners, drinking water cap liners, stationery such as writing implements, toys, leisure goods, disposable diapers, disposable underwear, sanitary materials and elastic materials such as sanitary napkins, clothing cases, buckets, washbasins, cooking utensils, various other cases, containers, agricultural films, sports ground equipment, boats and water Ship parts, garden furniture, roller bottles and culture medium bottles used for cultivation, diaper tabs, sterilization wrap, dustcloths, bedding, food packaging film, retort packaging materials, retort tableware containers, food packaging trays and beverage cups and bottles, various other bottles, cups, sheets, films, tubes, syringes, syringe barrels, ampoules, petri dishes and other medical equipment, 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, car interior lighting covers,It can be used for LED lamp covers in electrical and electronic components, covers for other display devices, solar cell sealing sheets, battery packaging, lithium ion battery packaging, etc.

[0206] <Film> Examples of applications of the olefin-based resin (β) or the resin composition (X) include films containing either of these. The film containing the olefin-based resin (β) or the resin composition (X) using the same may be a stretched film or an unstretched film, preferably an unstretched 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. In the case of a multilayer film, at least one layer may contain the olefin-based resin (β) or the resin composition (X). Examples of methods include co-extrusion using known multilayer film molding methods such as T-die film molding and inflation film molding, and lamination of a layer containing the olefin-based resin (β) or the resin composition (X) on a pre-formed substrate. The substrate is not particularly limited, but 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, all of the layers are unstretched.

[0207] The thickness of the unstretched film (total thickness if multilayer) is preferably 5 μm or more, more preferably 10 μm or more, and preferably 150 μm or less, more preferably 100 μm or less. Although no particular distinction is made between film and sheet in this specification, a film generally refers to a membranous body with a thickness of less than 250 μm, and a sheet generally refers to a thin plate-like body with a thickness of 250 μm or more. Films can be used, for example, as stretch films, shrink films, breathable films, adhesive films, process films, etc.

[0208] <Sheet> Examples of applications of the olefin resin (β) or the resin composition (X) include a sheet containing either of them. The sheet is not particularly limited, and the 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 must contain the olefin resin (β) or the resin composition (X). The thickness of the sheet (total thickness in the case of a multi-layered sheet) is preferably 250 to 2000 μm, more preferably 250 to 1500 μm. Specific applications of the sheet include, for example, packaging sheets for packaging food, liquids, pharmaceuticals, etc., and containers formed from the sheet (e.g., trays and cups thermoformed from the sheet, and containers formed by folding the sheet).

[0209] <Injection Molded Article and Blow Molded Article> 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 device under known conditions. The injection molded article can be widely used, for example, for trim materials for automobile interiors, exterior parts for automobiles, housings for home appliances, containers, tubes, or pipes.

[0210] 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 blow-molded articles include those produced by blow-molding into a desired shape using a conventionally known blow-molding apparatus under known conditions. The blow-molded article may be, for example, a multilayer molded article. In this case, at least one layer of the multilayer molded article contains the olefin-based resin (β) or the resin composition (X). Specific applications of injection-molded articles and blow-molded articles include, for example, food containers, beverage containers, caps, pharmaceutical containers, various other containers, daily necessities, housings for home appliances, automobile parts, tubes, and pipes. Examples of daily necessities include clothing cases, buckets, washbasins, stationery such as writing implements, containers, toys, cooking utensils, and various other cases.

[0211] <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 of the layer (X). The sealant film may have a layer (X) and a layer (another layer) other than the layer (X). The sealant film may have two or more of the other layers.

[0212] In this specification, there is no particular distinction between film and sheet. Generally, a film refers to a membranous body having a thickness of less than 250 μm, and a sheet refers to a thin plate-like body having a thickness of 250 μm or more. The shape, size, thickness, etc. of the sealant film can be appropriately selected depending on the desired application. The sealant film may be either a stretched film or an unstretched film, but is preferably an unstretched film. When the unstretched film is multilayered, "unstretched" means that none of the layers are stretched. The unstretched film is not particularly limited as long as it is an unstretched film, and the shape, size, thickness, etc. can be appropriately selected depending on the desired application. The unstretched film may be a single layer or a multilayer film having two or more layers. When the unstretched film is multilayered, at least one of the layers must be layer (X). That is, the unstretched film may be a single layer or multilayer film consisting of layer (X) alone, or may be a laminate having layer (X) and a substrate. Specific examples of the substrate will be described later.

[0213] The thickness of the sealant film or non-stretched film (the total thickness of all layers when the film is multilayered) is preferably 5 μm or more, more preferably 10 μm or more, and even more preferably 20 μm or more, and is preferably 150 μm or less, more preferably 130 μm or less, and even more preferably 100 μm or less, for example, 5 to 150 μm. Specific uses of the sealant film or non-stretched film include, for example, packaging films for packaging food, liquids, pharmaceuticals, electronic components, etc., and packaging materials obtained therefrom.

[0214] The sealant film or unstretched film can be produced, for example, using at least the resin composition (X) using a conventionally known monolayer or multilayer film molding machine. The method for producing the unstretched film is not particularly limited as long as it does not impair the objectives of the present disclosure. Examples of unstretched films include films obtained by coextrusion using known multilayer film molding methods such as T-die film molding and inflation film molding, and films obtained by laminating layer (X) onto a preformed substrate. The unstretched film may be obtained, for example, by a production method including a step of bonding a monolayer or multilayer film containing at least one layer (X) (e.g., a monolayer or multilayer 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.

[0215] <Laminate> An example of the molded article is a laminate. The laminate has 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-based polymer (α1), or a resin composition (X) containing an olefin-based resin (β), a propylene-based polymer (α1), and an ethylene-based polymer (α2). In one embodiment, the laminate has a substrate and the sealant film. In the laminate, for example, a substrate and a sealant film are laminated together.

