Olefin resins, their manufacturing methods and applications

Abstract

The present invention addresses the problem of providing a novel olefin resin useful as a compatibilizer for a polypropylene resin and a polyethylene resin, a method for manufacturing the olefin resin, and an application for the olefin resin.　The olefin resin (β) includes a graft-type olefin polymer [R1] having: a main chain which is constituted from a propylene homopolymer or a copolymer of propylene and ethylene and in which the content of propylene-derived structural units is 76-100 mol%, and the content of ethylene-derived structural units is 0-24 mol%; and a side chain which is constituted from an ethylene homopolymer or a copolymer of ethylene and propylene and in which the content of ethylene-derived structural units is 80-100 mol%, and the content of propylene-derived structural units is 0-20 mol%.

Description

[Technical Field]

[0001] The present invention relates to an olefin resin, a method for producing the same, a resin composition containing the same, and a molded article of the resin composition. [Background technology]

[0002] Plastic products are used in a variety of fields, and among them, products made from polyolefin resin materials are widely used as various containers and other items, and their production volume is large. In recent years, the recycling of plastic products has been promoted, but there is a need for further recycling of used products and waste plastics made from polyolefin resins.

[0003] Polypropylene resins and polyethylene resins are commonly used as polyolefin-based resin materials. However, because they are incompatible, attempts to mix and recycle them result in uneven dispersion, degraded physical properties, and limited applications. Therefore, the development of methods to make polypropylene resins and polyethylene resins compatible or miscible has been desired.

[0004] Methods for making polypropylene resins and polyethylene resins compatible include using a crystalline block composite comprising i) a crystalline ethylene polymer, ii) a crystalline propylene polymer, and iii) a block copolymer having crystalline ethylene blocks and crystalline propylene blocks (see Patent Documents 1-4), using a plastomer which is an ethylene-α-olefin copolymer having a specific weight-average molecular weight, density, and degree of crystallinity (see Patent Document 5), and using a thermoplastic random copolymer with a specific melting point containing ethylene and propylene obtained using a specific catalyst (see Patent Document 6). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Special Publication No. 2016-537449 [Patent Document 2] Japanese Patent Publication No. 2019-116638 [Patent Document 3] Patent No. 5860043 [Patent Document 4] Patent No. 6783851 [Patent Document 5] Special Publication No. 6-511028 [Patent Document 6] Patent No. 5466986 [Overview of the project] [Problems that the invention aims to solve]

[0006] The present invention aims to provide a novel olefin resin useful as a compatibilizer between polypropylene resins and polyethylene resins, as well as a method for producing the same and its applications. Furthermore, the present invention aims to provide a resin composition and molded article containing a polypropylene resin and a polyethylene resin, with improved impact resistance. [Means for solving the problem]

[0007] In view of the above circumstances, the inventors conducted diligent research and found that an olefin resin containing a graft-type olefin polymer having a main chain containing a large amount of structural units derived from propylene and side chains containing a large amount of structural units derived from ethylene can solve the aforementioned problems, thus completing the present invention.

[0008] In other words, the present invention relates to the following matters. [1] A main chain composed of a propylene homopolymer or a copolymer of propylene and ethylene, wherein the content of structural units derived from propylene is 76-100 mol%, and the content of structural units derived from ethylene is 0-24 mol%, and Side chains composed of ethylene homopolymers or copolymers of ethylene and propylene, with a content of 80-100 mol% of structural units derived from ethylene and 0-20 mol% of structural units derived from propylene. An olefin resin (β) comprising a graft-type olefin polymer [R1] having the following properties.

[0009] [2] The olefin resin (β) according to [1], wherein the graft-type olefin polymer [R1] has a main chain having a content of 78 to 99 mol% of structural units derived from propylene and a content of 0 to 22 mol% of structural units derived from ethylene. [3] The olefin resin (β) according to [1] or [2], wherein the olefin resin (β) contains 10 to 93% by weight of structural units derived from propylene.

[0010] [4] An olefin resin (β) according to any one of [1] to [3], wherein the weight-average molecular weight of the polymer or copolymer constituting the main chain of the graft-type olefin polymer [R1], determined as a styrene equivalent by gel permeation chromatography (GPC), is in the range of 50,000 to 1,000,000. [5] An olefin resin (β) according to any one of [1] to [4], wherein the weight-average molecular weight of the polymer or copolymer constituting the side chain of the graft-type olefin polymer [R1], determined as a styrene equivalent by gel permeation chromatography (GPC), is in the range of 5,000 to 200,000. [6] An olefin resin (β) according to any one of [1] to [5], wherein the total weight-average molecular weight, which is the product of the weight-average molecular weight per side chain (determined as a styrene equivalent value from gel permeation chromatography (GPC)) and the number of side chains per main chain, is in the range of 15,000 to 500,000.

[0011] [7] The method for producing an olefin resin (β) according to any one of [1] to [6], which includes the following steps (A) and (B). Step (A): A step of polymerizing ethylene in the presence of an olefin polymerization catalyst containing a transition metal compound represented by the following general formula [A-1] to produce a terminal unsaturated ethylene polymer, or a step of copolymerizing ethylene and propylene in the presence of an olefin polymerization catalyst containing a transition metal compound represented by the following general formula [A-2] to produce a terminal unsaturated ethylene-propylene copolymer.

Chemical formula

[0012] [8] An olefin resin composition containing one or more propylene resins (α1) and ethylene resins (α2), and an olefin resin (β) according to any one of claims 1 to 6. [9] The propylene resin (α1) and the ethylene resin (α2) are contained in a mass ratio of 51:49 to 99:1. The olefin resin (β) is contained in a total of 100 parts by mass of the ethylene resin (α1) and the propylene resin (α2), The olefin resin composition according to [8], wherein the olefin resin (β) contains 80 to 98 mol% of structural units derived from ethylene in the side chains of the graft-type olefin polymer [R1] and 2 to 20 mol% of structural units derived from propylene.

[0013]

[10] The propylene resin (α1) and the ethylene resin (α2) are contained in a mass ratio of 49:51 to 1:99. The olefin resin (β) is contained in a total of 100 parts by mass of the propylene resin (α1) and the ethylene resin (α2), The olefin resin composition according to [8], wherein the content of structural units derived from ethylene contained in the side chains of the graft-type olefin polymer [R1] contained in the olefin resin (β) is 80 to 100 mol%.

[11] A molded article of an olefin resin composition as described in any of [8] to

[10] . [Effects of the Invention]

[0014] According to the present invention, it is possible to provide a novel olefin resin useful as a compatibilizer between polypropylene resins and polyethylene resins, and a method for producing the same. Furthermore, according to the present invention, it is possible to provide a resin composition containing a polypropylene resin and a polyethylene resin, having improved compatibility and impact resistance, and a molded article thereof. [Brief explanation of the drawing]

[0015] [Figure 1] Figure 1 is a transmission electron microscope image of the olefin resin composition obtained in Example 11. [Figure 2] Figure 2 shows a transmission electron microscope image of the olefin-based resin composition obtained in Comparative Example 12. [Figure 3] Figure 3 shows a transmission electron microscope image of the olefin-based resin composition obtained in Comparative Example 13. [Modes for carrying out the invention]

[0016] The present invention will be described in more detail below. <Olefin-based resin (β)> The olefin resin (β) of the present invention contains the graft-type olefin polymer [R1] as an essential component. The graft-type olefin polymer [R1] is a graft copolymer having a main chain made of a propylene homopolymer or a copolymer of propylene and ethylene, and side chains made of an ethylene homopolymer or a copolymer of ethylene and propylene.

[0017] In this invention, the terms "grafted (co)polymer" or "grafted polymer" refer to a polymer in which one or more side chains are bonded to the main chain. Since the graft-type olefin polymer [R1] has a structure in which a side chain, composed of an ethylene homopolymer or an ethylene-propylene copolymer, is chemically bonded to a main chain composed of a propylene homopolymer or a copolymer of propylene and ethylene, the olefin resin (β) containing the graft-type olefin polymer [R1] has high compatibility with both propylene-based polymers and ethylene-based polymers.

[0018] The main chain of the graft-type olefin polymer [R1] has a content of 76 to 100 mol% of structural units derived from propylene and a content of 0 to 24 mol% of structural units derived from ethylene, preferably 78 to 99 mol%, more preferably 78 to 97 mol%, even more preferably 78 to 95 mol%, and a content of 1 to 22 mol%, more preferably 3 to 22 mol%, and even more preferably 5 to 22 mol% of structural units derived from ethylene.

[0019] The side chains of the graft-type olefin polymer [R1] are composed of an ethylene homopolymer or a copolymer of ethylene and propylene, with a content of 80-100 mol% of structural units derived from ethylene and 0-20 mol% of structural units derived from propylene, preferably 85-100 mol% of structural units derived from ethylene and 0-15 mol% of structural units derived from propylene.

[0020] The main chain and side chains of the graft-type olefin polymer [R1] may contain structural units other than those derived from ethylene and propylene (other structural units), as long as they achieve the effects of the present invention. 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 of the main chain and side chains. Examples of structural units other than those derived from ethylene and propylene include structural units derived from α-olefins having 4 to 20 carbon atoms, cyclic olefins, etc., preferably α-olefins having 4 to 10 carbon atoms, and more preferably α-olefins having 4 to 8 carbon atoms.

[0021] The olefin resin (β) of the present invention contains a graft-type olefin polymer [R1], and when the total content of structural units derived from ethylene, structural units derived from propylene, and structural units other than those derived from ethylene and propylene is taken as 100% by weight, the structural units derived from propylene are preferably 10 to 93% by weight, more preferably 15 to 88% by weight, even more preferably 20 to 83% by weight, and particularly preferably 20 to 78% by weight. If the content of structural units derived from propylene is less than 10% by weight, compatibility with propylene-based resin (α1) may not be sufficient, and if it is more than 93% by weight, compatibility with ethylene-based resin (α2) may not be sufficient. In other words, when the content of structural units derived from propylene is within the above numerical range, the olefin-based resin (β) becomes a good compatibilizer for propylene-based resin (α1) and ethylene-based resin (α2).

[0022] The presence of graft-type olefin polymer [R1] in olefin resin (β) can be confirmed by combining the content ratio of the main chain portion (propylene homopolymer, or copolymer of propylene and ethylene) and the side chain portion (ethylene homopolymer, or copolymer of ethylene and propylene) in the olefin resin (β) with peak separation using GPC. For example, by performing peak separation from the molecular weight distribution curve measured using GPC, the composition ratio of each portion can be determined, and the formation of graft-type olefin polymer [R1] can be confirmed from there. In addition, it can be confirmed using various analytical methods, and the means of confirmation are not particularly limited.

[0023] The graft-type olefin polymer [R1] preferably has a weight-average molecular weight of the polymer or copolymer constituting the main chain, determined as a styrene equivalent by gel permeation chromatography (GPC), in the range of 50,000 to 1,000,000, more preferably in the range of 50,000 to 600,000.

[0024] The graft-type olefin polymer [R1] preferably has a weight-average molecular weight of the polymer or copolymer constituting the side chain, determined as a styrene equivalent by gel permeation chromatography (GPC), in the range of 5,000 to 200,000, more preferably in the range of 5,000 to 150,000.

[0025] Furthermore, it is desirable that the graft-type olefin polymer [R1] has a total weight-average molecular weight, which is the product of the weight-average molecular weight per side chain (determined as a styrene equivalent value by gel permeation chromatography (GPC)) and the number of side chains per main chain, preferably in the range of 15,000 to 500,000, and more preferably in the range of 15,000 to 300,000.

[0026] When one or more, preferably two or more, and more preferably all, of the weight-average molecular weight of the main chain, the weight-average molecular weight of the side chains, and the total weight-average molecular weight of the graft-type olefin polymer [R1] described above satisfies the above-mentioned preferred range, the olefin resin (β) containing it exhibits excellent compatibility with polyolefin materials such as waste plastics, and the molded article of the olefin resin composition containing it exhibits excellent impact resistance, which is therefore preferable.

[0027] <Method for producing olefin resin (β)> Olefin resin (β) is produced by a manufacturing method that includes, for example, steps (A) and (B) below.

[0028] Step (A): A step of polymerizing ethylene in the presence of an olefin polymerization catalyst containing a transition metal compound represented by the following general formula [A-1] to produce a terminally unsaturated ethylene polymer, or a step of copolymerizing ethylene and propylene in the presence of an olefin polymerization catalyst containing a transition metal compound represented by the following general formula [A-2] to produce a terminally unsaturated ethylene-propylene copolymer.

[0029] [ka]

[0030] (In general formula [A-1], M represents a transition metal atom of group 4 or group 5 of the periodic table.) m represents an integer between 1 and 4. R 1 This is the general formula C n' H 2n'+1 This represents hydrocarbon groups with 1 to 8 carbon atoms, where n' is an integer from 1 to 8. R 2 ~R 5 These may be identical or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring. R 6 ~R 8 is a hydrocarbon group, of which at least one is an aromatic hydrocarbon group, and when m is an integer of 2 or more, R between the structural units of formula [A-1] 2 ~R 8 Two of the groups indicated by may be linked together. n is a number that satisfies the valency of M, and X represents a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group, or tin-containing group. If n is an integer greater than or equal to 2, multiple X groups may be identical or different, and multiple groups represented by X may bond to each other to form a ring.

[0031] [ka]

[0032] (In general formula [A-2], M is a transition metal atom of group 4 of the periodic table, n is an integer from 1 to 4 selected such that the transition metal compound [A-2] is electrically neutral. X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand that can coordinate with a lone pair of electrons, wherein the anionic ligand is a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a conjugated diene derivative group, and if n is 2 or more, the multiple groups represented by X may be the same or different from each other, and may bond to each other to form a ring. Q is an atom in Group 14 of the periodic table, R 1 , R 2 , R 5 , R 6 , R 7 , R 8 , R 10 , R 11 , R 13 and R 14 Each of these is independently a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group. R 3 and R 4 Each of these is independently a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group. R 9 and R 12 This is a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group (however, R 9 It is not a substituent represented by the following general formula [A-2-1].

[0033] [ka]

[0034] In general formula [A-2-1], R 9a , R 9b , R 9c , R 9d and R 9e Each of these is independently a hydrogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group. * indicates a bond to the indenyl ring. R 1 ~R 6 Adjacent substituents may bond to each other to form a ring which may also have substituents. R 7 ~R 12 Adjacent substituents may bond to each other to form a ring which may also have substituents. R 13 and R 14 These elements may bond to each other to form a ring containing Q, and this ring may have substituents.

[0035] Step (B): A step of copolymerizing the terminally unsaturated ethylene polymer or terminally unsaturated ethylene-propylene copolymer produced in Step (A) with propylene and ethylene in the presence of an olefin polymerization catalyst containing a transition metal compound [B] of Group 4 of the periodic table that has a ligand having a dimethylsilylbisindenyl skeleton.

[0036] The following explains steps (A) and (B) in order. [Process (A)] Step (A) is a step to produce a terminally unsaturated ethylene polymer or a terminally unsaturated cyclic ethylene-propylene copolymer that will serve as a raw material for the side chains of the graft-type olefin polymer [R1]. Specifically, Step (A) is a step to produce a terminally unsaturated ethylene polymer (Step (A1)) that will serve as a raw material for the side chains of the graft-type olefin polymer [R1], or a step to produce a terminally unsaturated ethylene-propylene copolymer (Step (A2)) that will serve as a raw material for the side chains of the graft-type olefin polymer [R1].

[0037] ·Process (A1) Step (A1), which is a process for producing a terminally unsaturated ethylene polymer, is a process for producing a terminally unsaturated ethylene polymer by polymerizing ethylene in the presence of an olefin polymerization catalyst containing a transition metal compound represented by the general formula [A-1] (hereinafter also referred to as the transition metal compound (A-1)), which will be described later. The terminally unsaturated ethylene polymer produced in step (A1) includes an ethylene polymer having a vinyl group at one end.

[0038] [Transition metal compound (A-1)] The transition metal compound (A-1) used in step (A1) is a specific compound having a structure represented by the following general formula [A-1], and functions as a catalyst for olefin polymerization, and functions more preferably in the presence of the catalyst component (C) described later. A catalyst for olefin polymerization containing a transition metal compound (A-1) can polymerize ethylene to produce terminally unsaturated ethylene polymers.