[0216] Examples of the substrate include resin films, metal foils, paper, and vapor-deposited films. Examples of the resins 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 an oriented film or a non-oriented 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 films, polystyrene films, polyester films, polyamide films, laminated films of polyolefin films and gas-barrier resin films, metal foils such as aluminum foil, paper, and vapor-deposited films.

[0217] The laminate can be produced, for example, using a conventionally known single-layer or multi-layer film molding machine. The laminate can be produced, for example, by a production method including a step of bonding a substrate and the sealant film by any one selected from the group consisting of melt extrusion lamination, thermal lamination, and dry lamination. The laminate can be produced, for example, by a production method including a step of bonding a substrate and a single-layer or multi-layer film consisting of only layer (X) by any one selected from the group consisting of melt extrusion lamination, thermal lamination, and dry lamination.

[0218] 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 whitening resistance when stretched and good heat resistance and tensile strength, and therefore, by taking advantage of the properties of the sealant film, can be suitably used as packaging for various items, such as daily necessities, food (food packaging materials), liquids, pharmaceuticals, electronic components, and building materials.

[0219] The sealant film or the laminate may be included in an electricity storage device such as a lithium ion battery or a lithium ion capacitor. The sealant film or the laminate can be suitably used, for example, as a packaging material for a lithium ion battery. From another perspective, the present disclosure can also be said to provide an electricity storage device containing the resin composition (X). Examples of such electricity storage devices include electricity storage devices containing the sealant film or the laminate, and specific examples thereof include packaging materials for lithium ion batteries containing the sealant film or the laminate.

[0220] <Lithium-ion battery> The sealant film or laminate can be suitably used as a package for a lithium-ion battery. 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 <Nonaqueous Solvent> section.

[0221] Lithium-ion batteries often have a packaging body (lithium-ion battery packaging body) around their periphery. A positive electrode, a negative electrode, a separator, and a nonaqueous electrolyte are enclosed inside the packaging body. Typically, a positive electrode terminal and a negative electrode terminal are connected to the positive electrode and the negative electrode, respectively. A portion of the positive electrode terminal and a portion of the negative electrode terminal are exposed to the outside of the packaging body.

[0222] The following describes the case where the sealant film or laminate is used as a package. 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 portions of the pair of sealant films or the pair of laminates so 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 package can be used, for example, in portable electronic devices, personal computers, robots, drones, automobiles, aircraft, wearable devices, and energy storage systems (ESS) for home use or renewable energy power generation.

[0223] <Non-aqueous solvent> A non-aqueous electrolyte for a lithium ion battery generally contains a non-aqueous solvent. Various known non-aqueous solvents can be appropriately selected as the non-aqueous solvent. 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.

[0224] (Cyclic Aprotic Solvent) Examples of cyclic aprotic solvents include cyclic carbonates, cyclic carboxylic acid esters, cyclic sulfones, and cyclic ethers. One type of cyclic aprotic solvent may be used, or two or more types may be mixed and used. 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.

[0225] 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. In the case of batteries using graphite as the negative electrode active material, ethylene carbonate is more preferred. Two or more cyclic carbonates may be used in combination.

[0226] 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 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 improve 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 preferred.

[0227] 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 chain carbonate can be mentioned. Examples of combinations of a cyclic carboxylic acid ester with a cyclic carbonate and / or chain carbonate 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, and γ-butyrolactone and propylene carbonate. Propylene carbonate and dimethyl carbonate, γ-butyrolactone, propylene carbonate and methyl ethyl 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 carboxylic acid carbonate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and diethyl carbonate, γ-butyrolactone, ethylene carbonate, dimethyl carbonate, and methyl ethyl carbonate, γ-butyrolactone, ethylene carbonate, dimethyl carbonate, and diethyl carbonate, γ-butyrolactone, ethylene carbonate, methyl ethyl carbonate, and diethyl carbonate, γ-butyrolactone and 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, ethylene carbonate, propylene carbonate, methyl ethyl carbonate, and diethyl carbonate,Examples include 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.

[0228] Examples of cyclic sulfones include sulfolane, 2-methylsulfolane, 3-methylsulfolane, dimethylsulfone, diethylsulfone, dipropylsulfone, methylethylsulfone, and methylpropylsulfone. Examples of cyclic ethers include dioxolane.

[0229] (Chain Aprotic Solvent) Examples of the chain aprotic solvent include chain carbonates, chain carboxylic acid esters, chain ethers, and chain phosphate esters. One type of chain aprotic solvent may be used, or two or more types may be mixed and used. 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.

[0230] Examples of chain carbonates 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 types of chain carbonates may be mixed and used. Examples of chain carboxylic acid esters include methyl pivalate. Examples of chain ethers include dimethoxyethane. An example of the chain phosphate ester is trimethyl phosphate.

[0231] (Solvent Combination) The nonaqueous solvent contained in the nonaqueous electrolyte may be one type or two or more types. One or more cyclic aprotic solvents alone may be used, one or more chain aprotic solvents alone may be used, or a mixture of a cyclic aprotic solvent and a chain protic solvent may be used. When specifically aiming 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 nonaqueous solvent. From the perspective 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.

[0232] Examples of combinations of cyclic carbonates and chain carbonates include 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, and ethylene carbonate and dimethyl carbonate. Examples of suitable carbonates include ethylene carbonate and diethyl carbonate, 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.

[0233] 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, more preferably 10:90 to 70:30. By using such a mixing ratio, an increase in the viscosity of the electrolyte can be suppressed and the degree of dissociation of the electrolyte can be increased, 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. Therefore, an electrolyte with excellent electrical conductivity at room temperature or low temperatures can be obtained, thereby improving the load characteristics of the battery at room temperature to low temperatures.

[0234] The lithium ion battery contains a nonaqueous electrolyte solution containing the nonaqueous solvent. Therefore, the packaging (lithium ion battery packaging) constituting the lithium ion battery is preferably resistant to leaching into the nonaqueous solvent and swelling due to 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 the laminate having a layer (layer (X)) formed from the resin composition (X) have excellent whitening resistance and, for example, are resistant to leaching into the nonaqueous solvent and swelling due to 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 the laminate can be suitably used as a packaging for a lithium ion battery.

[0235] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples as long as the gist of the invention is not exceeded. <Measurement and evaluation methods> In the following examples and comparative examples, each physical property was measured or evaluated by the following methods.

[0236] [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 GMH6-HT columns and two TSKgel GMH6-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).

[0237] [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 a 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 heating 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, when there were two melting peaks, the temperatures of both melting points (Tm) are listed. The heat of fusion (ΔH) was determined by calculating the area of ​​the melting peak. When the melting peak had multiple peaks, the area of ​​the entire melting peak was calculated.

[0238] [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, and the baseline shifting 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).

[0239] [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 type nuclear magnetic resonance apparatus, measurement nuclei: 1 H (400MHz); １３ C (125 MHz), measurement mode: single pulse, pulse width: 45° (5.25 μsec), number of points: 32k, measurement range: 20 ppm (-4 to 16 ppm), repetition time: 7.0 seconds, number of accumulations: 64, measurement solvent: orthodichlorobenzene-d4, 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 ratio of ethylene and propylene in the ethylene-propylene copolymer that is the main chain of the graft-type olefin polymer [R1] in the olefin resin (β), or the ratio of ethylene and 1-butene in the ethylene-1-butene copolymer that is the main chain of the graft-type olefin polymer [R1] in the olefin resin (β), is measured at 125 MHz. １３ The peak intensity derived from ethylene and the peak intensity (integrated value) derived from propylene or 1-butene obtained from C-NMR (JEOL ECX400P) were measured and quantified.

[0240] [Terminal vinyl ratio] The terminal vinyl ratio of terminally unsaturated polypropylene and terminally unsaturated propylene-ethylene copolymer is 400 MHz. １ The terminal vinyl ratio was determined 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 H-NMR (JEOL ECX400P).

[0241] [Proportion of P (total content of components (i) to (iv) above) in olefin resin (β)] (Method 1: Calculation from charged amount) The proportion of component P derived from terminally unsaturated polypropylene and terminally unsaturated propylene-ethylene copolymer in the olefin resin (β) described below (proportion of the total P content of components (i) to (iv) above) was calculated from the difference between the charged amount of terminally unsaturated polypropylene or terminally unsaturated propylene-ethylene copolymer and the amount of the obtained olefin resin (β). (Method 2: Calculation by analysis of 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 sum of components derived from the terminally unsaturated polypropylene and the terminally unsaturated propylene-ethylene copolymer, was calculated from a calibration curve based on the correlation between the heat of fusion (ΔH) (J / g) at the melting point (Tm) (°C) and the proportion (mass%) of P calculated from the above-mentioned charged amounts. 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 charged amounts of terminally unsaturated polypropylene and terminally unsaturated propylene-ethylene copolymer, to obtain multiple olefin-based resins with different proportions (mass%) of P. Next, polymerization was similarly carried out for multiple main chain ethylene compositions to obtain multiple olefin-based resins with different main chain ethylene composition proportions and different proportions (mass%) of P. Furthermore, a calibration curve was prepared based on the heat of fusion (ΔH) (J / g) at the melting point (Tm) of these multiple olefin-based resins and the proportion (mass%) of P calculated from the above-mentioned charged amounts. The P content in the olefin resin (β-1) produced in Example 1A described below was 46.1% by mass by Method 1 (calculated from the charged amount) and 46.3% by mass by Method 2 (analysis results using the created calibration curve), which were equivalent. Furthermore, the P content in the olefin resin (β-2) produced in Example 2A described below 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), the values ​​calculated by Method 1 are shown.

[0242] [Confirmation of Graft Olefin Polymer [R1]] By performing peak separation on 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.

[0243] [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. After dissolving approximately 20 mg of copolymer in 25 mL of decalin, the specific viscosity ηsp was measured in an oil bath at 135 ° C. using an Ubbelohde viscometer. After diluting this 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 intrinsic viscosity [η] (unit: dl / g) (see the following formula). [η] = lim(ηsp / C) (C → 0)

[0244] [Melt flow rate (MFR)] The melt flow rate (MFR) of the olefin resin (β) described below was measured at 190°C and a load of 2.16 kg in accordance with ASTM D1238E. [Density] Using the strand resin flowed out in the above-mentioned melt flow rate (MFR) measurement, the density was measured at 23°C by the density gradient tube method in accordance with JIS K7112.

[0245] <Reagents> [Reagents] Toluene was purified using a GlassContour organic solvent purification system. Xylene, grade 1, manufactured by Junsei Chemical Co., Ltd., was passed through a 500 mL alumina column. The alumina column used was E. Merck's activated alumina 90 (neutral, activity level I), dried at 150°C for at least 4 hours. A toluene solution of aluminoxane was prepared by diluting a 20% by mass methylaluminoxane / toluene solution manufactured by Nippon Alkyl Aluminum Co., Ltd. with toluene (1.0 M). Triisobutylaluminum was prepared by diluting a 1.0 M triisobutylaluminum manufactured by Tosoh Finechem Corporation with toluene. Triphenylcarbenium tetrakis(pentafluorophenyl)borate was prepared by dissolving triphenylcarbenium tetrakis(pentafluorophenyl)borate manufactured by Asahi Glass Co., Ltd. in toluene at 4.0 mmol / L. 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.

[0246]

[0247] [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, and polymerization was carried out for 30 minutes at 87°C 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 108.3 g of a propylene polymer (terminally unsaturated polypropylene (M-1)). The obtained terminally unsaturated polypropylene (M-1) had a polypropylene-equivalent Mw of 22,907 and a Mw / Mn of 1.88. １ The vinyl percentage at one end measured by H-NMR was 72%.