[0039] The transition metal compound (A-1) according to the present invention is a transition metal compound represented by the following general formula [A-1].

[0040] [ka]

[0041] In general formula [A-1], N...M generally indicates coordination, but in the present invention, coordination may or may not occur. M represents a transition metal atom of Group 4 or Group 5 of the periodic table, specifically a transition metal atom such as titanium, zirconium, hafnium, vanadium, niobium, or tantalum, preferably a transition metal atom of Group 4 of the periodic table such as titanium, zirconium, or hafnium, and more preferably zirconium.

[0042] m represents an integer between 1 and 4, preferably 1 or 2, and particularly preferably 2. R 1 This is the general formula C n' H 2n'+1This represents hydrocarbon groups with 1 to 8 carbon atoms, where n' is an integer from 1 to 8. 1 These hydrocarbon groups are preferable because they allow for the synthesis of terminally unsaturated ethylene polymers within an appropriate molecular weight range (for example, a weight-average molecular weight of 5,000 to 200,000).

[0043] R 2 ~R 5 These may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring, and if m is 2 or more, R 2 ~R 5 Two of the groups shown may be linked together, and examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0044] Specifically, hydrocarbon groups include linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, and n-hexyl groups; linear or branched alkenyl groups having 2 to 30 carbon atoms, preferably 2 to 20, such as vinyl, allyl, and isopropenyl groups; linear or branched alkynyl groups having 2 to 30 carbon atoms, preferably 2 to 20, such as ethynyl and propargyl groups; cyclopropyl, cyclobutyl, and cyclopropyl groups. Examples include cyclic saturated hydrocarbon groups having 3 to 30 carbon atoms, preferably 3 to 20, such as cyclopentyl, cyclohexyl, and adamantyl groups; cyclic unsaturated hydrocarbon groups having 5 to 30 carbon atoms, such as cyclopentadienyl, indenyl, and fluorenyl groups; aryl groups having 6 to 30 carbon atoms, preferably 6 to 20, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, and anthracenyl groups; and alkyl-substituted aryl groups such as tolyl, isopropylphenyl, t-butylphenyl, dimethylphenyl, and di-t-butylphenyl groups.

[0045] The hydrocarbon group described above may have hydrogen atoms substituted with halogens, for example, halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20, such as trifluoromethyl, pentafluorophenyl, and chlorophenyl groups. Furthermore, the hydrocarbon group described above may be substituted with other hydrocarbon groups, for example, aryl-substituted alkyl groups such as benzyl and cumyl groups.

[0046] Furthermore, the above hydrocarbon groups include heterocyclic compound residues; oxygen-containing groups such as alkoxy groups, allyloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxyl groups, peroxy groups, and carboxylic acid anhydride groups; nitrogen-containing groups such as amino groups, imino groups, amide groups, imide groups, hydrazino groups, hydrazono groups, nitro groups, nitroso groups, cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, and ammonium salts of amino groups; and boranediyl groups, borantriyl groups, and diboranyl groups. It may also have boron-containing groups; sulfur-containing groups such as mercapto groups, thioester groups, dithioester groups, alkylthio groups, arylthio groups, thioacyl groups, thioether groups, thiocyanate groups, isothianeate groups, sulfone ester groups, sulfonamide groups, thiocarboxyl groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, sulfenyl groups, sulfenyl groups, etc.; phosphorus-containing groups such as phosphine groups, phosphoryl groups, thiophosphoryl groups, phosphat groups, silicon-containing groups, germanium-containing groups, or tin-containing groups.

[0047] Of these, particularly preferred are linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, and n-hexyl groups; aryl groups having 6 to 30 carbon atoms, preferably 6 to 20, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, and anthracenyl groups; and substituted aryl groups in which these aryl groups are substituted with 1 to 5 substituents, such as halogen atoms, alkyl or alkoxy groups having 1 to 30 carbon atoms, preferably 1 to 20, or aryl or aryloxy groups having 6 to 30 carbon atoms.

[0048] Examples of oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, and phosphorus-containing groups are the same as those exemplified above. Examples of heterocyclic compound residues include nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine; oxygen-containing compounds such as furan and pyran; sulfur-containing compounds such as thiophene; and groups obtained by further substituting these heterocyclic compound residues with substituents such as alkyl groups and alkoxy groups having 1 to 30, preferably 1 to 20, carbon atoms.

[0049] Examples of silicon-containing groups include silyl groups, siloxy groups, hydrocarbon-substituted silyl groups, and hydrocarbon-substituted siloxy groups. Specifically, examples include methylsilyl groups, dimethylsilyl groups, trimethylsilyl groups, ethylsilyl groups, diethylsilyl groups, triethylsilyl groups, diphenylmethylsilyl groups, triphenylsilyl groups, dimethylphenylsilyl groups, dimethyl-t-butylsilyl groups, and dimethyl(pentafluorophenyl)silyl groups. Among these, methylsilyl groups, dimethylsilyl groups, trimethylsilyl groups, ethylsilyl groups, diethylsilyl groups, triethylsilyl groups, dimethylphenylsilyl groups, and triphenylsilyl groups are preferred. Trimethylsilyl groups, triethylsilyl groups, triphenylsilyl groups, and dimethylphenylsilyl groups are particularly preferred. Specific examples of hydrocarbon-substituted siloxy groups include trimethylsiloxy groups. Examples of germanium-containing groups and tin-containing groups include those obtained by substituting the silicon in the silicon-containing group with germanium and tin, respectively.

[0050] Next, R explained above 2 ~R 5 Let's explain the examples in more detail. Specific examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, and t-butoxy groups.

[0051] Examples of alkylthio groups include methylthio groups and ethylthio groups. Examples of allyloxy groups include phenoxy groups, 2,6-dimethylphenoxy groups, and 2,4,6-trimethylphenoxy groups. Examples of arylthio groups include phenylthio groups, methylphenylthio groups, and naphthylthio groups.

[0052] Examples of acyl groups include formyl, acetyl, benzoyl, p-chlorobenzoyl, and p-methoxybenzoyl groups. Examples of ester groups include acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl, and p-chlorophenoxycarbonyl groups.

[0053] Examples of thioester groups include acetylthio, benzoylthio, methylthiocarbonyl, and phenylthiocarbonyl groups. Examples of amide groups include acetamide, N-methylacetamide, and N-methylbenzamide groups. Examples of imide groups include acetimide and benzimide groups. Examples of amino groups include dimethylamino, ethylmethylamino, and diphenylamino groups.

[0054] Examples of imino groups include methylimino group, ethylimino group, propylimino group, butylimino group, and phenylimino group. Examples of sulfone ester groups include methyl sulfonate, ethyl sulfonate, and phenyl sulfonate. Examples of sulfonamide groups include phenylsulfonamide group, N-methylsulfonamide group, and N-methyl-p-toluenesulfonamide group.

[0055] R 2 ~R 5 Two or more of these groups, preferably two or more adjacent groups, may be linked to each other to form an antimicrobial ring, an aromatic ring, or a hydrocarbon ring containing heteroatoms such as nitrogen atoms, and these rings may further have substituents.

[0056] R 6 ~R 8 These are hydrocarbon groups, of which at least one is an aromatic hydrocarbon group. Examples of aromatic hydrocarbon groups include aryl groups and alkyl-substituted aryl groups. Specific examples of the hydrocarbon group include linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, and n-hexyl group; linear or branched alkenyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as vinyl group, allyl group, and isopropenyl group; linear or branched alkynyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as ethynyl group and propargyl group; cyclic saturated hydrocarbon groups having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and adamantyl group; cyclic unsaturated hydrocarbon groups having 5 to 30 carbon atoms, such as cyclopentadienyl group, indenyl group, and fluorenyl group; aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as phenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group, and anthracenyl group; alkyl-substituted aryl groups such as tolyl group, isopropylphenyl group, t-butylphenyl group, dimethylphenyl group, and di-t-butylphenyl group, etc.

[0057] In the above hydrocarbon group, a hydrogen atom may be substituted with a halogen. For example, halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as trifluoromethyl group, pentafluorophenyl group, and chlorophenyl group, etc. are included. R 6 ~R 8 At least one of them is an aromatic hydrocarbon group such as an aryl group or an alkyl-substituted aryl group. R 6 ~R 8 Since at least one of them is an aromatic hydrocarbon group, the polymerizability of ethylene in step (A1) is improved.

[0058] When m is an integer of 2 or more, two of the groups represented by R 2 ~R 8 may be linked to each other. Further, when m is an integer of 2 or more, R 1 with each other, R 2 with each other, R3 each other, R 4 each other, R 5 each other, R 6 each other, R 7 each other, R 8 The "each other" may be the same or different from each other.

[0059] n is a number that satisfies the valence of M, specifically an integer of 0 to 5, preferably 1 to 4, more preferably 1 to 3. X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. When n is 2 or more, they may be the same or different from each other.

[0060] Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Examples of the hydrocarbon group include the same as those exemplified for the above R 2 ~R 5 Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, nonyl group, dodecyl group, icosyl group; cycloalkyl groups having 3 to 30 carbon atoms such as cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group; alkenyl groups such as vinyl group, propenyl group, cyclohexenyl group; arylalkyl groups such as benzyl group, phenylethyl group, phenylpropyl group; aryl groups such as phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group, anthryl group, phenanthryl group, etc. are included, but not limited thereto. These hydrocarbon groups also include halogenated hydrocarbons, specifically groups in which at least one hydrogen of a hydrocarbon group having 1 to 20 carbon atoms is substituted with a halogen. Among these, those having 1 to 20 carbon atoms are preferred.

[0061] Examples of the heterocyclic compound residue include the same as those exemplified for the above R 2~R 5 Examples similar to those exemplified earlier can be given.

[0062] As for oxygen-containing groups, the above R 2 ~R 5 Examples similar to those exemplified above include, but are not limited to, hydroxyl groups; alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups; aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy groups; arylalkoxy groups such as phenylmethoxy and phenylethoxy groups; acetoxy groups; and carbonyl groups.

[0063] As for the sulfur-containing group, the above R 2 ~R 5 Examples similar to those exemplified above include, specifically, sulfonate groups such as methyl sulfonate, trifluoromethanesulfonate, phenyl sulfonate, benzyl sulfonate, p-toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, and pentafluorobenzenesulfonate; sulfinate groups such as methyl sulfinate, phenyl sulfinate, benzyl sulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, and pentafluorobenzenesulfinate; alkylthio groups; and arylthio groups, but are not limited to these.

[0064] Specifically, the nitrogen-containing group is the aforementioned R 2 ~R 5 Examples similar to those exemplified above include, but are not limited to, amino groups; alkylamino groups such as methylamino group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, and dicyclohexylamino group; arylamino groups or alkylarylamino groups such as phenylamino group, diphenylamino group, ditolylamino group, dinaphthylamino group, and methylphenylamino group.

[0065] Specific examples of boron-containing groups include BR4 (where R represents hydrogen, an alkyl group, an optionally substituted aryl group, a halogen atom, etc.). Specific examples of phosphorus-containing groups include, but are not limited to, trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine; triarylphosphine groups such as triphenylphosphine and tritlylphosphine; phosphite groups such as methylphosphine, ethylphosphine, and phenylphosphine; phosphonic acid groups; and phosphinic acid groups.

[0066] Specifically, the silicon-containing group is the aforementioned R 2 ~R 5 Examples similar to those exemplified above include, specifically, hydrocarbon-substituted silyl groups such as phenylsilyl group, diphenylsilyl group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, methyldiphenylsilyl group, tritrilsilyl group, and trinaphthylsilyl group; hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether group; silicon-substituted alkyl groups such as trimethylsilylmethyl group; and silicon-substituted aryl groups such as trimethylsilylphenyl group.

[0067] Specifically, the germanium-containing group is the aforementioned R 2 ~R 5 Examples similar to those exemplified above include, specifically, groups in which the silicon in the silicon-containing group is replaced with germanium. Specifically, as a tin-containing group, the R 2 ~R 5 Examples similar to those exemplified above include, and more specifically, groups in which the silicon in the silicon-containing group is replaced with tin.

[0068] Examples of halogen-containing groups include, but are not limited to, fluorine-containing groups such as PF6 and BF4, chlorine-containing groups such as ClO4 and SbCl6, and iodine-containing groups such as IO4. Examples of aluminum-containing groups include, but are not limited to, AlR4 (where R represents hydrogen, an alkyl group, an optionally substituted aryl group, a halogen atom, etc.).

[0069] Furthermore, if n is 2 or greater, the multiple groups represented by X may be the same or different from each other, and the multiple groups represented by X may be bonded to each other to form a ring. As described above, the transition metal compound (A-1) represented by the general formula [A-1] can be used alone or in combination of two or more types. Such transition metal compounds (A-1) are preferred in terms of the proportion of terminal vinyl groups and the polymerizability of ethylene.

[0070] [Polymerization catalyst] The catalyst for olefin polymerization used in step (A1) is not particularly limited as long as it contains the transition metal compound (A-1) described above, but it is preferable that in addition to the transition metal compound (A-1), it contains catalyst component (C) selected from (C1) organometallic compounds, (C2) organoaluminum oxy compounds, and (C3) compounds that react with the transition metal compound (A-1) to form ion pairs. Details of catalyst component (C) will be described later.

[0071] [Process (A1)] Step (A1) is a step to produce a terminally unsaturated ethylene polymer by polymerizing ethylene in the presence of an olefin polymerization catalyst containing the transition metal compound (A-1) described above, and is preferably carried out in solution polymerization. The polymerization conditions are not particularly limited and can be those of a solution polymerization process used to produce olefin polymers, but it is preferable to use an aliphatic hydrocarbon or aromatic hydrocarbon as the polymerization solvent and polymerize ethylene in the presence of an olefin polymerization catalyst containing the transition metal compound (A-1) described above to obtain a polymerization reaction solution.

[0072] Examples of polymerization solvents for step (A1) include aliphatic hydrocarbons and aromatic hydrocarbons. Specifically, these 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 can be used individually or in combination of two or more. Furthermore, the polymerization solvent for step (A1) may be the same as or different from the polymerization solvent for step (B), which will be described later.

[0073] The polymerization temperature in step (A1) is preferably in the range of 15°C to 200°C, and more preferably in the range of 20°C to 150°C. The polymerization pressure in step (A1) is usually atmospheric pressure to 10 MPa gauge pressure, preferably atmospheric pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in batch, semi-continuous, or continuous manner.

[0074] The reaction time in step (A1) (or average residence time if polymerization is carried out by a continuous method) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 5 minutes to 3 hours. The molecular weight of the terminally unsaturated ethylene polymer obtained in step (A1) can be adjusted by introducing hydrogen into the polymerization system or by changing the polymerization temperature. It can also be adjusted by using catalyst component (C) described later, such as triisobutylaluminum, methylaluminoxane, or diethylzinc. When hydrogen is added, the appropriate amount is about 0.001 to 100 NL per kg of olefin. To increase the content of terminal vinyl groups, it is preferable to carry out the process under hydrogen-free conditions.

[0075] ·Process (A2) Step (A2), which is a process for producing a terminally unsaturated ethylene-propylene copolymer, is a process for producing a terminally unsaturated ethylene-propylene copolymer by copolymerizing ethylene and propylene in the presence of an olefin polymerization catalyst (hereinafter also referred to as the transition metal compound (A-2)) containing a transition metal compound represented by the general formula [A-2] described later. The terminally unsaturated ethylene-propylene copolymer produced in step (A2) includes an ethylene-propylene copolymer having a vinyl group at one end.

[0076] [Transition metal compound (A-2)] The transition metal compound (A-2) used in step (A2) is a specific compound having a structure represented by the following general formula [A-2], and functions as a catalyst for olefin polymerization, and functions more preferably in the presence of the catalyst component (C) described later. A catalyst for olefin polymerization containing a transition metal compound (A-2) can copolymerize ethylene and propylene to produce a terminally unsaturated ethylene-propylene copolymer.

[0077] The transition metal compound (A-2) according to the present invention is a transition metal compound represented by the following general formula [A-2].

[0078] [ka]

[0079] In general formula [A-2], M is a transition metal atom of group 4 of the periodic table, preferably a zirconium atom or a hafnium atom, and more preferably a zirconium atom. n is an integer from 1 to 4, preferably 1 or 2, selected such that the transition metal compound (A-2) is electrically neutral.

[0080] X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand that can coordinate with a lone pair of electrons, wherein the anionic ligand is a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a conjugated diene derivative group. Preferably, X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group. If n is 2 or greater, the multiple X elements may be identical or different from each other, and they may be joined together to form a ring. Furthermore, if there are multiple such rings, these rings may be identical or different from each other.

[0081] Examples of the halogen atom include fluorine, chlorine, bromine, and iodine, with chlorine or bromine being preferred.

[0082] Examples of the hydrocarbon group include: Linear or branched alkyl groups such as methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl group (butan-2-yl group), tert-butyl group (2-methylpropane-2-yl group), iso-butyl group (2-methylpropyl group), pentan-2-yl group, 2-methylbutyl group, iso-pentyl group (3-methylbutyl group), neopentyl group (2,2-dimethylpropyl group), siamyl group (1,2-dimethylpropyl group), iso-hexyl group (4-methylpentyl group), 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group (2,3-dimethylbuta-2-yl group), and 4,4-dimethylpentyl group; Vinyl group, allyl group, propenyl group (propa-1-en-1-yl group), iso-propenyl group (propa-1-en-2-yl group), allenyl group (propa-1,2-dien-1-yl group), buta-3-en-1-yl group, clotyl group (buta-2-en-1-yl group), buta-3-en-2-yl group, metharyl group (2-methylallyl group), buta-1,3-dienyl group, pen Linear or branched alkenyl groups or unsaturated double bond-containing groups such as ta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl group (3-methylbuta-3-en-1-yl group), 2-methylbuta-3-en-1-yl group, penta-4-en-2-yl group, and prenyl group (3-methylbuta-2-en-1-yl group); Linear or branched alkynyl groups or unsaturated triple bond-containing groups such as ethynyl groups, propa-2-in-1-yl groups, and propargyl groups (propa-1-in-1-yl groups); Aromatic linear or branched alkyl groups and unsaturated double bond-containing groups such as benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group (4-iso-propylbenzyl group), 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, and benzhydryl group (diphenylmethyl group); Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cycloheptatrienyl group, norbornyl group, norborneyl group, 1-adamantyl group, 2-adamantyl group, and other cyclic saturated hydrocarbon groups; Aromatic substituents include phenyl group, tolyl group (methylphenyl group), xylyl group (dimethylphenyl group), mesityl group (2,4,6-trimethylphenyl group), cumenyl group (iso-propylphenyl group), juryl group (2,3,5,6-tetramethylphenyl group), 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group, and ferrocenyl group.

[0083] Among the hydrocarbon groups mentioned above, methyl, iso-butyl, neopentyl, siamyl, benzyl, phenyl, tolyl, xylyl, mesityl, and cumenyl groups are preferred.

[0084] Examples of the halogen-containing groups include fluoromethyl group, trifluoromethyl group, trichloromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, and hexachloroantimonate anion.

[0085] Among the halogen-containing groups, the pentafluorophenyl group is preferred. Examples of the silicon-containing groups include trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, diphenylmethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiphenylsilyl group, triphenylsilyl group, tris(trimethylsilyl)silyl group, and trimethylsilylmethyl group. Among the silicon-containing groups mentioned above, the trimethylsilylmethyl group is preferred.

[0086] Examples of the oxygen-containing groups include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, allyloxy group, n-butoxy group, sec-butoxy group, iso-butoxy group, tert-butoxy group, benzyloxy group, methoxymethoxy group, phenoxy group, 2,6-dimethylphenoxy group, 2,6-di-iso-propylphenoxy group, 2,6-di-tert-butylphenoxy group, 2,4,6-trimethylphenoxy group, 2,4,6-tri-iso-propylphenoxy group, acetoxy group, pivaloyloxy group, benzoyloxy group, trifluoroacetoxy group, perchlorate anion, and periodate anion. Among the oxygen-containing groups, methoxy groups, ethoxy groups, iso-propoxy groups, and tert-butoxy groups are preferred.

[0087] Examples of the aforementioned sulfur-containing groups include mesyl group (methanesulfonyl group), phenylsulfonyl group, tosyl group (p-toluenesulfonyl group), trifuryl group (trifluoromethanesulfonyl group), nonafuryl group (nonafluorobutanesulfonyl group), mesylate group (methanesulfonate group), tosylate group (p-toluenesulfonate group), triflate group (trifluoromethanesulfonate group), and nonaflate group (nonafluorobutanesulfonate group). Among the aforementioned sulfur-containing groups, the triflate group (trifluoromethanesulfonate group) is preferred.

[0088] Examples of the nitrogen-containing groups include amino groups, cyano groups, methylamino groups, dimethylamino groups, ethylamino groups, diethylamino groups, allylamino groups, diallylamino groups, benzylamino groups, dibenzylamino groups, pyrrolidinyl groups, piperidinyl groups, morpholyl groups, pyrrolyl groups, and bistrifurylimide groups. Among the nitrogen-containing groups, dimethylamino group, diethylamino group, pyrrolidinyl group, pyrrolyl group, and bistrifurylimide group are preferred.

[0089] Examples of the phosphorus-containing group include the hexafluorophosphate anion. Examples of the boron-containing groups include tetrafluoroborate anion, tetrakis(pentafluorophenyl)borate anion, (methyl)(tris(pentafluorophenyl))borate anion, (benzyl)(tris(pentafluorophenyl))borate anion, tetrakis((3,5-bistrifluoromethyl)phenyl)borate anion, and groups represented by BR4 (where R independently represents hydrogen, an alkyl group, an optionally substituted aryl group, or a halogen atom).

[0090] Examples of the aforementioned aluminum-containing group are: [ka] (M represents M in the general formula [A-2] above.) Examples of groups that can form a molecule include AlR4 (where R represents hydrogen, an alkyl group, an optionally substituted aryl group, or a halogen atom, etc.).

[0091] Examples of the aforementioned conjugated diene derivative groups include metallocyclopentene groups such as 1,3-butadienyl group, isoprenyl group (2-methyl-1,3-butadienyl group), piperilenyl group (1,3-pentadienyl group), 2,4-hexadienyl group, 1,4-diphenyl-1,3-pentadienyl group, and cyclopentadienyl group.

[0092] Examples of neutral ligands that can coordinate with a lone pair of electrons include ethers such as diethyl ether, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane; amines such as triethylamine and diethylamine; heterocyclic compounds such as pyridine, picoline, lutidine, oxazoline, oxazole, thiazole, imidazole, and thiophene; and organophosphorus compounds such as triphenylphosphine, tricyclohexylphosphine, and tri-tert-butylphosphine.

[0093] In the general formula [A-2] above, Q is an atom of Group 14 of the periodic table, such as a carbon atom, a silicon atom, a germanium atom, or a tin atom, preferably a carbon atom or a silicon atom, and more preferably a silicon atom.

[0094] In the above general formula [A-2], R 1 , R 2 , R 5 , R 6 , R 7 , R 8 , R 10 , R 11 , R 13 and R 14 Each of these is independently a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group. R 3 and R 4 Each of these is independently a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group. R 9 and R 12 This is a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group (however, R 9 It is not a substituent represented by the following general formula [A-2-1].

[0095] [ka] In general formula [A-2-1], R 9a , R 9b , R 9c , R 9d and R 9e Each of these is independently a hydrogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group. * indicates a bond to the indenyl ring.

[0096] R 1 ~R 14Examples of hydrocarbon groups having 1 to 40 carbon atoms include hydrocarbon groups having 1 to 20 carbon atoms, and more specifically, specific examples of the hydrocarbon groups listed as examples of X above can be cited.

[0097] The C1-C40 hydrocarbon group is preferably a C1-C20 hydrocarbon group (excluding aromatic hydrocarbon groups) or a C6-C40 aromatic hydrocarbon group. The C1-C20 hydrocarbon group is preferably an aliphatic or alicyclic hydrocarbon group. The C1-C20 hydrocarbon group also includes substituents having an aromatic structure, such as arylalkyl groups.

[0098] Examples of the hydrocarbon group having 1 to 40 carbon atoms are, Methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decanyl group, 1-undecanyl group, 1-dodecanyl group, 1-eicosanyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, pentan-2-yl group, 2-methylbutyl group, iso-pentyl group, neopentyl group, tert-pentyl group (1,1-dimethylpropyl group), siamyl group, pentan-3-yl group, 2-methylpentyl group, 3-methylpentyl group, iso-hexyl group, 1,1-dimethylbutyl group (2-methylpentan-2-yl group), 3-methylpentane Linear or branched alkyl groups having 1 to 40 carbon atoms, such as -2-yl group, 4-methylpentan-2-yl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group, 3-methylpentan-3-yl group, 3,3-dimethylbuta-2-yl group, hexane-3-yl group, 2-methylpentan-3-yl group, heptane-4-yl group, 2,4-dimethylpentan-2-yl group, 3-ethylpentan-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptan-4-yl group, 2,3,3-trimethylbutan-2-yl group, and 2,4,4-trimethylpentan-2-yl group;

[0099] Vinyl group, allyl group, propenyl group, iso-propenyl group, allenyl group, buta-3-en-1-yl group, clotyl group, buta-3-en-2-yl group, methallyl group, buta-1,3-dienyl group, penta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl group, 2-methylbuta-3-en-1-yl group, penta-4-en-2-yl group, prenyl group, 2-methylbuta-2-en-1- Iyl group, penta-3-en-2-yl group, 2-methyl-buta-3-en-2-yl group, penta-1-en-3-yl group, penta-2,4-dien-1-yl group, penta-1,3-dien-1-yl group, penta-1,4-dien-3-yl group, iso-prenyl group (2-methyl-buta-1,3-dien-1-yl group), penta-2,4-dien-2-yl group, hexa-5-en-1-yl group, hexa-4-en-1-yl group, hexa-3-en- 1-yl group, hexa-2-en-1-yl group, 4-methyl-penta-4-en-1-yl group, 3-methyl-penta-4-en-1-yl group, 2-methyl-penta-4-en-1-yl group, hexa-5-en-2-yl group, 4-methyl-penta-3-en-1-yl group, 3-methyl-penta-3-en-1-yl group, 2,3-dimethyl-buta-2-en-1-yl group, 2-methylpenta-4-en-2-yl group, 3-ethylpenta-1-en-3 -yl group, hexa-3,5-dien-1-yl group, hexa-2,4-dien-1-yl group, 4-methylpenta-1,3-dien-1-yl group, 2,3-dimethylbuta-1,3-dien-1-yl group, hexa-1,3,5-trien-1-yl group, 2-(cyclopentadienyl)propan-2-yl group, 2-(cyclopentadienyl)ethyl group, etc., linear or branched alkenyl groups or unsaturated double bond-containing groups with 2 to 40 carbon atoms;

[0100] Ethynyl group, propa-2-in-1-yl group, propargyl group, buta-1-in-1-yl group, buta-2-in-1-yl group, buta-3-in-1-yl group, penta-1-in-1-yl group, penta-2-in-1-yl group, penta-3-in-1-yl group, penta-4-in-1-yl group, 3-methylbuta-1-in-1-yl group, penta-3-in-2-yl group, 2-methylbuta-3-yl Linear or branched alkynyl groups or unsaturated triple bond-containing groups with 2 to 40 carbon atoms, such as 1-yl group, penta-4-in-2-yl group, hexa-1-in-1-yl group, 3,3-dimethylbuta-1-in-1-yl group, 2-methylpenta-3-in-2-yl group, 2,2-dimethylbuta-3-in-1-yl group, hexa-4-in-1-yl group, and hexa-5-in-1-yl group;

[0101] Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cumyl group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl group, cumyl group (2-phenylpropan-2-yl group), 2-(4-methylphenyl)propan-2-yl group, 2-(3,5-dimethylphenyl)propan-2-yl group, 2-(4-tert-butylphenyl)propan-2-yl group, 2-(3,5-di-tert-butylphenyl)propan-2-yl group, 3-phenylpentan-3-yl group, 4-phenylhepta-1, 6-dien-4-yl group, 1,2,3-triphenylpropane-2-yl group, 1,1-diphenylethyl group, 1,1-diphenylpropyl group, 1,1-diphenyl-buta-3-en-1-yl group, 1,1,2-triphenylethyl group, trityl group (triphenylmethyl group), tri-(4-methylphenyl)methyl group, 2-phenylethyl group, styryl group (2-phenylvinyl group), 2-(2-methylphenyl)ethyl group, 2-(4-methylphenyl)ethyl group, 2-(2,4,6-trimethylphenyl)ethyl group, 2-(3,5-dimethylphenyl)ethyl group, 2-(2,4,6-tri-iso-propylphenyl)ethyl group, 2-(4-tert-butylphenyl)ethyl group, 2-(3,5-di-tert-butylphenyl)ethyl group, 2-methyl-1-phenylpropane-2-yl group, 3-phenylpropyl group, cinnamyl group (3-phenylallyl group), neophyll group (2-methyl-2-phenylpropyl group), 3-methyl-3-phenylbutyl group, 2-methyl-4-phenylbutan-2-yl group, cyclopentadienyldiphenylmethyl group, 2-(1-indenyl)propane-2-yl group, (1-indenyl)diphenylmethyl group, 2-(1-indenyl)ethyl group, 2-(tetrahydro-1-indacenyl)propane-2-yl group, (tetrahydro-1-indacenyl) Aromatic linear or branched alkyl groups and unsaturated double bond-containing groups having 7 to 40 carbon atoms, such as diphenylmethyl group, 2-(tetrahydro-1-indacenyl)ethyl group, 2-(1-benzoindenyl)propan-2-yl group, (1-benzoindenyl)diphenylmethyl group, 2-(1-benzoindenyl)ethyl group, 2-(9-fluorenyl)propan-2-yl group, (9-fluorenyl)diphenylmethyl group, 2-(9-fluorenyl)ethyl group, 2-(1-azlenyl)propan-2-yl group, (1-azlenyl)diphenylmethyl group, and 2-(1-azlenyl)ethyl group;

[0102] Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, dimethylcyclopentadienyl group, n-butylcyclopentadienyl group, n-butyl-methylcyclopentadienyl group, tetramethylcyclopentadienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, cyclohexadienyl group, 1-methylcyclohexyl Syl group, 1-allylcyclohexyl group, 1-benzylcyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, cyclooctatrienyl group, 1-methylcyclooctyl group, 1-allylcyclooctyl group, 1-benzylcyclooctyl group, 4-cyclohexyl- tert-butyl group, norbornyl group, norbornenyl group, norbornadienyl group, 2-methylbicyclo[2.2.1]heptan-2-yl group, 7-methylbicyclo[2.2.1]heptan-7-yl group, bicyclo[2.2.2]octane-1-yl group, bicyclo[2.2.2]octane-2-yl group, 1-adamantyl group, 2-adamantyl group, 1-(2-methyladamantyl), 1-(3-methyladamantyl), 1-(4-methyladamantyl), 1 -(2-phenyladamantyl), 1-(3-phenyladamantyl), 1-(4-phenyladamantyl), 1-(3,5-dimethyladamantyl), 1-(3,5,7-trimethyladamantyl), 1-(3,5,7-triphenyladamantyl), pentarenyl group, indenyl group, fluorenyl group, indacenyl group, tetrahydroindacenyl group, benzoindenyl group, azurenyl group, and other cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms;

[0103] Examples include aromatic substituents with 6 to 40 carbon atoms, such as phenyl, tolyl, xylyl, mesityl, cumenyl, juryl, 2,6-di-iso-propylphenyl, 2,4,6-tri-iso-propylphenyl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl, allylphenyl, (buta-3-en-1-yl)phenyl, (buta-2-en-1-yl)phenyl, methallylphenyl, prenylphenyl, 4-adamantylphenyl, 3,5-diadamantylphenyl, naphthyl, biphenyl, terphenyl, binaphthyl, acenaphthalenyl, phenanthryl, anthracenyl, pyrenyl, and ferrocenyl groups.

[0104] Among the linear or branched alkyl groups having 1 to 40 carbon atoms, the following are particularly important: methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, iso-pentyl group, neopentyl group, tert-pentyl group, pentan-3-yl group, iso-hexyl group, 1,1-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group, 3-methylpentan-3-yl group, heptane-4 -yl group, 2,4-dimethylpentan-2-yl group, 3-ethylpentan-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptan-4-yl group, 2,4,4-trimethylpentan-2-yl group, etc. are preferred, and methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, iso-propyl group, tert-butyl group, neopentyl group, 2,4-dimethylpentan-2-yl group, 2,4,4-trimethylpentan-2-yl group are more preferred.