[0248] 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 ethylene and propylene were continuously supplied, 3.0 mL (3.0 mmol) of a toluene solution (1.0 mol / L) of triisobutylaluminum (also referred to as iBuAl), 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 PhCB(CF)) were added, and polymerization was carried out at atmospheric 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 21.7 g of olefin resin (β-1). It was confirmed by gel permeation chromatography that the terminally unsaturated polypropylene had been consumed, and 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.

[0249] Example 2A: 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 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), to obtain 22.2 g of olefin-based resin (β-2). Gel permeation chromatography confirmed that the terminally unsaturated polypropylene had been consumed, and that a graft-type olefin-based polymer [R1-2] had been produced. The analytical results of the obtained olefin-based resin (β-2) are shown in Table 1-1.

[0250] [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). Gel permeation chromatography confirmed 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.

[0251] [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). Gel permeation chromatography confirmed 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.

[0252] 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 to obtain 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 obtained olefin resin (β-5) are shown in Table 1-1.

[0253] Example 6A: The same procedure as in Example 5A was carried out, except that in step (B) of Example 5A, the amount of terminally unsaturated polypropylene (M-1) added was changed to 6.0 g, the amount of 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 amount of the toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl)borate (4.0 mmol / L) was changed to 5.0 mL (0.020 mmol), to obtain 20.9 g of an olefin-based resin (β-6). Gel permeation chromatography confirmed that the terminally unsaturated polypropylene had been consumed, confirming the formation of a graft-type olefin-based polymer [R1-6]. The analytical results of the obtained olefin-based resin (β-6) are shown in Table 1-1.

[0254] 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.

[0255] 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 resin (β-8). 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 [R1-8] had been produced. The analytical results of the obtained olefin resin (β-8) are shown in Table 1-1.

[0256] Example 9A The same procedure as in Example 1A was carried out, except that in step (B) of Example 1A, the ethylene supply rate was changed to 120.0 L / hr, the propylene supply rate to 18.0 L / hr, the amount of triisobutylaluminum toluene solution (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.

[0257] 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 to obtain 20.1 g of an olefin-based resin (β-10). Gel permeation chromatography confirmed that the terminally unsaturated polypropylene had been consumed, and it was confirmed that a graft-type olefin-based polymer [R1-10] had been produced. The analytical results of the obtained olefin-based resin (β-10) are shown in Table 1-1.

[0258] [Example 11A] Step (A): Production of Terminally Unsaturated Polypropylene (M-1) Terminally unsaturated polypropylene (M-1) was synthesized by the same procedure 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 interior of the polymerization vessel at 600 rpm, ethylene, propylene, and hydrogen were continuously fed at 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.

[0259] [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) was changed to 3.0 g, to obtain 18.2 g of an olefin resin (β-12). Gel permeation chromatography confirmed 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.

[0260] 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 resin (β-13). It was confirmed by gel permeation chromatography that the terminally unsaturated polypropylene had been consumed, and that a graft-type olefin polymer [R1-13] had been produced. The analytical results of the obtained olefin resin (β-13) are shown in Table 1-1.

[0261] [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 for 15 minutes at 100°C 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 tertiary carboxylic acid of 1,297. １ The vinyl percentage at one end measured by H-NMR was 80%.

[0262] 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 iBuAl), 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 PhCB(CF)) 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.

[0263] Example 15A: In step (B) of Example 14A, the amount of terminally unsaturated polypropylene (M-2) added was changed to 4.5 g, the amount of 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 amount of 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 14A was carried out to obtain 13.1 g of an olefin-based resin (β-15). It was confirmed by gel permeation chromatography 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.

[0264] [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 inside 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. Then, 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 and a Mw / Mn of 1.99. １ The vinyl percentage at one end measured by H-NMR was 74%.

[0265] 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 was changed from (M-2) 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.

[0266] [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). Gel permeation chromatography confirmed 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.

[0267] [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 to 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, and polymerization was carried out at normal pressure and 90°C for 15 minutes. The polymerization was terminated by adding a small amount of isobutanol. The obtained 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 obtained terminally unsaturated propylene-ethylene copolymer (M-4) had a polypropylene-equivalent Mw of 20,735 and a Mw / Mn of 1.91. １ The vinyl percentage at one end measured by H-NMR was 69%, and the propylene composition was 88.7 mol% based on a calibration curve showing the correlation between the ethylene composition ratio (mol%) and the melting point (Tm) (°C).

[0268] 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, and 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.

[0269] 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 feed rate was changed to 102.0 L / hr, the propylene feed rate was changed to 14.4 L / hr, the hydrogen feed 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 to obtain 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 obtained olefin-based resin (β-19) are shown in Table 1-2.

[0270] 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, confirming the formation of a graft-type olefin-based polymer [R1-20]. The analytical results of the obtained olefin-based resin (β-20) are shown in Table 1-2.

[0271] 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 to obtain 20.5 g of an olefin-based resin (β-21). It was confirmed by gel permeation chromatography that the terminally unsaturated polypropylene had been consumed, and it was confirmed that a graft-type olefin-based polymer [R1-21] had been produced. The analytical results of the obtained olefin-based resin (β-21) are shown in Table 1-2.

[0272] 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.

[0273] [Example 23A] Step (A): Production of Terminally Unsaturated Polypropylene (M-1) Terminally unsaturated polypropylene (M-1) was synthesized by the same procedure 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 interior of the polymerization vessel at 600 rpm, ethylene, 1-butene, and hydrogen were continuously fed at 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.

[0274] [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) was changed to 5.5 g, to obtain 19.7 g of an olefin resin (β-24). Gel permeation chromatography confirmed 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.