[0105] Among the linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 40 carbon atoms, vinyl groups, allyl groups, buta-3-en-1-yl groups, clotyl groups, methallyl groups, penta-4-en-1-yl groups, prenyl groups, penta-1,4-dien-3-yl groups, hexa-5-en-1-yl groups, 2-methylpenta-4-en-2-yl groups, 2-(cyclopentadienyl)propane-2-yl groups, and 2-(cyclopentadienyl)ethyl groups are preferred, with vinyl groups, allyl groups, buta-3-en-1-yl groups, penta-4-en-1-yl groups, prenyl groups, and hexa-5-en-1-yl groups being more preferred.

[0106] Among the linear or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 40 carbon atoms, ethynyl group, propa-2-in-1-yl group, propargyl group, buta-2-in-1-yl group, buta-3-in-1-yl group, penta-3-in-1-yl group, penta-4-in-1-yl group, 3-methyl-buta-1-in-1-yl group, 3,3-dimethyl-buta-1-in-1-yl group, hexa-4-in-1-yl group, hexa-5-in-1-yl group, and more preferably propa-2-in-1-yl group, propargyl group, buta-2-in-1-yl group, and buta-3-in-1-yl group.

[0107] Among the aromatic linear or branched alkyl groups and unsaturated double bond-containing groups having 7 to 40 carbon atoms, there are benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, 2-(4-methylphenyl)ethyl group, 2-(2,4,6-trimethylphenyl)ethyl group, 2-(3,5-dimethylphenyl)ethyl group, 2-(2,4,6-tri-iso-propylphenyl)ethyl group, 2-(4-t The following are preferred: ert-butylphenyl)ethyl group, 2-(3,5-di-tert-butylphenyl)ethyl group, styryl group, 2-methyl-1-phenylpropan-2-yl group, 3-phenylpropyl group, cinnamyl group, neophyll group, cyclopentadienyldiphenylmethyl group, 2-(1-indenyl)propan-2-yl group, (1-indenyl)diphenylmethyl group, 2-(1-indenyl)ethyl group, 2-(9-fluorenyl)propan-2-yl group, (9-fluorenyl)diphenylmethyl group, 2-(9-fluorenyl)ethyl group, and more preferably, benzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, 3-phenylpropyl group, and cinnamyl group.

[0108] Among the aforementioned cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzylcyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzyl The following are preferred: a cycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, 2-methylbicyclo[2.2.1]heptan-2-yl group, bicyclo[2.2.2]octan-1-yl group, 1-adamantyl group, 2-adamantyl group, pentarenyl group, indenyl group, fluorenyl group, etc., and more preferably cyclopentyl group, cyclopentenyl group, 1-methylcyclopentyl group, cyclohexyl group, cyclohexenyl group, 1-methylcyclohexyl group, and 1-adamantyl group.

[0109] Among the aromatic substituents having 6 to 40 carbon atoms, phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, prenylphenyl group, 4-adamanthylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, phenanthryl group, anthracenyl group, and ferrocenyl group are preferred, and phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, 4-adamanthylphenyl group, naphthyl group, biphenyl group, phenanthryl group, and anthracenyl group are more preferred.

[0110] Examples of the halogen-containing groups include fluoromethyl group, trifluoromethyl group, trichloromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, heptafluoropropyl group, 3,3,3-trifluoropropyl group, nonafluorobutyl group, 4,4,4-trifluorobutyl group, dodecafluorohexyl group, 6,6,6-trifluorohexyl group, chlorophenyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, di-tert-butyl-fluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, trifluoromethoxyphenyl group, bistrifluoromethoxyphenyl group, trifluoromethylthiophenyl group, bistrifluoromethylthiophenyl group, fluorobiphenyl group, difluorobiphenyl group, Examples include trifluorobiphenyl group, tetrafluorobiphenyl group, pentafluorobiphenyl group, di-tert-butyl-fluorobiphenyl group, trifluoromethylbiphenyl group, bistrifluoromethylbiphenyl group, trifluoromethoxybiphenyl group, bistrifluoromethoxybiphenyl group, trifluoromethyldimethylsilyl group, trifluoromethoxy group, pentafluoroethoxy group, fluorophenoxy group, difluorophenoxy group, trifluorophenoxy group, pentafluorophenoxy group, di-tert-butyl-fluorophenoxy group, trifluoromethylphenoxy group, bistrifluoromethylphenoxy group, trifluoromethoxyphenoxy group, bistrifluoromethoxyphenoxy group, difluoromethylenedioxyphenyl group, bistrifluoromethylphenyliminomethyl group, trifluoromethylthio group, and the like.

[0111] Among the halogen-containing groups, a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoropropyl group, a 4,4,4-trifluorobutyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a trifluoromethoxyphenyl group, a pentafluorobiphenyl group, a trifluoromethylbiphenyl group, a bistrifluoromethylbiphenyl group, a trifluoromethoxy group, a pentafluorophenoxy group, a bistrifluoromethylphenoxy group, a bistrifluoromethylphenoxy group, a difluoromethylene dioxyphenyl group, a trifluoromethylthio group are preferable, and a trifluoromethyl group, a fluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a pentafluorobiphenyl group, a trifluoromethoxy group, a pentafluorophenoxy group are more preferable.

[0112] Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a tri-iso-propylsilyl group, a diphenylmethylsilyl group, a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, a triphenylsilyl group, a tris(trimethylsilyl)silyl group, a cyclopentadienyldimethylsilyl group, a di-n-butyl(cyclopentadienyl)silyl group, a cyclopentadienyldiphenylsilyl group, an indenylmethylsilyl group, a di-n-butyl(indenyl)silyl group, an indenylphenylsilyl group, a fluorenyldimethylsilyl group, a di-n-butyl(fluorenyl)silyl group, a fluorenyldiphenylsilyl group, a 4-trimethylsilylphenyl group, a 4-triethylsilylphenyl group, a 4-tri-iso-propylsilylphenyl group, a 4-tert-butyldiphenylsilylphenyl group, a 4-triphenylsilylphenyl group, a 4-tris(trimethylsilyl)silylphenyl group, a 3,5-bis(trimethylsilyl)phenyl group, and the like.

[0113] Among the silicon-containing groups mentioned above, trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, cyclopentadienyldimethylsilyl group, cyclopentadienyldiphenylsilyl group, indenyldimethylsilyl group, indenyldiphenylsilyl group, fluorenyldimethylsilyl group, fluorenyldiphenylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, 4-triphenylsilylphenyl group, and 3,5-bis(trimethylsilyl)phenyl group are preferred, and trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, and 3,5-bis(trimethylsilyl)phenyl group are more preferred.

[0114] Examples of the oxygen-containing groups include: methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, allyloxy group, n-butoxy group, sec-butoxy group, iso-butoxy group, tert-butoxy group, methallyloxy group, prenyloxy group, benzyloxy group, methoxymethoxy group, methoxyethoxy group, phenoxy group, naphthoxy group, toluyloxy group, iso-propylphenoxy group, allylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, iso-propoxyphenoxy group, allyloxyphenoxy group, biphenyloxy group, binaphthyloxy group, methoxymethyl group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxyethyl group, allyloxyethyl group, benzyloxyethyl group, phenoxyethyl group, methoxypropyl group, allyloxypropyl Examples include the ropyl group, benzyloxypropyl group, phenoxypropyl group, methoxyvinyl group, allyloxyvinyl group, benzyloxyvinyl group, phenoxyvinyl group, methoxyallyl group, allyloxyallyl group, benzyloxyallyl group, phenoxyallyl group, dimethoxymethyl group, di-iso-propoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxanyl group, dimethyldioxanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylenedioxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, furyl group, methylfuryl group, tetrahydrofuryl group, pyranyl group, tetrahydropyranyl group, furyl group, benzofuryl group, and dibenzofuryl group.

[0115] Among these oxygen-containing groups, an alkoxy group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) is preferable. Specifically, a methoxy group, an ethoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, a tert-butoxy group, a prenyl oxy group, a benzyloxy group, a phenoxy group, a naphthoxy group, a toluoyloxy group, an iso-propyl phenoxy group, an allyl phenoxy group, a tert-butyl phenoxy group, a methoxy phenoxy group, a biphenyl oxy group, a binaphthyl oxy group, an allyloxy methyl group, a benzyloxy methyl group, a phenoxy methyl group, a methoxy ethyl group, a methoxy allyl group, a benzyloxy allyl group, a phenoxy allyl group, a dimethoxy methyl group, a dioxolanyl group, a tetramethyl dioxolanyl group, a dioxanyl group, a dimethyl dioxanyl group, a methoxy phenyl group, an iso-propoxy phenyl group, an allyloxy phenyl group, a phenoxy phenyl group, a methylene dioxy phenyl group, a 3,5-dimethyl-4-methoxy phenyl group, a 3,5-di-tert-butyl-4-methoxy phenyl group, a furyl group, a methyl furyl group, a tetrahydropyranyl group, a furofuryl group, a benzofuryl group, a dibenzofuryl group, etc. are preferable, and a methoxy group, an iso-propoxy group, a tert-butoxy group, an allyloxy group, a phenoxy group, a dimethoxy methyl group, a dioxolanyl group, a methoxy phenyl group, an iso-propoxy phenyl group, an allyloxy phenyl group, a phenoxy phenyl group, a 3,5-dimethyl-4-methoxy phenyl group, a 3,5-di-tert-butyl-4-methoxy phenyl group, a furyl group, a methyl furyl group, a benzofuryl group, a dibenzofuryl group are more preferable.

[0116] Examples of the nitrogen-containing groups include amino groups, dimethylamino groups, diethylamino groups, allylamino groups, diallylamino groups, didecylamino groups, benzylamino groups, dibenzylamino groups, pyrrolidinyl groups, piperidinyl groups, morpholyl groups, azepinyl groups, dimethylaminomethyl groups, dibenzylaminomethyl groups, pyrrolidinylmethyl groups, dimethylaminoethyl groups, benzylaminomethyl groups, benzylaminoethyl groups, pyrrolidinylethyl groups, dimethylaminovinyl groups, benzylaminovinyl groups, pyrrolidinylvinyl groups, dimethylaminopropyl groups, benzylaminopropyl groups, pyrrolidinylpropyl groups, dimethylaminoallyl groups, benzylaminoallyl groups, pyrrolidinylallyl groups, aminophenyl groups, dimethylaminophenyl groups, 3,5-dimethyl-4-dimethylaminophenyl groups. Examples include 3,5-di-iso-propyl-4-dimethylaminophenyl group, jurolidinyl group, tetramethyljurolidinyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, pyridylphenyl group, quinolylphenyl group, isoquinolylphenyl group, indolinylphenyl group, indolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, methylpyrrolyl group, phenylpyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzimidazolyl group, oxazolyl group, oxazolidinyl group, and benzoxazolyl group.

[0117] Among the nitrogen-containing groups, amino groups having 1 to 20 carbon atoms (preferably 1 to 10) are preferred, specifically amino groups, dimethylamino groups, diethylamino groups, allylamino groups, benzylamino groups, dibenzylamino groups, pyrrolidinyl groups, piperidinyl groups, morpholyl groups, dimethylaminomethyl groups, benzylaminomethyl groups, pyrrolidinylmethyl groups, dimethylaminoethyl groups, pyrrolidinylethyl groups, dimethylaminopropyl groups, pyrrolidinylpropyl groups, dimethylaminoallyl groups, pyrrolidinylallyl groups, aminophenyl groups, dimethylaminophenyl groups, 3,5-dimethyl-4-dimethylaminophenyl groups, 3,5-di-iso-propyl-4-dimethylaminophenyl groups, jurolidinyl groups, tetramethyljurolidinyl groups, pyrrolidinylphenyl groups, pyrrolylphenyl groups, and carbazolylphenyl groups. The following are preferred groups: di-tert-butylcarbazolylphenyl group, pyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzimidazolyl group, oxazolyl group, oxazolidinyl group, benzoxazolyl group, etc. More preferred are amino group, dimethylamino group, diethylamino group, pyrrolidinyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, jurolidinyl group, tetramethyljurolidinyl group, pyrrolidinylphenyl group, pyrrolyl group, pyridyl group, carbazolyl group, and imidazolyl group.

[0118] Examples of the sulfur-containing groups include methylthio group, ethylthio group, benzylthio group, phenylthio group, naphthylthio group, methylthiomethyl group, benzylthiomethyl group, phenylthiomethyl group, naphthylthiomethyl group, methylthioethyl group, benzylthioethyl group, phenylthioethyl group, naphthylthioethyl group, methylthiovinyl group, benzylthiovinyl group, phenylthiovinyl group, naphthylthiovinyl group, methylthiopropyl group, benzylthiopropyl group, phenylthiopropyl group, naphthylthiopropyl group, methylthioallyl group, benzylthioallyl group, and phenyl Examples include thioallyl group, naphthylthioallyl group, mercaptophenyl group, methylthiophenyl group, thienylphenyl group, methylthienylphenyl group, benzothienylphenyl group, dibenzothienylphenyl group, benzodithienylphenyl group, thienyl group, tetrahydrothienyl group, methylthienyl group, thienofuryl group, thienothienyl group, benzothienyl group, dibenzothienyl group, thienobenzofuryl group, benzodithienyl group, dithiolanyl group, dithianyl group, oxathiolanyl group, oxathianyl group, thiazolyl group, benzothiazolyl group, and thiazolidinyl group.

[0119] Among the sulfur-containing groups mentioned above, thienyl group, methylthienyl group, thienofuryl group, thienothienyl group, benzothienyl group, dibenzothienyl group, thienobenofuryl group, benzodithienyl group, thiazolyl group, and benzothiazolyl group are preferred.

[0120] R 1 ~R 6 Among adjacent substituents (e.g., R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , and R 5 and R 6The rings may bond to each other to form a ring which may have substituents. In this case, the ring formed is preferably a 5-8 membered ring consisting of saturated hydrocarbons (excluding the hydrocarbon of the indenyl ring portion) or unsaturated hydrocarbons which may have substituents and fuse with the indenyl ring portion. If there are multiple rings, they may be the same or different from each other. The present invention is not particularly limited as long as it achieves its effects, but the ring is more preferably a 5 or 6 membered ring, and in this case, the structure formed by combining the ring and the indenyl ring portion of the parent nucleus may include, for example, a benzoindenyl ring, a tetrahydroindacenyl ring, or a tetrahydrobenzoindenyl ring (which may have substituents), with benzoindenyl rings and tetrahydroindacenyl rings (which may have substituents) being preferred.

[0121] R 7 ~R 12 Among adjacent substituents (e.g., R 7 and R 8 , R 8 and R 9 , R 9 and R 10 , R 10 and R 11 , and R 11 and R 12 The rings may bond to each other to form a ring which may have substituents. In this case, the ring formed is preferably a 5-8 membered ring consisting of saturated hydrocarbons (excluding the hydrocarbon of the indenyl ring portion) or unsaturated hydrocarbons which may have substituents and fuse with the indenyl ring portion. If there are multiple rings, they may be the same or different from each other. The present invention is not particularly limited as long as it achieves its effects, but the ring is more preferably a 5 or 6 membered ring, and in this case, the structure formed by combining the ring and the indenyl ring portion of the parent nucleus may include, for example, a benzoindenyl ring, a tetrahydroindacenyl ring, a tetrahydrobenzoindenyl ring, a tetrahydrofluorenyl ring, or a fluorenyl ring (which may have substituents), with benzoindenyl rings and tetrahydroindacenyl rings (which may have substituents) being preferred.

[0122] R 13 and R 14 These may bond to each other to form a ring containing Q. In this case, the formed ring is preferably a saturated or unsaturated ring of 3 to 8 members, which may have substituents. While not particularly limited as long as the effects of the present invention are achieved, the ring is preferably a 4 to 6 member ring, in which case R 13 and R 14 Examples of structures combining Q include a substituted cyclobutane ring, a substituted cyclopentane ring, a substituted fluorene ring, a substituted silacyclobutane (silate) ring, a substituted silacyclopentane (silorane) ring, a substituted silacyclohexane (silinane), and a substituted silafluorene ring, with the substituted cyclopentane ring, substituted silacyclobutane ring, and substituted silacyclopentane ring being preferred.