[0275] [Example 25A] Step (A): Production of Terminally Unsaturated Polypropylene (M-1) Terminally unsaturated polypropylene (M-1) was synthesized by the same procedure 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 interior of the polymerization vessel at 600 rpm, ethylene and 1-butene were continuously fed 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.

[0276] [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) 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.

[0277] 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 a toluene solution (1.0 mol / L) to 2.5 mL (2.5 mmol), the amount of the bridged metallocene compound (B-1) in a toluene solution (0.0020 mol / L) to 2.5 mL (0.0050 mmol), and the amount of triphenylcarbenium tetrakis(pentafluorophenyl)borate in a toluene solution (4.0 mmol / L) to 5.0 mL (0.020 mmol), to obtain 26.9 g of an 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.

[0278] [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, to obtain 14.2 g of an olefin-based resin (β'-1). The analytical results of the obtained olefin-based 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-based resin (β'-2). The analytical results of the obtained olefin-based resin (β'-2) are shown in Table 1-2.

[0279] 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, to obtain 12.8 g of an olefin-based resin (β'-9). The analytical results of the obtained olefin-based 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, to obtain 16.7 g of an olefin-based resin (β'-10). The analytical results of the obtained olefin-based 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, to obtain 17.4 g of an olefin-based resin (β'-11). The analytical results of the obtained olefin-based resin (β'-11) are shown in Table 1-2.

[0280] [Comparative Example 6A] Step (A): Production of Terminally Unsaturated Polypropylene (M-1) Terminally unsaturated polypropylene (M-1) was synthesized by the same procedure 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 interior of the polymerization vessel at 600 rpm, ethylene and hydrogen were continuously fed 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.

[0281] Comparative Example 7A: The same procedure as in Comparative Example 6A was carried out, except that 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 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), to obtain 12.4 g of an olefin-based resin (β'-4). Gel permeation chromatography confirmed that the terminally unsaturated polypropylene had been consumed, and that a graft-type olefin-based polymer [R1-29] had been produced. The analytical results of the obtained olefin-based resin (β'-4) are shown in Table 1-2.

[0282] [Example 28A] Step (A): Production of terminally unsaturated polypropylene (M-1) Terminally unsaturated polypropylene (M-1) was synthesized by the same procedure 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 interior of the polymerization vessel at 600 rpm, ethylene and propylene were continuously fed 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.

[0283] 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 to obtain 11.7 g of an olefin resin (β'-6). Gel permeation chromatography confirmed that the terminally unsaturated polypropylene had been consumed, and it was confirmed that a graft-type olefin polymer [R1-31] ​​had been produced. The analytical results of the obtained olefin resin (β'-6) are shown in Table 1-2.

[0284] [Comparative Example 8A] Step (A): Production of Terminally Unsaturated Polypropylene (M-1) Terminally unsaturated polypropylene (M-1) was synthesized by the same procedure 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 interior of the polymerization vessel at 600 rpm, ethylene, propylene, and hydrogen were continuously fed at 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.

[0285] Comparative Example 9A: The same procedure as in Comparative Example 8A was carried out, except that 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), to obtain 9.0 g of an olefin resin (β'-8). Gel permeation chromatography confirmed that the terminally unsaturated polypropylene had been consumed, and 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.

[0286] 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, to obtain 21.7 g of an olefin-based resin (β'-12). The analytical results of the obtained olefin-based 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, to obtain 13.5 g of an olefin-based resin (β'-13). The analytical results of the obtained olefin-based 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, to obtain 14.5 g of an olefin-based resin (β'-14). The analytical results of the obtained olefin-based resin (β'-14) are shown in Table 1-3.

[0287]

[0288]

[0289]

[0290] [Examples 1B to 20B, Examples 1C to 18C, Reference Examples 1B, 1C, Comparative Examples 1B to 7B, and Comparative Examples 1C to 3C] Preparation of Resin Composition (X) The raw materials listed 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) listed 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 raw materials, propylene polymer (α1) and ethylene polymer (α2), 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) Using each of the obtained resin compositions, the physical properties were measured or evaluated by the following test methods. The results are shown in Table 2-1, Table 2-2, Table 3-1 or Table 3-2.

[0291] [Tensile Test] Using a hydraulic hot press molding machine set to 200°C, the resin composition was heated for 6 minutes and then molded under a pressure of 10 MPa for 2 minutes. The resin composition was then 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 at room temperature from molding, a tensile test was performed on the produced sheet in accordance with JIS K7162 under the following conditions. The tensile elongation was determined from this test. <Measurement Conditions> Test piece: JIS K7162-5A dumbbell, 5 mm (width) x 2 mm (thickness) x 75 mm (length), Tensile speed: 50 mm / min, Grip distance: 50 mm, Gauge distance: 20 mm, Temperature: 23°C

[0292] [Transmission Electron Microscope Observation] The prepared resin composition was heated for 6 minutes using a hydraulic heat press molding machine set to 200 ° C., and then molded for 2 minutes under a pressure of 10 MPa. The resin composition was then cooled for 2 minutes at 20 ° C. under a pressure of 10 MPa to produce a 3 mm thick sheet. The resulting molded body was cut into 0.5 mm square pieces and stained with ruthenic acid (RuO 4 ). The resulting pieces 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).

[0293] [Izod Impact Strength] Using a hydraulic hot press molding machine set to 200°C, the resin composition was heated for 6 minutes and then molded under a pressure of 10 MPa for 2 minutes. The resin composition was then cooled at 20°C under a pressure of 10 MPa for 2 minutes to produce a 3 mm thick sheet. After 72 hours at room temperature from molding, the Izod impact strength of the produced sheet was measured under the following conditions in accordance with ASTM D256. The fracture morphology after the test at a temperature of 23°C or -30°C was visually confirmed. <Test Conditions> Hammer capacity: 3.92 J; Idle angle: 149.0 degrees; Notch is machined; Temperature: 23°C or -30°C

[0294] [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 for Examples 1B to 20B and Comparative Examples 1B to 7B, and the Izod impact strength of Reference Example 1C was used for 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.

[0295] [Change in tensile elongation] The change in tensile elongation was calculated using the following formula: Change (%) = (Tensile elongation - Tensile elongation of Reference Example) × 100 / 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. It was determined that the larger the change (%), the better the tensile elongation.

[0296] [Balance between impact resistance and elongation] Resin compositions are required to have high impact resistance and high elongation. As an index showing this balance, 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, and the balance between impact resistance and elongation of the resin compositions was evaluated. Balance index (1) (10 ４ J / m%) = Izod impact strength (J / m) × tensile elongation (%) × 10 －４ Balance Indicator (2) (10 ４ ・J / m・%)=(((Izod impact strength (23℃) (J / m)) ２ + (Izod impact strength (-30℃) (J / m)) ２ ) / 2) １／２ × tensile elongation (%) × 10 －４

[0297] In the above formula for balance index (1), "Izod impact strength" is the Izod impact strength measured by the above method at a test temperature of 23°C. In the above formula for 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 balance index (1) and balance index (2), the better the balance between impact resistance and elongation of the resin composition or the like can be evaluated to be.

[0298] 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, demonstrating 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, confirming that the independent presence of the ethylene-propylene copolymer and terminally unsaturated polypropylene alone did not have the effect of improving impact resistance and elongation, and that the inclusion of the graft-type olefin polymer [R1] improved impact resistance and elongation. Furthermore, Comparative Examples 4B and 5B show that when the ethylene content of the main chain of the graft-type olefin polymer [R1] is as high as 100 mol%, the elongation is exhibited but the impact resistance is poor, whereas the resin compositions of the Examples achieve 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, whereas the resin compositions of the Examples achieve both impact resistance and elongation.

[0299] 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.

[0300]

[0301]

[0302]

[0303]

[0304] [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 Seisakusho Co., Ltd. in the blending ratios (parts by mass) listed in Table 4, and melt-kneaded for approximately 5 minutes at 200 ° C and 60 rpm 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 Examples 20A to 23A, Examples 25A to 27A, Comparative Examples 2A, 4A to 5A, and Comparative Examples 10A to 12A, respectively. The raw material propylene polymer (α1-2), propylene polymer (α1-3), and ethylene polymer (α2-2) were as follows. [Propylene-based polymer (α1-2)] Random polypropylene (MFR (230°C, 2.16 kg load, ASTM D1238): 7 g / 10 min, melting point: 140°C, propylene content: 95 mol%, ethylene content: 1 mol%, 1-butene content: 4 mol%) [Propylene-based polymer (α1-3)] Propylene-based polymer (α1-3) prepared according to the method for propylene-based polymer 1 described in the Examples section of JP-A No. 2024-116045 (MFR (230°C, 2.16 kg load, ASTM D1238): 6 g / 10 min) [Ethylene-based 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)

[0305] Measurement of Molded Product Properties The physical properties of the molded products of the prepared resin compositions were measured using the following methods. The results are shown in Table 4. [Bleaching 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. The resin composition was then cooled at 20°C under a pressure of 10 MPa for 2 minutes to produce a 0.5 mm thick sheet. After 7 days or more had passed at room temperature after molding, a No. 2 dumbbell shape as specified in JIS K6251 was produced from the sheet. The hue of the dumbbell before stretching (L value (before stretching)) and the hue after stretching the dumbbell 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: The smaller the ΔL value, the better the whitening resistance of the polymer composition. ΔL = L value (after stretching) - L value (before stretching).

[0306] [Tensile Test] Using a hydraulic hot press molding machine set to 200°C, the resin composition was heated for 6 minutes and then molded under a pressure of 10 MPa for 2 minutes. The resin composition was then cooled at 20°C under a pressure of 10 MPa for 2 minutes to produce a 2 mm thick sheet. 72 hours after molding, a tensile test was performed on the produced sheet at room temperature under the following conditions in accordance with JIS K7162. The elastic modulus and breaking stress were determined from this test. <Measurement Conditions> Test piece: JIS K7162-5A dumbbell 5 mm (width) x 2 mm (thickness) x 75 mm (length) Tensile speed: 50 mm / min Grip distance: 50 mm Gauge distance: 20 mm Temperature: 23°C

[0307] [High-Speed ​​Surface Impact Test] Using a hydraulic hot press molding machine set to 200°C, the resin composition was heated for 6 minutes and then molded under a pressure of 10 MPa for 2 minutes. The resin composition was then 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. The puncture point energy was determined from this test. <Measurement Conditions> Striker diameter: 20 mmΦ Support table diameter: 40 mmΦ Test speed: 4.4 m / s Temperature: -20°C

[0308] [Balance between impact resistance and stress] Resin compositions are required to have high impact resistance and high stress. As an index showing this balance, in Examples 1D to 7D and Comparative Examples 1D to 6D, the value of balance index (3) was calculated using the following formula to evaluate the balance between impact resistance and stress of the resin compositions. Balance index (3) [10 J MPa] = Puncture point energy (J) × Fracture stress (MPa) × 10 －１ The larger the balance index (3) value, the better the balance between impact resistance and stress can be evaluated.

[0309] [Balance of Whitening Resistance, Elastic Modulus, Impact Resistance, and Stress] Resin compositions are required to have high whitening resistance, high elastic modulus, high impact resistance, and high stress. As an index showing the balance of these properties, in Examples 1D to 7D and Comparative Examples 1D to 6D, the value of balance index (4) calculated by the following formula was calculated, and the balance of whitening resistance, elastic modulus, impact resistance, and stress of the resin compositions was evaluated. Balance index (4) [10 ３ ・J・MPa ２ ] = puncture point energy (J) × breaking 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.