[0123] R 1 , R 2 , R 5 , R 6 , R 7 , R 8 , R 10 and R 11 Each of these is independently preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group, and more preferably a hydrogen atom.

[0124] R 3 and R 4 Each of these is independently preferably a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group; more preferably a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms; and even more preferably a hydrocarbon group having 1 to 20 carbon atoms.

[0125] R 9 and R 12Each of these is independently preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group, and more preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms.

[0126] R 13 and R 14 Each of these is independently preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group, and more preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms. Note, R 7 In this case, the oxygen-containing group, nitrogen-containing group, or sulfur-containing group may be a heterocyclic aromatic group as described later.

[0127] A preferred embodiment of the transition metal compound (A-2) is: In the above general formula [A-2], M is a zirconium atom or a hafnium atom, X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or an oxygen-containing group. Q is a carbon atom or a silicon atom, R 1 , R 2 , R 5 , R 6 , R 8 , R 10 , R 11 , R 13 and R 14 However, each is independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms (e.g., an alkoxy group), a nitrogen-containing group having 1 to 20 carbon atoms (e.g., an amino group), or a sulfur-containing group having 1 to 20 carbon atoms. R 3 and R 4However, each of these can be independently a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, a nitrogen-containing group having 1 to 20 carbon atoms, or a sulfur-containing group having 1 to 20 carbon atoms, and may be bonded to each other to form a ring which may have substituents. R 7 However, the substituents are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or an aromatic heterogeneous five-membered ring substituent (for example, a furyl group or thienyl group, which may have substituents) that contains at least one atom selected from nitrogen, oxygen, and sulfur within the heterocycle. R 9 and R 12 However, examples of transition metal compounds [A-2-I] that are independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms (e.g., an alkoxy group), a nitrogen-containing group having 1 to 20 carbon atoms (e.g., an amino group), or a sulfur-containing group having 1 to 20 carbon atoms are, respectively.

[0128] A more preferred embodiment of the transition metal compound (A-2-I) is: In the above general formula [A-2], Q is a silicon atom, R 1 , R 2 , R 5 , R 6 , R 8 , R 10 , R 11 , R 13 and R 14 However, each is independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms. R 3 and R 4 However, each of these can independently be a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms, and they may be bonded to each other to form a ring which may have substituents. R 9 and R 12Examples of the transition metal compound [A-2-II] include, independently of each other, a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms.

[0129] A more preferred embodiment of the transition metal compound [A-2-II] is the transition metal compound [A-2-III] in which R 1 and R 6 in the general formula [A-2] are hydrogen atoms. A more preferred embodiment of the transition metal compound [A-2-III] is the transition metal compound [A-2-IV] in which R 2 and R 5 in the general formula [A-2] are hydrogen atoms.

[0130] A more preferred embodiment of the transition metal compound [A-2-IV] is the transition metal compound [A-2-V] in which R 7 and R 8 in the general formula [A-2] are hydrogen atoms. A more preferred embodiment of the transition metal compound [A-2-V] is the transition metal compound [A-2-VI] in which R 10 and R 11 in the general formula [A-2] are hydrogen atoms.

[0131] A more preferred embodiment of the transition metal compound [A-2-VI] is the transition metal compound [A-2-VII] in which at least one of R 3 and R 4 is a hydrocarbon group having 1 to 20 carbon atoms (when only one of R 3 and R 4 is a hydrocarbon group having 1 to 20 carbon atoms, the other one is a hydrogen atom).

[0132] A more preferred embodiment of the transition metal compound [A-2-VII] is the transition metal compound [A-2-VII] in which R 3 and R 4However, examples of transition metal compounds [A-2-VIII] include hydrocarbon groups having 1 to 20 carbon atoms, which may be bonded to each other to form a ring that may have substituents.

[0133] A more preferred embodiment of the transition metal compound [A-2-VII] or [A-2-VIII] is one in which R in the general formula [A-2] 9 However, examples include transition metal compounds [A-2-IX] which are hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms, and more preferably hydrocarbon groups having 1 to 20 carbon atoms.

[0134] A more preferred embodiment of the transition metal compound [A-2-VIII] is one in which R in the general formula [A-2] 12 However, examples include transition metal compounds [A-2-X] which are hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms, and more preferably hydrocarbon groups having 1 to 20 carbon atoms.

[0135] In the above general formula [A-2], R 7 One example of a heterocyclic aromatic group that may have substituents, having a five-membered ring (hereinafter also referred to as a "hetero-five-membered ring") as its parent skeleton, which contains at least one atom selected from the group consisting of nitrogen, oxygen, and sulfur, is the group represented by the following general formulas [4a] to [4h].

[0136] [ka]

[0137] In the above general formulas [4a] to [4h], Ch is an oxygen atom or a sulfur atom, and R d Each of these is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and they may be the same or different. In addition, the dashed lines in the general formulas [4a] to [4h] indicate the bonding site with the indenyl ring.

[0138] Examples of the hydrocarbon groups having 1 to 20 carbon atoms include the above-mentioned R 1 ~R 14Among the examples of hydrocarbon groups having 1 to 40 carbon atoms, those having 1 to 20 carbon atoms are particularly noteworthy, and preferably include methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, iso-pentyl group, neopentyl group, tert-pentyl group, allyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctenyl group, norbornyl group, bicyclo[2.2.2]octan-1-yl group, 1-adamantyl group, 2-adamantyl group, benzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, and 3-phenyl Examples of groups include propyl group, cinnamyl group, phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, phenanthryl group, anthracenyl group, and ferrocenyl group. More preferably, examples include methyl group, ethyl group, 1-propyl group, 1-butyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, allyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, benzyl group, phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, biphenyl group, and terphenyl group.

[0139] R d Each is independent of the adjacent R dThey may bond with each other and fuse to form saturated or unsaturated hydrocarbon groups that constitute a 5- to 8-membered ring together with the atoms of the heterogeneous 5-membered ring, which may have substituents. The 5- to 8-membered ring is not particularly limited as long as it achieves the effects of the present invention, but is preferably a 5 or 6-membered ring. In this case, examples of structures formed by combining this ring with the heterogeneous 5-membered ring of the parent nucleus include a benzofuran ring, a benzothiophene ring, an indole ring, a carbazole ring, a benzoxazole ring, a benzothiazole ring, a benzimidazole ring, and a benzopyrazole ring.

[0140] Among the heterocyclic aromatic groups represented by the general formulas [4a] to [4h], the heterocyclic aromatic group represented by the general formula [4a] is preferred. Among the heterocyclic aromatic groups represented by the general formula [4a], the 2-furyl group, the 5-methyl-2-furyl group, the 2-thienyl group, and the 5-methyl-2-thienyl group are preferred.

[0141] Specific examples of the transition metal compound (A-2) are shown below, but the transition metal compound (A-2) according to the present invention is not limited to these. For convenience, the ligand structure obtained by removing the MXn (metal portion) of the general formula [A-2] is referred to as the 2-indenyl ring portion, the 1-indenyl ring portion, and the indenyl ring portion R 1 , R 6 and R 8 Substituents, indenyl ring portion R 2 , R 5 , R 9 , and R 12 Substituents, indenyl ring portion R 3 , R 4 , R 10 , and R 11 Substituents, 1-indenyl ring portion R 7 The structure is divided into seven parts: substituents and bridging regions. The abbreviation for the 2-indenyl ring portion is α, the abbreviation for the 1-indenyl ring portion is β, and the abbreviation for the indenyl ring portion is R. 1 , R 6 and R 8 The abbreviation for the substituent is γ, and the indenyl ring portion is R. 2 , R 5 , R9 , and R 12 The abbreviation for substituent is δ, and the indenyl ring portion is R. 3 , R 4 , R 19 , and R 11 The substituent is abbreviated as ε, and the 1-indenyl ring portion is R. 7 The abbreviation for substituents is ζ, and the abbreviation for the structure of the bridging portion is η. The abbreviations for each substituent are shown in [Table 1] to [Table 7].

[0142] [Table 1]

[0143] [Table 2]

[0144] The dashed lines in [Table 1] to [Table 2] indicate the connection points with the bridged sections.

[0145] [Table 3]

[0146] R in [Table 3] above 1 , R 6 and R 8 The substituents may be identical or different from one another in their combination.

[0147] [Table 4]

[0148] R in [Table 4] above 2 , R 5 , R 9 , and R 12 The substituents may be identical or different in their combination. However, R 9 The substituents are not δ-1, δ-20 to δ-54.

[0149] [Table 5]

[0150] R in [Table 5] above 3 , R 4 , R 10 , and R 11 The substituents may be identical or different in their combination. However, R 3 , R 4 The substituent will not be ε-1.

[0151] [Table 6]

[0152] [Table 7]

[0153] Specific examples of the metallic part MXn include TiF2, TiCl2, TiBr2, TiI2, Ti(Me)2, Ti(Bn)2, Ti(Allyl)2, Ti(CH2-tBu)2, Ti(1,3-butadienyl), Ti(1,3-pentadienyl), Ti(2,4-hexadienyl), Ti(1,4-diphenyl-1,3-pentadienyl), and Ti(CH2-S i(Me)3)2, Ti(OMe)2, Ti(OiPr)2, Ti(NMe2)2, Ti(OMs)2, Ti(OTs)2, Ti(OTf)2, ZrF2, ZrCl2, ZrBr2, ZrI2, Zr(Me)2, Zr(Bn)2, Zr(Allyl)2, Zr(CH2-tBu)2, Zr(1,3-butadienyl), Zr(1,3-pentadienyl), Zr(2, 4-Hexadienyl), Zr(1,4-diphenyl-1,3-pentadienyl), Zr(CH2-Si(Me)3)2, Zr(OMe)2, Zr(OiPr)2, Zr(NMe2)2, Zr(OMs)2, Zr(OTs)2, Zr(OTf)2, HfF2, HfCl2, HfBr2, HfI2, Hf(Me)2, Hf(Bn)2, Hf(Allyl)2, Hf(C Examples include H2-tBu)2, Hf(1,3-butadienyl), Hf(1,3-pentadienyl), Hf(2,4-hexadienyl), Hf(1,4-diphenyl-1,3-pentadienyl), Hf(CH2-Si(Me)3)2, Hf(OMe)2, Hf(OiPr)2, Hf(NMe2)2, Hf(OMs)2, Hf(OTs)2, and Hf(OTf)2. Me is a methyl group, Bn is a benzyl group, tBu is a tert-butyl group, Si(Me)3 is a trimethylsilyl group, OME is a methoxy group, OiPr is an iso-propoxy group, NMe2 is a dimethylamino group, OMs is a methanesulfonate group, OTs is a p-toluenesulfonate group, and OTf is a trifluoromethanesulfonate group.

[0154] According to the above notation, the 2-indenyl ring portion is α-3 in [Table 1], the 1-indenyl ring portion is β-1 in [Table 2], and the indenyl ring portion is R 1 , R 6 and R 8 All substituents are the γ-1,2-indenyl ring portion R in [Table 3]. 2 and R 5All substituents are the δ-1,1-indenyl ring moiety R in [Table 4] 7 The substituent is ζ-30, 1-indenyl ring portion R in [Table 6] 9 The substituent is the δ-2,1-indenyl ring portion R in [Table 4] 12 When the substituent is composed of δ-3 from [Table 4] and the bridging portion is composed of η-20 from [Table 7], and the metal portion MXn is ZrCl2, the compound represented by the following formula [A-2-(1)] is an example.

[0155] [ka]

[0156] Furthermore, the 2-indenyl ring portion is α-3 in [Table 1], the 1-indenyl ring portion is β-1 in [Table 2], and the indenyl ring portion R 1 , R 6 and R 8 The substituents are all γ-1 and the indenyl ring portion R in [Table 3]. 2 , R 5 , R 9 and R 12 The substituents are all δ-2 and indenyl ring portion R in [Table 4]. 10 and R 11 All substituents are the ε-1,1-indenyl ring moiety R in [Table 5] 7 When the substituent is composed of ζ-2 from [Table 6] and the bridging portion is composed of η-20 from [Table 7], and the metal portion MXn is ZrCl2, the compound represented by the following formula [A-2-(2)] is an example.

[0157] [ka]

[0158] Furthermore, the 2-indenyl ring portion is α-3 in [Table 1], the 1-indenyl ring portion is β-1 in [Table 2], and the 2-indenyl ring portion is R 1 and R 6 All substituents are the γ-2,2-indenyl ring portion R in [Table 3]. 2 and R 5All substituents are the δ-1,1-indenyl ring moiety R in [Table 4] 7 The substituent is the ζ-12, 1-indenyl ring portion R in [Table 6] 8 The substituent is the γ-1,1-indenyl ring portion R in [Table 3] 9 The substituent is the δ-4,1-indenyl ring portion R in [Table 4] 10 The substituent is the ε-1,1-indenyl ring portion R in [Table 5] 11 The substituent is the ε-12,1-indenyl ring portion R in [Table 5] 12 When the substituent is composed of δ-3 from [Table 4] and the bridging portion is composed of η-31 from [Table 7], and the MXn of the metal portion is HfMe2, the compound represented by the following formula [A-2-(3)] is given as an example.

[0159] [ka]

[0160] Furthermore, the 2-indenyl ring portion is α-1 in [Table 1], the 1-indenyl ring portion is β-1 in [Table 2], and the 2-indenyl ring portion is R 1 and R 6 All substituents are the γ-1,2-indenyl ring portion R in [Table 3]. 2 and R 5 The substituent is the δ-1,2-indenyl ring portion R in [Table 4] 3 and R 4 The substituent is the ε-2,1-indenyl ring portion R in [Table 5] 10 and R 11 The substituent is the ε-1,1-indenyl ring portion R in [Table 5] 7 The substituent is the ζ-1,1-indenyl ring portion R in [Table 6] 8 The substituent is the γ-9,1-indenyl ring portion R in [Table 3] 9 The substituents are δ-5 and R in [Table 4]. 12 When the substituent is composed of δ-22 from [Table 4] and the bridging portion is composed of η-4 from [Table 7], and the MXn of the metal portion is Ti(1,3-pentadienyl), the compound represented by the following formula [A-2-(4)] is given as an example.

[0161] [ka]

[0162] Furthermore, the transition metal compound (A-2) has two planes (front and back) for the indenyl ring portion that bond to the central metal, flanking the bridging portion. Therefore, if there is no plane of symmetry for the 2-indenyl ring portion, there are two structural isomers, as an example, represented by the following general formulas [A-2-(5a)] or [A-2-(5b)].

[0163] [ka]

[0164] Similarly, substituent R in the crosslinked portion 13 and R 14 Even when they are not identical, there are two structural isomers, as an example, represented by the following general formulas [A-2-(6a)] or [A-2-(6b)].

[0165] [ka]

[0166] The purification, separation, or selective production of these structural isomer mixtures is possible by known methods, and the production method is not particularly limited. Known production methods include those listed above as methods for producing the transition metal compound [A], as well as methods disclosed in Japanese Patent Publication No. 10-109996, "Organometallics 1999, 18, 5347," "Organometallics 2012, 31, 4340," and Japanese Patent Publication No. 2011-502192.

[0167] Furthermore, the transition metal compound (A-2) may be used alone, in combination of two or more types, or as a mixture of structural isomers, within the range that satisfies the general formula [A-2]w, or as a single structural isomer or as a mixture of two or more structural isomers. In addition, other transition metal compounds may be used in combination, as long as the effects of the present invention are not impaired.

[0168] The transition metal compound (A-2) can be produced using conventionally known methods, for example, the method described in

[0097] to

[0115] of Japanese Patent Publication No. 2019-59933, or the method described in

[0098] to

[0116] of Japanese Patent Publication No. 2019-59724, where R 1 ~R 14 It can be manufactured by substituting Q, M, X, and n with the same meanings as those described in the general formula [A-2] above.

[0169] [Polymerization catalyst] The olefin polymerization catalyst used in step (A2) is not particularly limited as long as it contains the transition metal compound (A-2) described above, but it is preferable that in addition to the transition metal compound (A-2), it contains catalyst component (C) selected from (C1) organometallic compounds, (C2) organoaluminum oxy compounds, and (C3) compounds that react with the transition metal compound (A-2) to form ion pairs. Details of catalyst component (C) will be described later.