[0310] 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.

[0311]

[0312] [Reference Example 1E, Examples 1E to 14E, and Comparative Examples 1E to 7E] Preparation of Resin Compositions The raw materials listed 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) listed in Tables 5-1 and 5-2, and melt-kneaded for approximately 5 minutes at 200 °C and 60 rpm to prepare resin compositions. The raw material olefin resins (β-19) to (β-26), (β'-2), and (β'-9) to (β'-13) were obtained in Examples 19A to 26A, Comparative Examples 2A to 5A, and Comparative Examples 10A to 11A, respectively. The raw material propylene polymer (α1-4) and ethylene polymer (α2-3) were as follows: [Propylene-based 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-based polymer (α2-3)] Ethylene-1-butene copolymer (MFR (190°C, 2.16 kg load) = 1.2 g / 10 min, density 885 kg / m ３ )

[0313] Measurement of Molded Product Properties The physical properties of the molded products of the prepared resin compositions were measured by the following methods. The results are shown in Tables 5-1 and 5-2. [Tensile Test] Using a hydraulic hot press molding machine set to 200°C, the resin composition was heated for 6 minutes and then molded for 2 minutes under a pressure of 10 MPa. The resin composition was then cooled for 2 minutes at 20°C under a pressure of 10 MPa to produce a sheet having a thickness of 2 mm. After 72 hours at room temperature after molding, a tensile test was performed on the produced sheet in accordance with JIS K7162 under the following conditions. The elastic modulus and tensile elongation were determined from this test. <Measurement Conditions> Test piece: JIS K7162-5A dumbbell 5 mm (width) x 2 mm (thickness) x 75 mm (length) Tensile speed: 50 mm / min Grip distance: 50 mm Gauge distance: 20 mm

[0314] [High-Speed ​​Surface Impact Test] Using a hydraulic hot press molding machine set to 200°C, the resin composition was heated for 6 minutes and then molded under a pressure of 10 MPa for 2 minutes. The resin composition was then 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. The puncture point energy was determined from this test. <Measurement Conditions> Striker diameter: 20 mmΦ Support table diameter: 40 mmΦ Test speed: 4.4 m / s Temperature: -20°C

[0315] [Change in tensile elongation] In Table 5-1, the change in tensile elongation was calculated using the following formula: Change (%) = (Tensile elongation - Tensile elongation of Reference Example 1E) x 100 / Tensile elongation of Reference Example 1E It was determined that the larger the change (%), the better the tensile elongation. [Change in tensile modulus] In Table 5-1, the change in tensile modulus was calculated using the following formula: Change (%) = (Tensile modulus - Tensile modulus of Reference Example 1E) x 100 / Tensile modulus of Reference Example 1E

[0316] [Rate of change in breaking 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) x 100 / breaking stress of Reference Example 1E It was determined that the larger the value of the rate of change (%), the better the breaking stress. [Rate of change in puncture point energy] In Table 5-1, the rate of change in puncture point energy was calculated using the following formula: Rate of change (%) = (puncture point energy - puncture point energy of Reference Example 1E) x 100 / puncture point energy of Reference Example 1E It was determined that the larger the value of the rate of change (%), the better the puncture point energy.

[0317] [Balance between impact resistance and stress] Resin compositions are required to have high impact resistance and high stress. As an index showing the balance between these, the value of the balance index (5) according to the following formula was calculated in Reference Example 1E, Examples 1E to 14E, and Comparative Examples 1E to 7E, and the balance between impact resistance and stress of the resin compositions was evaluated. Balance index (5) [10 ２ · J · MPa] = puncture point energy (J) × fracture stress (MPa) × 10 －２ The larger the value of the balance index (5), the better the balance between impact resistance and stress can be evaluated.

[0318] [Balance of elongation, flexibility, impact resistance, and stress] Resin compositions are 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 balance index (6) according to the following formula was calculated to evaluate the balance of flexibility, impact resistance, and stress of the resin compositions. Balance index (6) [% J] = Tensile elongation (%) × Puncture point energy (J) × Fracture stress (MPa) / Elastic modulus (MPa) The larger the value of balance index (6), the better the balance of elongation, flexibility, impact resistance, and stress can be evaluated.

[0319] 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.

[0320]

[0321]

[0322] [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 Seisakusho, Ltd. in the blending ratios (parts by mass) listed in Table 6, and melt-kneaded for approximately 5 minutes at 200°C and 60 rpm to prepare resin compositions. The raw material olefin resins (β-20) and (β-25) were obtained in Examples 20A and 25A, respectively. The raw material propylene polymer (α1-5) and ethylene polymer (α2-4) used 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 )

[0323] Measurement of Molded Product Properties The physical properties of the molded products of the prepared resin compositions were measured by the following methods. The results are shown in Table 6. [Izod Impact Strength] Using a hydraulic hot press molding machine set to 200°C, the resin composition was heated for 6 minutes and then molded for 2 minutes under a pressure of 10 MPa. The resin composition was then cooled for 2 minutes at 20°C under a pressure of 10 MPa to produce a 3 mm thick sheet. 72 hours after molding, the Izod impact strength of the produced sheet was measured four times in total when tested under the following conditions in accordance with ASTM D256. The fracture morphology after the four tests was also visually confirmed. <Test Conditions> Hammer capacity: 3.92 J; Idle angle: 149.0 degrees; Notch is machined; Temperature: -40°C

[0324] [Bending Test] Using a hydraulic hot press molding machine set to 200°C, the resin composition was heated for 6 minutes and then molded under a pressure of 10 MPa for 2 minutes. The resin composition was then 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, 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

[0325] [Tensile Test] Using a hydraulic hot press molding machine set to 200°C, the resin composition was heated for 6 minutes and then molded under a pressure of 10 MPa for 2 minutes. The resin composition was then cooled at 20°C under a pressure of 10 MPa for 2 minutes to produce a sheet having a thickness of 2 mm. 72 hours after molding, a tensile test was performed on the produced sheet at room temperature under the following conditions in accordance with JIS K7162. The elastic modulus and tensile elongation were determined from this test. <Measurement Conditions> Test piece: JIS K7162-5A dumbbell 5 mm (width) x 2 mm (thickness) x 75 mm (length) Tensile speed: 50 mm / min Grip distance: 50 mm Gauge distance: 20 mm

[0326] [Balance between impact resistance and elongation] Resin compositions are required to have high impact resistance and high elongation. As an index showing the balance between these, in Examples 1F to 4F and Comparative Examples 1F to 2F, the value of balance index (7) was calculated by the following formula, and the balance between impact resistance and elongation of the resin compositions was evaluated. 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.