[0170] [Process (A2)] Step (A2) is a step to produce a terminally unsaturated ethylene-propylene copolymer by copolymerizing ethylene and propylene in the presence of an olefin polymerization catalyst containing the transition metal compound (A-2) described above, and is preferably carried out in solution polymerization. The polymerization conditions are not particularly limited and can be those of a solution polymerization process used to produce olefin polymers, but it is preferable to use an aliphatic hydrocarbon or aromatic hydrocarbon as the polymerization solvent and polymerize ethylene in the presence of an olefin polymerization catalyst containing the transition metal compound (A-2) described above to obtain a polymerization reaction solution.

[0171] Examples of polymerization solvents for step (A2) include aliphatic hydrocarbons and aromatic hydrocarbons. Specifically, the polymerization solvents exemplified above for step (A1) can be used. Furthermore, the polymerization conditions for step (A2), such as polymerization temperature, polymerization pressure, reaction time, and reaction method, can preferably be the same as those for step (A1) described above.

[0172] In the terminally unsaturated ethylene polymer or terminally unsaturated ethylene-propylene copolymer produced in step (A) (step (A1) or step (A2)), the terminal vinyl content (ratio of vinyl groups to total unsaturated carbon-carbon bonds) is usually 40% or more, preferably 50%, and more preferably 60% or more.

[0173] Furthermore, the proportion of terminal vinyl groups in the terminally unsaturated ethylene polymer or terminally unsaturated ethylene-propylene copolymer produced in step (A) (step (A1) or step (A2)) is usually 0.1 to 15 per 1000 carbon atoms, but preferably in the range of 0.4 to 15.

[0174] If the terminal vinyl ratio (the ratio of vinyl groups to the total unsaturated carbon-carbon bonds) and the ratio of terminal vinyl groups per 1000 carbon atoms are low, the amount of terminally unsaturated ethylene polymer or terminally unsaturated ethylene-propylene copolymer (specifically, an ethylene polymer or ethylene-propylene copolymer with a vinyl group at one end) introduced into the main chain in the subsequent step (B) will be low, resulting in a low amount of graft-type olefin polymer [R1] being produced, and thus the desired effect may not be obtained.

[0175] The terminal vinyl ratio (the ratio of vinyl groups to the total unsaturated carbon-carbon bonds) and the ratio of terminal vinyl groups per 1000 carbon atoms are: 1 It can be calculated using conventional methods by analyzing the polymer structure using 1H-NMR measurement.

[0176] [Process (B)] Step (B) is carried out in the presence of an olefin polymerization catalyst containing a transition metal compound [B] of Group 4 of the periodic table that has a ligand having a dimethylsilylbisindenyl skeleton, The process involves copolymerizing the terminally unsaturated ethylene polymer or terminally unsaturated ethylene-propylene copolymer produced in step (A) with propylene, or copolymerizing the terminally unsaturated ethylene polymer or terminally unsaturated ethylene-propylene copolymer produced in step (A) with propylene and ethylene.

[0177] [Transition metal compounds [B]] In step (B), an olefin polymerization catalyst is used that contains a transition metal compound [B] of Group 4 of the periodic table (hereinafter also simply referred to as transition metal compound [B]) which has a ligand having a dimethylsilylbisindenyl skeleton. The transition metal compound [B] functions as a polymerization catalyst for copolymerization of the terminally unsaturated ethylene polymer or terminally unsaturated ethylene-propylene copolymer produced in step (A) with propylene, or with propylene and ethylene, and functions more preferably when used in combination with catalyst component (C) described later.

[0178] As the transition metal compound [B], any transition metal compound of Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton can be used, but compounds disclosed in, for example, Japanese Patent Publication Nos. Hei 6-100579, 2001-525461, 2005-336091, 2009-299046, 11-130807, and 2008-285443 can be preferably used.

[0179] More specifically, suitable examples of the transition metal compound [B] include compounds selected from the group consisting of crosslinked bis(indenyl) zirconosenes or hafnocenes. More preferably, dimethylsilyl crosslinked bis(indenyl) zirconosene or hafnocene. Even more preferably, dimethylsilyl crosslinked bis(indenyl) zirconosene, and by selecting zirconosene, an olefin resin (β) containing a desired graft-type olefin polymer [R1] can be efficiently produced.

[0180] More specifically, dimethylsilyl-bis{1-(2-n-propyl-4-(9-phenanthryl)indenyl)}zirconium dichloride, dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride, dimethylsilylbis(2-methyl-4-phenylindenyl)zirconiumdimethyl, etc., can be used as suitable compounds. The transition metal compounds [B] described above can be used individually or in combination of two or more.

[0181] [Polymerization catalyst] The olefin polymerization catalyst used in step (B) may contain a transition metal compound [B] of Group 4 of the periodic table containing the ligand having the dimethylsilylbisindenyl skeleton described above, and is not particularly limited. However, it is preferable that the catalyst also contains a catalyst component (C) selected from (C1) organometallic compounds, (C2) organoaluminum oxy compounds, and (C3) compounds that react with the transition metal compound [B] to form an ion pair. Details of catalyst component (C) will be described later.

[0182] [Process (B)] Step (B) is carried out in the presence of an olefin polymerization catalyst containing a transition metal compound [B] of Group 4 of the periodic table that includes the ligand having the dimethylsilylbisindenyl skeleton described above, The process involves copolymerizing the terminally unsaturated ethylene polymer or terminally unsaturated ethylene-propylene copolymer produced in step (A) with propylene, or copolymerizing the terminally unsaturated ethylene polymer or terminally unsaturated ethylene-propylene copolymer produced in step (A) with propylene and ethylene. In other words, step (B) involves copolymerizing the terminally unsaturated ethylene polymer or terminally unsaturated ethylene-propylene copolymer produced in step (A) with propylene and, if necessary, further with ethylene.

[0183] The polymerization method of step (B) is not particularly limited, but is preferably carried out in solution polymerization. The polymerization conditions are not particularly limited and can be any solution polymerization process used to produce olefin polymers. For example, it is preferable to use an aliphatic hydrocarbon or aromatic hydrocarbon as the polymerization solvent and copolymerize propylene, optionally with ethylene, and the terminally unsaturated ethylene polymer or terminally unsaturated ethylene-propylene copolymer produced in step (A) in the presence of an olefin polymerization catalyst containing the transition metal compound [B] described above, to obtain a polymerization reaction solution containing a graft-type olefin polymer [R1].

[0184] In step (B), the terminally unsaturated ethylene polymer or terminally unsaturated ethylene-propylene copolymer produced in step (A) is usually fed into the reactor in step (B) in solution or slurry form. The feeding method is not particularly limited; the polymerization reaction solution obtained in step (A) may be continuously fed into the reactor in step (B), or the polymerization reaction solution obtained in step (A) may be temporarily stored in a buffer tank or the like before being fed into step (B).

[0185] Examples of polymerization solvents for step (B) include aliphatic hydrocarbons and aromatic hydrocarbons. Specifically, these 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 can be used individually or in combination of two or more. Furthermore, the polymerization solvent for step (B) may be the same as or different from the polymerization solvent for step (A). The polymerization temperature in step (B) is typically in the range of 50°C to 200°C, preferably 80°C to 200°C, and more preferably 90°C to 200°C.

[0186] The polymerization pressure in step (B) is typically between atmospheric pressure and 10 MPa gauge pressure, preferably between atmospheric pressure and 5 MPa gauge pressure, and the polymerization reaction can be carried out in batch, semi-continuous, or continuous manner. Furthermore, polymerization can be carried out in two or more stages with different reaction conditions. In this invention, it is preferable to employ a method in which monomers are continuously supplied to the reactor to carry out copolymerization.

[0187] The reaction time in step (B) (or average residence time if copolymerization is carried out by a continuous process) 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.

[0188] The polymer concentration in step (B) is, for example, 0.5 to 40% by mass during steady-state operation, preferably 1 to 35% by mass. From the viewpoint of viscosity limitation in polymerization capacity, post-treatment (solvent removal) load, and productivity, 1.5 to 35% by mass is preferred.

[0189] The molecular weight of the resulting copolymer, the graft-type olefin polymer [R1], can be adjusted by introducing hydrogen into the polymerization system or by changing the polymerization temperature. Furthermore, it can also be adjusted by the amount of catalyst component (C1) used, as described below. Specifically, examples include triisobutylaluminum, methylaluminoxane, and diethylzinc. When hydrogen is added, an appropriate amount is approximately 0.001 to 100 NL per kg of olefin.

[0190] [Catalyst component (C)] In the method for producing the olefin resin (β) according to the present invention, it is also preferable that the olefin polymerization catalyst used in steps (A) and (B) described above includes, in addition to the transition metal compound (A-1) or (A-2) described above and a transition metal compound [B] of Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton, a catalyst component (C). The catalyst component (C) may be used as a catalyst component for the olefin polymerization catalyst in both steps (A) and (B), or as a catalyst component for the olefin polymerization catalyst in either step (A) or step (B). When the catalyst component (C) is used as a catalyst component for 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.

[0191] The catalyst component (C) is one or more compounds selected from (C1) organometallic compounds, (C2) organoaluminum oxy compounds, and (C3) compounds that react with transition metal compounds contained in olefin polymerization catalysts to form ion pairs. The compounds (C1) to (C3) will be explained in order below.

[0192] ((C1) Organometallic compound) As the (C1) organometallic compound used in the present invention, specifically, an organoaluminum compound represented by the following general formula (C1-a), a complex alkyl compound of a Group 1 metal of the periodic table and aluminum represented by the general formula (C1-b), and a dialkyl compound of a Group 2 or Group 12 metal of the periodic table represented by the general formula (C1-c) can be mentioned. Note that the (C1) organometallic compound does not include the (C2) organoaluminum oxy compound described later.

[0193] 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 as or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, p is 0 < p ≤ 3, q is 0 ≤ q < 3, r is 0 ≤ r < 3, s is 0 ≤ s < 3, and p + q + r + s = 3. )

[0194] M 3 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. )

[0195] R d R e M 4 …(C1-c) In the above general formula (C1-c), R d and R e may be the same as or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M 4 is Mg, Zn or Cd.

[0196] 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). R a p Al(OR b ) 3-p …(C-1a-1) (In formula (C-1a-1), R a and R b may be the same as or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably a number such that 1.5 ≦ p ≦ 3.) An organoaluminum compound represented by

[0197] R a p AlY 3-p …(C-1a-2) (In formula (C-1a-2), R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, and p is preferably a number such that 0 < p < 3.) An organoaluminum compound represented by R a p AlH 3-p …(C-1a-3) (In formula (C-1a-3), R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably a number such that 2 ≦ p < 3.) An organoaluminum compound represented by

[0198] R a p Al(OR b ) q Y s …(C-1a-4) (In formula (C-1a-4), R a and R b may be the same as or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, p is a number such that 0 < p ≦ 3, q is a number such that 0 ≦ q < 3, s is a number such that 0 ≦ s < 3, and p + q + s = 3.) An organoaluminum compound represented by

[0199] More specifically, organoaluminum compounds belonging to general formula (C1-a) include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, and other tri-n-alkylaluminum compounds; Tri-branched alkylaluminum compounds such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, and tri-2-ethylhexylaluminum; Tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum; Triarylaluminum, such as triphenylaluminum and tritrilaluminum; Dialkylaluminum hydrides such as diisobutylaluminum hydride; (i-C4H9) x Al y (C5H 10 ) z Trialkenyl aluminum, such as triisoprenyl aluminum, represented by the formula (where 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(ORb ) 0.5 Partially alkoxylated alkylaluminum having an average composition represented by the formula (wherein R a and R b These may be identical or different from each other, and represent hydrocarbon groups having 1 to 15, preferably 1 to 4, carbon atoms. Dialkylaluminum allyloxides 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; Alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide; Partially halogenated alkylaluminums such as alkylaluminum dihalides, ethylaluminum dichloride, propylaluminum dichloride, and butylaluminum dibromide; Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; Other partially hydrogenated alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride; Examples include partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, and ethylaluminum ethoxybromide.

[0200] Compounds similar to (C1-a) can also be used in the present invention, and examples of such compounds include organoaluminum compounds in which two or more aluminum compounds are bonded via a nitrogen atom. Specifically, examples of such compounds include (C2H5)2AlN(C2H5)Al(C2H5)2.

[0201] Examples of compounds belonging to the general formula (C1-b) include LiAl(C2H5)4 and LiAl(C7H 15 Examples include 4. Examples of compounds belonging to the general formula (C1-c) include dimethylmagnesium, diethylmagnesium, dibutylmagnesium, butylethylmagnesium, dimethylzinc, diethylzinc, diphenylzinc, di-n-propylzinc, diisopropylzinc, di-n-butylzinc, diisobutylzinc, bis(pentafluorophenyl)zinc, dimethylcadmium, and diethylcadmium.

[0202] In addition, other (C1) organometallic compounds that can be used include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, and butylmagnesium chloride.

[0203] Furthermore, compounds such as a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium, which form the above-mentioned organoaluminum compound within the polymerization system, can also be used as the (C1) organometallic compound. The (C1) organometallic compounds described above can be used individually or in combination of two or more.

[0204] (C1) The organometallic compound is used in an amount such that the molar ratio (C1 / M) of the (C1) organometallic compound to the transition metal atoms (M) in the transition metal compound contained in the olefin polymerization catalyst is usually 0.01 to 100,000, preferably 0.05 to 50,000.

[0205] ((C2) organoaluminum oxy compounds) The (C2) organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, or a benzene-insoluble organoaluminum oxy compound as exemplified in Japanese Patent Application Publication No. 2-78687. Specific examples of (C2) organoaluminum oxy compounds include methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane. Conventionally known aluminoxanes can be produced by methods such as those described in (1) to (3) below, and are usually obtained as solutions in a hydrocarbon solvent.

[0206] (1) A method of reacting the adsorbed water or crystal water with the organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to a suspension of a hydrocarbon medium containing a compound or salt containing crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, or cerium chloride hydrate.

[0207] (2) A method of directly reacting an organoaluminum compound such as trialkylaluminum with water, ice, or water vapor in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran.

[0208] (3) A method of reacting organoaluminum compounds such as trialkylaluminum with organotin oxides such as dimethyltin oxide and dibutyltin oxide in a medium such as decane, benzene, or toluene.

[0209] The aluminoxane may contain a small amount of organometallic components. Alternatively, after removing the solvent or unreacted organoaluminum compounds from the recovered aluminoxane solution by distillation, the obtained aluminoxane may be redissolved in a solvent or suspended in a poor solvent for aluminoxane.

[0210] Specific examples of organoaluminum compounds used in the preparation of aluminoxanes include those similar to those exemplified as organoaluminum compounds belonging to the general formula (C1-a) above.

[0211] Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred. The organoaluminum compounds described above can be used individually or in combination of two or more.

[0212] Solvents used in the preparation of aluminoxanes 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 fuel; or halogenated compounds of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, particularly chlorinated and brominated hydrocarbon solvents. Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferred.

[0213] Furthermore, the benzene-insoluble organoaluminum oxy compounds used in the present invention are preferably those in which the Al component that dissolves in benzene at 60°C is typically 10% or less, preferably 5% or less, and particularly preferably 2% or less in terms of Al atoms; in other words, they are preferably insoluble or sparingly soluble in benzene.

[0214] Examples of (C2) organoaluminum oxy compounds used in the present invention include organoaluminum oxy compounds containing boron represented by the following general formula (III).

[0215] [ka] (In general formula (III), R 17 This indicates a hydrocarbon group with 1 to 10 carbon atoms, and four R 18 These may be identical or different from each other, and represent hydrogen atoms, halogen atoms, or hydrocarbon groups with 1 to 10 carbon atoms.

[0216] The boron-containing organoaluminum oxy compound represented by the general formula (III) can be produced by reacting an alkylboronic acid represented by the general formula (IV) below 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. R 19 -B(OH)2…(IV) (In general formula (IV), R 19 R in the above general formula (III) is 17 (It shows the same base.)

[0217] Specific examples of alkylboronic acids represented by the general formula (IV) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, and 3,5-bis(trifluoromethyl)phenylboronic acid. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These can be used individually or in combination of two or more.

[0218] Specific examples of organoaluminum compounds that react with such alkylboronic acids include organoaluminum compounds similar to those exemplified as organoaluminum compounds belonging to the general formula (C1-a) above.

[0219] The organoaluminum compounds mentioned above are preferably trialkylaluminum and tricycloalkylaluminum, and particularly preferably trimethylaluminum, triethylaluminum, and triisobutylaluminum. These can be used individually or in combination of two or more. It is preferable for the olein polymerization catalyst to contain a (C2) organoaluminum oxy compound, as this results in high polymerization activity towards olefin compounds.

[0220] The (C2) organoaluminum oxy compounds described above can be used individually or in combination of two or more. The organoaluminum oxy compound (C2) is used in such an amount that the molar ratio (C2 / M) of aluminum atoms in the organoaluminum oxy compound (C2) to transition metal atoms (M) in the transition metal compound contained in the olefin polymerization catalyst is typically 10 to 500,000, preferably 20 to 100,000.

[0221] ((C3) Compounds that react with transition metal compounds to form ion pairs) (C3) Compounds that react with transition metal compounds to form ion pairs are compounds that react with transition metal compounds contained in the olefin polymerization catalyst to form ion pairs. The transition metal compounds contained in the olefin polymerization catalyst refer to the transition metal compounds (A-1) or (A-2) used in step (A) described above, or the Group 4 transition metal compounds [B] of the periodic table that contain ligands having a dimethylsilylbisindenyl skeleton used in step (B).

[0222] Examples of compounds used in the present invention that react with (C3) transition metal compounds to form ion pairs (hereinafter referred to as "ionized ionic compounds") include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in Japanese Patent Publication No. 1-501950, Japanese Patent Publication No. 1-502036, Japanese Patent Application Publication No. 3-179005, Japanese Patent Application Publication No. 3-179006, Japanese Patent Application Publication No. 3-207703, Japanese Patent Application Publication No. 3-207704, and USP-5321106. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

[0223] Specifically, examples of the Lewis acid include compounds represented by BR3 (where R is a phenyl group or fluorine which may have substituents such as fluorine, a methyl group, or a trifluoromethyl group), such as trifluoroborone, triphenylborone, tris(4-fluorophenyl)borone, tris(3,5-difluorophenyl)borone, tris(4-fluoromethylphenyl)borone, tris(pentafluorophenyl)borone, tris(p-tolyl)borone, tris(o-tolyl)borone, and tris(3,5-dimethylphenyl)borone. Examples of the aforementioned ionic compounds include those represented by the following general formula (V).

[0224] [ka] (In general formula (V), R 20 is H + R is a carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, or ferrocenium cation having a transition metal. 21 ~R 24 These may be the same or different groups, and are organic groups, preferably aryl groups or substituted aryl groups.

[0225] Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

[0226] Examples of the aforementioned ammonium cations 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.

[0227] Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation.

[0228] R 15 As such, carbonium cations and ammonium cations are preferred, and triphenylcarbonium cations, N,N-dimethylanilinium cations, and N,N-diethylanilinium cations are particularly preferred.

[0229] Other examples of ionic compounds include trialkylsubstituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

[0230] Specific examples of the aforementioned trialkyl-substituted ammonium salts include triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tri(n-butyl)ammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(m,m-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(p-trifluoromethylphenyl)boron, tri(n-butyl)ammonium tetra(3,5-ditrifluoromethylphenyl)boron, and tri(n-butyl)ammonium tetra(o-tolyl)boron.

[0231] Specifically, the aforementioned N,N-dialkylanilinium salts include, for example, N,N-dimethylanilinium tetra(phenyl)boron and N,N-diethylanilinium tetra(phenyl Examples include boron and N,N,2,4,6-pentamethylaniliniumtetra(phenyl)boron.

[0232] Examples of the aforementioned dialkylammonium salts include, for example, di(1-propyl)ammonium tetra(pentafluorophenyl)boron and dicyclohexylammonium tetra(phenyl)boron.

[0233] Furthermore, as ionic compounds, we can also mention 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 formulas (VI) or (VII).

[0234] [ka] (In formula (VI), Et represents an ethyl group.)

[0235] [ka] (In formula (VII), Et represents an ethyl group.)

[0236] Examples of ionized ionic compounds (compound [C3]) include, specifically, 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; Examples include 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).

[0237] Examples of ionized ionic compounds include, specifically, carborane compounds such as 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-dicarbowndecaborane, 2,7-dicarbowndecaborane, and undecahydride-7,8-dimethyl Lu-7,8-Dicarboundecaporane, Dodecahydride-11-methyl-2,7-Dicarboundecaporane, Tri(n-butyl)ammonium 1-carbadecaborate, Tri(n-butyl)ammonium 1-carbadodecaborate, 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-carbadecaborate, tri(n-butyl)ammonium 7,8-diccarbadecaborate, tri(n-butyl)ammonium 2,9-diccarbadecaborate, tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-diccarbadecaborate, tri(n-butyl)ammonium undecahydride-8-ethyl-7,9-dica Salts of anions such as ulbounde decaborate, tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dicbounde decaborate, tri(n-butyl)ammonium undecahydride-8-allyl-7,9-dicbounde decaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dicbounde decaborate, and tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carbounde decaborate; Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate)cobaltate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)ferrate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)cobaltate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)niclate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)copperate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)goldate (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbowndecaborate)ferric acid Examples include salts of metal carborane anions such as salt (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarboundecaborate)chromate (III), tri(n-butyl)ammonium bis(tribromooctahydride-7,8-dicarboundecaborate)cobaltate (III), tris[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)chromate (III), bis[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)manganate (IV), bis[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)cobaltate (III), and bis[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)nickelate (IV).

[0238] Heteropoly compounds, which are examples of ionized ionic compounds, are compounds containing an atom selected from silicon, phosphorus, titanium, germanium, arsenic, and tin, and one or more atoms selected from vanadium, niobium, molybdenum, and tungsten. Specifically, these include, but are not limited to, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic 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, phosphomolybdotungstovanadic acid, phosphomolybdoniobic acid, and salts of these acids. Furthermore, examples of the salt include salts of the acid with metals from Group 1 or Group 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc., as well as organic salts such as triphenylethyl salts.

[0239] Isopolycompounds, which are examples of ionized ionic compounds, are compounds composed of a metal ion of one atom selected from vanadium, niobium, molybdenum, and tungsten, and can be considered as molecular ionic species of metal oxides. Specifically, examples include, but are not limited to, vanadic acid, niobic acid, molybdic acid, tungstic acid, and salts of these acids. Furthermore, examples of the salts include salts of the acid with metals from Group 1 or Group 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc., as well as organic salts such as triphenylethyl salts.

[0240] The ionized ionic compounds described above (compounds that react with transition metal compounds contained in (C3) olefin polymerization catalysts to form ion pairs) are used individually or in combination of two or more types.

[0241] The ionized ionic compound (C3) is used in an amount such that the molar ratio (C3 / M) of the ionized ionic compound (C3) to the transition metal atoms (M) in the transition metal compound contained in the olefin polymerization catalyst is usually 1 to 10, preferably 1 to 5.

[0242] [Other processes] The olefin resin (β) production method according to the present invention may, in addition to steps (A) and (B) described above, optionally include a step of recovering the polymer produced in step (A) or (B), or both steps (A) and (B). This step is a step of separating the organic solvent used in steps (A) and (B) to extract the polymer, and is not particularly limited as long as it is a known step such as solvent concentration, extrusion degassing, pelletizing, or crystallization.

[0243] <Olefin-based resin composition> The olefin resin composition of the present invention is a composition containing one or more propylene resins (α1) and ethylene resins (α2), and the olefin resin (β) of the present invention described above.

[0244] [Propylene resin (α1)] As the propylene resin (α1), either a propylene homopolymer or a propylene copolymer containing more than 50 mol% of structural units derived from propylene can be used. The propylene resin (α1) 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 propylene.

[0245] Preferably, the propylene-based resin (α1) is a homopolymer of propylene, or is composed of a copolymer of propylene and ethylene and at least one selected from α-olefins having 4 to 20 carbon atoms. The copolymer may be a random copolymer or a block copolymer. Specific examples of the aforementioned α-olefins having 4 to 20 carbon atoms include 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, and dimethyl-1- Examples include 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 of 1-butene, 1-pentene, 1-hexene, and 1-octene can be preferably used.

[0246] The propylene resin (α1) may be composed of a single polymer or a plurality of polymers from among the aforementioned polymers. In this invention, the propylene resin (α1) can be any of the following: a product manufactured by polymerization or copolymerization, a commercially available product, or a recycled product.

[0247] When the propylene resin (α1) is a product manufactured by polymerization or copolymerization, it can be produced by polymerizing or copolymerizing a monomer mainly composed of propylene using a known olefin polymerization catalyst, for example, by polymerizing or copolymerizing using a Ziegler-Natta catalyst.

[0248] If the propylene resin (α1) is a commercially available product, any commercially available propylene resin can be used without particular restriction. Examples of commercially available propylene resins include so-called homopolypropylene resins, random polypropylene resins, and block polypropylene resins, with homopolypropylene resins and block polypropylene resins being preferred, and homopolypropylene resins being even more preferred.

[0249] If the propylene resin (α1) is a recycled product, recycled plastics mainly composed of propylene resin, or plastic products mainly composed of propylene resin that have been washed, crushed, or pelletized can be used.

[0250] Homopolypropylene resin is a resin composed of essentially a homopolymer of propylene. It is generally inexpensive and easy to manufacture, and while it has excellent rigidity and surface hardness, it is inferior in impact resistance and toughness. In the propylene-based resin composition of the present invention, when homopolypropylene resin is used as the propylene-based resin (α1), the olefin-based resin (β) can be used to improve impact resistance and toughness while maintaining the excellent characteristics of the homopolypropylene resin, such as its rigidity.

[0251] The following describes preferred embodiments of the propylene resin (α1). The propylene resin (α1) preferably has a melt flow rate (MFR) of 0.1 to 500 g / 10 min, measured at 230°C and a load of 2.16 kg in accordance with ASTM D1238. The lower limit of the MFR is preferably 0.2 g / 10 min, more preferably 0.3 g / 10 min, and the upper limit is preferably 300 g / 10 min, more preferably 100 g / 10 min, and particularly preferably 50 g / 10 min. If the MFR of the propylene resin (α1) is less than 0.1 g / 10 min, the fluidity is low and moldability may be problematic. If the MFR of the propylene resin (α1) is greater than 500 g / 10 min, the strength of the propylene resin (α1) itself is low, and the mechanical strength of the resulting resin composition may be low.

[0252] MFR serves as an indicator of the molecular weight of the propylene resin (α1), but the weight-average molecular weight of the propylene resin (α1), as determined by gel permeation chromatography (GPC) in terms of polystyrene, is preferably in the range of 80,000 to 900,000, more preferably 100,000 to 700,000, and particularly preferably 150,000 to 700,000.

[0253] The terminal structure of propylene resins (α1) is usually substantially saturated hydrocarbon, and specifically, the proportion of unsaturated terminals in propylene resins (α1) is usually less than 0.1 per 1000 carbon atoms.

[0254] [Ethylene-based resin (α2)] As the ethylene-based resin (α2), either an ethylene homopolymer or an ethylene-based copolymer containing more than 50 mol% of structural units derived from ethylene can be used. The ethylene-based resin (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.

[0255] Preferably, the ethylene-based resin (α2) is a homopolymer of ethylene, or a copolymer of ethylene and at least one α-olefin selected from those having 3 to 20 carbon atoms. The copolymer may be a random copolymer or a block copolymer. Specific examples of the aforementioned α-olefins 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, and dimethyl Examples include 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 of propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene can be preferably used.

[0256] The ethylene resin (α2) may be composed of a single polymer from the aforementioned polymers, or it may be composed of multiple polymers. In this invention, the ethylene resin (α2) can be any of the following: a product manufactured by polymerization or copolymerization, a commercially available product, or a recycled product.

[0257] When the ethylene-based resin (α2) is a product manufactured by polymerization or copolymerization, it can be produced by polymerization or copolymerization of monomers mainly composed of ethylene using known olefin polymerization catalysts, for example, by polymerization or copolymerization using a Ziegler-Natta catalyst.

[0258] If the ethylene resin (α2) is a commercially available product, any commercially available ethylene resin can be used without any particular restrictions. Examples of commercially available ethylene resins include polyethylene resins such as so-called homopolyethylene resins, ethylene-α-olefin copolymers, and ethylene elastomers.

[0259] If the ethylene resin (α2) is a recycled product, recycled plastics mainly composed of ethylene resin, or plastic products mainly composed of ethylene resin that have been washed, crushed, or pelletized can be used.

[0260] The following describes preferred embodiments of the ethylene resin (α2). The ethylene resin (α2) preferably has a melt flow rate (MFR) of 0.1 to 500 g / 10 min, measured at 190°C and a load of 2.16 kg in accordance with ASTM D1238. The lower limit of the MFR is preferably 0.2 g / 10 min, more preferably 0.3 g / 10 min, and the upper limit is preferably 300 g / 10 min, more preferably 100 g / 10 min, and particularly preferably 50 g / 10 min. If the MFR of the ethylene resin (α2) is less than 0.1 g / 10 min, the fluidity is low and moldability may be problematic. If the MFR of the ethylene resin (α2) is greater than 500 g / 10 min, the strength of the ethylene resin (α2) itself is low, and the mechanical strength of the resulting resin composition may be low.

[0261] MFR serves as an indicator of the molecular weight of the ethylene resin (α2), and the weight-average molecular weight of the ethylene resin (α2), as determined by gel permeation chromatography (GPC) in terms of polystyrene, is preferably in the range of 40,000 to 900,000, more preferably 60,000 to 700,000, and particularly preferably 80,000 to 700,000.

[0262] The terminal structure of ethylene resins (α2) is usually substantially saturated hydrocarbon, and specifically, the proportion of unsaturated terminals in ethylene resins (α2) is usually less than 0.1 per 1000 carbon atoms.

[0263] [Resin composition] The resin composition of the present invention is a resin composition containing one or more of the above-mentioned propylene-based resin (α1) and ethylene-based resin (α2), and an olefin-based resin (β). The resin composition of the present invention may contain these components in any proportion.

[0264] The resin composition of the present invention may contain only one of the propylene resin (α1) or the ethylene resin (α2), but it is preferable to contain both the propylene resin (α1) and the ethylene resin (α2), and more preferably to contain the propylene resin (α1) and the ethylene resin (α2) in a mass ratio of 1:99 to 99:1. In the resin composition of the present invention containing both the propylene resin (α1) and the ethylene resin (α2), the inclusion of an olefin resin (β) allows for a homogeneous dispersion of the propylene resin (α1) and the ethylene resin (α2), which normally have poor compatibility.

[0265] Preferred examples of the olefin-based resin composition of the present invention include resin compositions having the following configurations (1) and (2). (1) Contains propylene resin (α1) and ethylene resin (α2) in a mass ratio of 51:49 to 99:1, The olefin resin (β) is contained in a total of 100 parts by mass of the propylene resin (α1) and the ethylene resin (α2), An olefin resin composition in which the side chains of the graft-type olefin polymer [R1] contained in the olefin resin (β) contain 80 to 98 mol% of structural units derived from ethylene and 2 to 20 mol% of structural units derived from propylene.

[0266] (2) Contains propylene resin (α1) and ethylene resin (α2) in a mass ratio of 49:51 to 1:99, The olefin resin (β) is contained in a total of 100 parts by mass of the propylene resin (α1) and the olefin resin (α2), An olefin resin composition wherein the content of structural units derived from ethylene contained in the side chains of the graft-type olefin polymer [R1] contained in the olefin resin (β) is 80 to 100 mol%.

[0267] In the olefin-based resin compositions of the above (1) and (2), the propylene-based resin (α1) and ethylene-based resin (α2) can be dispersed more homogeneously, resulting in a resin composition with excellent moldability and a molded article with excellent impact resistance, which is preferable.

[0268] The olefin resin composition according to the present invention may contain other components besides the propylene resin (α1), the ethylene resin (α2), and the olefin resin (β), to the extent that the objectives of the present invention are not impaired. Examples of other components include other resins, rubber, inorganic fillers, and additives. Examples of additives include weather-resistant stabilizers, heat-resistant stabilizers, antistatic agents, anti-slip agents, anti-blocking agents, anti-fogging agents, lubricants, pigments, dyes, plasticizers, anti-aging agents, hydrochloric acid absorbers, antioxidants, and crystal nucleating agents.