[0327] [Balance of elongation, flexibility, impact resistance, and stress] A resin composition is required to have high elongation, high flexibility, high impact resistance, and high stress. As an index showing the balance of these properties, in Examples 1F to 4F and Comparative Examples 1F to 2F, the value of 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.

[0328] 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.

[0329]

Claims

1. An olefin resin (β) comprising a graft-type olefin polymer [R1] having a main chain and side chains, which 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 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 not constituting 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 olefin resin (β) according to claim 1, wherein the main chain of the graft-type olefin polymer [R1] is an ethylene-propylene copolymer, the content of structural units derived from ethylene in the ethylene-propylene copolymer is 70 to 99 mol %, and 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 claim 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 claim 2, 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 claim 2, wherein the melt flow rate (MFR) of the olefin-based resin (β) is 0.01 to 30 g / 10 min, as measured at 190°C under a load of 2.16 kg in accordance with ASTM D1238.

6. The olefin-based resin (β) according to claim 2, wherein the ethylene-propylene copolymer contains 75 to 85 mol% of structural units derived from ethylene, the ethylene-propylene copolymer contains 15 to 25 mol% of structural units derived from propylene, and the olefin-based resin (β) has an intrinsic viscosity [η] of 0.9 to 1.25 dL / g as measured in decalin at 135°C.

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

8. The olefin-based resin (β) according to claim 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 olefin-based resin (β) according to claim 7, wherein the ethylene / 1-butene copolymer contains 78 to 87 mol% of structural units derived from ethylene, and the ethylene / 1-butene copolymer contains 13 to 22 mol% of structural units derived from 1-butene.

10. The olefin-based resin (β) according to claim 7, 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 olefin resin (β) according to any one of claims 1 to 10, wherein 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 olefin polymer [R1] is 0 to 20 mol %, and the weight average molecular weight (Mw) of the polymer or copolymer constituting the side chains of the graft olefin polymer [R1], calculated as a polypropylene equivalent value by gel permeation chromatography (GPC), is in the range of 5,000 to 50,000.

12. 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) 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, 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; (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 represents a hydrogen atom, a hydrocarbon group, a silicon-containing group, or a heteroatom-containing group other than a silicon-containing group; R 1 ~R 4 Two adjacent groups among R may be bonded to each other to form a ring. 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, and 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, and 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. 13 and R 14 each independently represents an aryl group. 1 represents a carbon atom or a silicon atom. 1 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; 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. A resin composition (X) comprising the olefin resin (β) according to any one of claims 1 to 10, a propylene polymer (α1), and an ethylene polymer (α2).

14. The resin composition (X) according to claim 13, wherein the main chain of the graft-type olefin polymer [R1] in the olefin resin (β) is an ethylene-propylene copolymer, and 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 0.02 to 0.

23.

15. Resin composition (X) according to claim 13, wherein the main chain of the graft-type olefin polymer [R1] in the olefin resin (β) is an ethylene-propylene copolymer, and 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.

16. The resin composition (X) according to claim 13, wherein the main chain of the graft-type olefin polymer [R1] in the olefin resin (β) is an ethylene-propylene copolymer, 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 0.01 to 2.0 g / 10 min.

17. The resin composition (X) according to claim 13, wherein the main chain of the graft olefin polymer [R1] in the olefin resin (β) is an ethylene-1-butene copolymer, and 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 0.08 to 0.

20.

18. Resin composition (X) according to claim 13, wherein the main chain of the graft-type olefin polymer [R1] in the olefin resin (β) is an ethylene-1-butene copolymer, and 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.

19. Resin composition (X) according to claim 13, wherein the main chain of the graft-type olefin polymer [R1] in the olefin resin (β) is an ethylene-1-butene copolymer, 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.

20. The main chain of the graft-type olefin polymer [R1] in the olefin resin (β) is an ethylene-1-butene copolymer, and the density of the ethylene polymer (α2) measured at 25°C in accordance with ASTM D1505 is 850 to 900 kg / m ３ The resin composition (X) according to claim 13, 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, and the density of the ethylene polymer (α2) measured in accordance with ASTM D1505 at 25°C is 850 to 900 kg / m ３ The resin composition (X) according to claim 13, 22. The resin composition (X) according to claim 13, wherein the main chain of the graft 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 amount 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.

23. Resin composition (X) according to any one of claims 13 to 22, wherein 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 olefin polymer [R1] is 0 to 20 mol %, and the weight average molecular weight (Mw) of the polymer or copolymer constituting the side chains of the graft olefin polymer [R1], calculated as a polypropylene equivalent value by gel permeation chromatography (GPC), is in the range of 5,000 to 50,000.

24. The olefin-based resin (β) according to any one of claims 1 to 10, which is used as packaging for lithium-ion batteries.

25. The resin composition (X) according to any one of claims 13 to 22, which is used as a packaging material for lithium ion batteries.

26. A molded article comprising 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.

27. A packaging body for a lithium ion battery, comprising 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.

28. An electricity storage device comprising the packaging for a lithium ion battery according to claim 27.

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