[0269] The olefin resin composition according to the present invention may be a used-recycled (PCR) blend. For example, a PCR blend may be used to prepare articles alone or in combination with a non-recycled (fresh / unused) polymer resin. The composition can be combined with non-recycled plastic resins in ratios such as 1:99 to 99:1 (e.g., 20:80 to 80:20, 40:60 to 60:40, etc.). Used plastic resins may be formed to form a resin composition for preparing articles.

[0270] <Molded body> The molded article according to the present invention is obtained by molding the olefin-based resin composition according to the present invention described above by a known molding method. For example, it can be obtained by known thermoforming methods such as extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calendering, and foam molding. The molded article according to the present invention is obtained from an olefin-based resin composition in which the components are highly dispersed, and therefore exhibits excellent impact resistance. In the present invention, even when both propylene-based resin and ethylene-based resin are contained, each component is more highly dispersed, resulting in a molded article with superior impact resistance compared to cases containing conventionally known compatibilizers.

[0271] The molded articles according to the present invention include door trims, rear package trims, instrument panels, gaskets, seat back garnishes, column covers, bumpers, fenders, side moldings, wheel covers, mudguards, mirror covers, instrument panels, exterior doors, hoods, spoilers, wind deflectors, hub caps, mirror frames, body panels, protective side moldings, shoe soles, shoe midsoles, insoles, soles, sandals, wire sheaths for automotive or equipment wires, wire insulators, other wire and cable coverings, and housings for home appliances. Gaskets, hot plates, rice cooker and pot bodies, washing machine and other home appliance components, battery containers and other 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 protective sheets, TV cabinets, stereo speaker boxes, video cabinets, various storage furniture, modular furniture and other home appliances and furniture products, doors, door frames, window frames, moldings, baseboards, opening frames and other housing components, kitchen and storage furniture doors and other furniture components, office floor mats, etc. Pet anti-slip pads, low-temperature heat-sealable films, easy-peel films, packaging films, individual pharmaceutical packaging materials, grips, gaskets, multi-layer hoses, infusion bottles, sanitary bottles such as shampoo bottles, cosmetic bottles and cases, caps, cap liners, beverage cap liners, stationery such as writing instruments, toys, leisure goods, disposable diapers, disposable underwear, sanitary napkins and other sanitary and elastic components, clothing cases, buckets, washbasins, cooking utensils, various other cases, containers, agricultural films, sports field equipment. Boat and surface vessel parts, garden furniture, roller bottles and culture medium bottles used for cultivation, diaper tubs, sterile wrap, cleaning cloths, bedding, food packaging film, retort food 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 instruments, medical cases, bandages, intravenous injection bags, pouches and liquid storage containers such as bottles, medical gowns and aprons, surgical drapes, covers for home appliances and residential lighting fixtures, automotive interior lighting covers,It can be used for LED lamp covers in electrical and electronic components, covers for other display devices, and sheets for encapsulating solar cells. [Examples]

[0272] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples unless it exceeds the essence of the invention.

[0273] <Measurement and evaluation methods> In the following examples and comparative examples, each physical property was measured or evaluated by the following methods.

[0274] [Molecular weight measurement] The molecular weight and molecular weight distribution of polymer samples were measured using a gel permeation chromatograph (HLC-8321 GPC / HT type, manufactured by Tosoh Corporation) with two TSKgel GMH6-HT columns and two TSKgel GMH6-HTL columns (both with an inner diameter of 7.5 mm and a length of 300 mm) connected in series. The mobile phase medium was o-dichlorobenzene with 0.025% by mass of BHT (Wako Pure Chemical Industries) added as an antioxidant. Measurements were taken at a sample concentration of 0.15% (W / V), a flow rate of 1.0 ml / min, and 140°C. Standard polystyrene samples with molecular weights from 590 to 20,600,000 were manufactured by Tosoh Corporation. The obtained chromatograms were analyzed using Waters Empower3 data processing software, employing known methods and calibration curves using standard polystyrene samples to calculate the number-average molecular weight (Mn), weight-average molecular weight (Mw), and dispersion (Mw / Mn).

[0275] [Measurement of melting point (Tm), heat of fusion (ΔH), and glass transition temperature (Tg)] The melting point (Tm), heat of fusion (ΔH), and glass transition temperature (Tg) were determined by DSC measurement under the following conditions. Using a differential scanning calorimeter (SII DSC220), approximately 5.0 mg of the 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. It was then cooled to 30°C at a cooling rate of 10°C / min, held at that temperature for 5 minutes, and then heated again to 200°C at a heating rate of 10°C / min. The endothermic peak observed during this second heating was defined as the melting peak, and the temperature at which the melting peak appeared was determined as the melting point (Tm). The heat of fusion (ΔH) was calculated by determining the area of ​​the melting peak. If the melting peak was multi-peaked, the area of ​​the entire melting peak was calculated. The glass transition temperature (Tg) is detected during the second heating by the bending of the DSC curve due to the change in specific heat, resulting in a parallel shift of the baseline. The temperature at the intersection of the tangent to the baseline at a lower temperature than this bend and the tangent to the point where the slope is maximum in the bent portion was defined as the glass transition temperature (Tg).

[0276] [Composition of each monomer component] The repeating units derived from each monomer of the ethylene-α-olefin copolymer were determined by analyzing the nuclear magnetic resonance spectrum of the polymer using the following method. (Measurement conditions) Equipment: JEOL ECX400P nuclear magnetic resonance spectrometer, nucleus measured: 1 H (400MHz); 13 C (125MHz), Measurement mode: Single pulse, Pulse width: 45° (5.25μsec), Number of points: 32k, Measurement range: 20ppm (-4~16ppm), Repeat time: 7.0 seconds, Number of accumulations: 64, Measurement solvent: Orthodichlorobenzene-d4, Sample concentration: Ca.20mg / 0.6mL, Measurement temperature: 120℃, Window function: Exponential (BF: 0.12Hz), Chemical shift reference: Orthodichlorobenzene (7.1ppm). The ratio of ethylene to propylene in the ethylene-propylene copolymer obtained in step (A) described in the examples below is 125 MHz. 13The peak intensities (integral values) derived from ethylene and propylene, obtained from 13C-NMR (JEOL ECX400P), were measured and quantified. Furthermore, the repeating units derived from each monomer of the propylene-ethylene copolymer of the olefin resin (β) obtained in step (B) were measured at 125 MHz. 13 The substances were measured and quantified by the intensity ratio (integral value) of the peaks derived from propylene and ethylene, obtained from 1C-NMR (JEOL ECX400P).

[0277] For the olefin resin (β-3) described later, the calibration curve was calculated from the correlation between the ethylene composition ratio (mol%) of the propylene-ethylene copolymer and the glass transition temperature [Tg] (°C). The calibration curve was created by carrying out polymerization in the same manner as in Example 3 described later, except that compound (A-1-1) was not used, and further by changing the supply ratio of propylene and ethylene in the continuous supply, several propylene-ethylene copolymer resins with different ethylene composition ratios were obtained. For the obtained propylene-ethylene copolymer resins, the ethylene composition ratio and glass transition temperature were measured using the method described above, and a calibration curve was created.

[0278] [Measurement of end-level vinyl content] The measurement of the terminal vinyl content of terminally unsaturated cyclic olefin copolymers is performed at 400 MHz. 1 The terminal vinyl ratio was quantified as the amount of vinyl groups in the total unsaturated amount at the terminals, based on the intensity ratio of peaks originating from unsaturated bonds obtained from 1H-NMR (JEOL ECX400P).

[0279] [Percentage of macromonomers] The proportion of macromonomers contained in the olefin resin (β) was calculated from the difference between the amount of macromonomers charged and the amount of olefin resin (β) obtained when the olefin resin was produced by the method described in the examples below. For the olefin resin (β-3) described later, the proportion of macromonomers contained in the olefin resin was calculated using the following method. Specifically, the proportion of macromonomers was calculated using a calibration curve based on the correlation between the heat of fusion ΔH (J / g) derived from macromonomers and the macromonomer content (weight %). Calibration Curve Preparation Method: In Example 3 described later, the procedure was carried out similarly except that dimethylsilylbis(2-methyl-4-phenylindenyl)zirconiumdimethyl was not used to obtain terminally unsaturated polyethylene. The obtained terminally unsaturated polyethylene, propylene, and ethylene were copolymerized using a polymerization catalyst containing dimethylsilylbis(2-methyl-4-phenylindenyl)zirconiumdimethyl by batch polymerization. Here, by changing the amount of terminally unsaturated polyethylene charged, several types of olefin resins with different proportions of macromonomers were collected. The macromonomer content (wt%) of the obtained olefin resins was determined from the ratio of the amount of terminally unsaturated polyethylene charged to the amount of olefin resin produced, and the heat of fusion ΔH (J / g) was measured by the method described above. A calibration curve was created from the correlation between these two values.

[0280] [Confirmation of graft-type olefin polymer [R1]] By separating the peaks in the chromatogram obtained by gel permeation chromatography, we confirmed that macromonomers were consumed and that graft-type olefin polymers [R1-1]~[R1-5], [R1'-4], and [R1'-5] were formed.

[0281] [Calculation of the number of side chains] The chromatogram obtained by gel permeation chromatography was analyzed by peak separation and calculated using the following formula. (Consumption of macromonomers ÷ Number-average molecular weight of macromonomers) ÷ (Content of main chain ÷ Number-average molecular weight of main chain)

[0282] <Reagents> The following reagents were used in the following examples and comparative examples. [reagent] Toluene was purified using an organic solvent purification system manufactured by GlassContour. The toluene solution for aluminoxane was a 20% by weight methylaluminoxane / toluene solution manufactured by Nippon Alkylaluminum Co., Ltd. Triisobutylaluminum was used, diluted with toluene (1.0 M) from Tosoh Finechem Co., Ltd.

[0283] [Example 1] <Manufacturing of olefin resin (β-1)> Process (A): Production of terminally unsaturated polyethylene (M-1) According to [Synthesis Example 2] of Japanese Patent Publication No. 2013-220992, a transition metal compound represented by the following formula (A-1-1) was synthesized and ethylene was polymerized using it to obtain terminally unsaturated polyethylene (M-1). The obtained terminally unsaturated polyethylene (M-1) had Mw = 9,660 and Mw / Mn = 2.25 in terms of polystyrene equivalent. 1 The single-ended unsaturation rate measured by 1H-NMR was 97.0 mol%. In the following formula (A-1-1), Et represents the ethyl group and Ph represents the phenyl group.

[0284] [ka]

[0285] Process (B): Dimethylsilyl-bis{1-(2-n-propyl-4-(9-phenanthryl)indenyl)}zirconium dichloride was synthesized according to the method disclosed in Japanese Patent Publication No. 7-286005. A 1 L stainless steel autoclave, thoroughly purged with nitrogen, was opened, and 15.0 g of the terminally unsaturated polyethylene (M-1) synthesized above was placed into the autoclave reaction vessel. The autoclave flange was closed, and nitrogen was flowed at room temperature for 15 hours. Under nitrogen flow, 500 mL of toluene and 0.90 mL (0.90 mmol) of a toluene solution of triisobutylaluminum (also written as iBu3Al) (1.00 mol / L) were added, and the autoclave was closed. The temperature was raised to 95°C and stirred for 5 minutes, then the temperature was lowered to 90°C. The ethylene partial pressure was increased to 0.10 MPaG, then the ethylene supply was stopped, and then the propylene partial pressure was increased to 0.42 MPaG, bringing the internal pressure of the autoclave to 0.60 MPaG. To this, 5.0 mL of toluene, 1.5 mL (0.15 mmol) of a toluene solution of triisobutylaluminum (0.1 mol / L), and 2.0 mL (0.00020 mmol) of a toluene solution of dimethylsilyl-bis{1-(2-n-propyl-4-(9-phenanthryl)indenyl)}zirconium dichloride (0.00010 mol / L) were added under pressure. Next, 8.0 mL (0.00080 mmol) of a toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl) borate (also written as Ph3CB(C6F5)4) (0.00010 mmol / L) was added under pressure to initiate polymerization. The pressure was maintained while continuously supplying propylene gas, and polymerization was carried out at 90°C for 3 minutes, after which polymerization was stopped by adding 5 mL of methanol under pressure. The resulting polymerization reaction solution was added to 3.0 L of methanol containing a small amount of hydrochloric acid to precipitate the polymer. The precipitate obtained by filtration was dried under reduced pressure at 130°C for 10 hours to obtain 21.2 g of olefin resin (β-1). Gel permeation chromatography confirmed the consumption of terminally unsaturated polyethylene and the formation of a graft-type olefin polymer [R1-1]. The analytical results of the obtained polymer are shown in Table 8.

[0286] [Example 2] <Manufacturing of olefin resin (β-2)> Step (A): The terminally unsaturated polyethylene (M-1) synthesized in Example 1 was used. Process (B): A 1 L stainless steel autoclave, thoroughly purged with nitrogen, was opened, and 15.0 g of terminally unsaturated polyethylene (M-1) synthesized in Example 1 was placed into the autoclave reaction vessel. The autoclave flange was closed, and nitrogen was flowed at room temperature for 15 hours. Under nitrogen flow, 500 mL of toluene and 0.90 mL (0.90 mmol) of a toluene solution of triisobutylaluminum (1.00 mol / L) were added, and the autoclave was closed. The temperature was raised to 95°C and stirred for 5 minutes, then the temperature was lowered to 90°C. The propylene partial pressure was increased to 0.45 MPaG, then the supply of propylene was stopped, and then the ethylene partial pressure was increased to 0.61 MPaG inside the autoclave by 0.07 MPaG. To this, 5.0 mL of toluene, 0.10 mL (0.10 mmol) of a toluene solution of triisobutylaluminum (1.0 mol / L), and 1.0 mL (0.00010 mmol) of a toluene solution of dimethylsilylbis(2-methyl-4-phenylindenyl)zirconiumdimethyl (0.00010 mol / L) were added under pressure. Next, 4.0 mL (0.00040 mmol) of a toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl)borate (0.00010 mmol / L) was added under pressure to start polymerization. The pressure was maintained while continuously supplying ethylene gas, and polymerization was carried out at 90°C for 5 minutes, after which polymerization was stopped by adding 5 mL of methanol under pressure. The obtained polymerization reaction solution was added to 3.0 L of methanol containing a small amount of hydrochloric acid to precipitate the polymer. The precipitate obtained by filtration was dried under reduced pressure at 130°C for 10 hours to obtain 19.9 g of olefin resin (β-2). Gel permeation chromatography confirmed the consumption of terminally unsaturated polyethylene and the formation of a graft-type olefin polymer [R1-2]. The analysis results of the obtained polymer are shown in Table 8.

[0287] [Example 3] <Manufacturing of olefin resin (β-3)> Steps (A) and (B): Dehydrated and purified n-heptane was supplied to a 950 mL continuous polymerizer from one of its feed ports at a rate of 1554 mL / hr. Simultaneously, a toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl) borate (0.3 mmol / L) was supplied at a rate of 163 mL / hr, a toluene solution of dimethylsilylbis(2-methyl-4-phenylindenyl) zirconium dimethyl (0.15 mmol / L) was supplied at a rate of 46 mL / hr, a toluene solution of the transition metal compound represented by formula (A-1-1) (0.15 mmol / L) was supplied at a rate of 76 mL / hr, and a toluene solution of triisobutylaluminum (8 mmol / L) was supplied at a rate of 61 mL / hr. (Total supply rate of components: 1900 mL / hr). Simultaneously, propylene was continuously supplied at a rate of 900 g / hr and ethylene at a rate of 170 g / hr from another supply port of the continuous polymerizer, and continuous solution polymerization was carried out under conditions of polymerization temperature of 110°C, total pressure of 0.82 MPa-G, residence time of approximately 30 min, and stirring speed of 970 rpm. The heptane solution of the propylene / ethylene / polyethylene graft copolymer produced in the polymerizer was continuously discharged at a flow rate of approximately 1900 mL / hr through an outlet provided on the upper wall of the polymerizer, and the polymerization reaction solution was collected in a collection bottle. The obtained polymerization reaction solution was dried under reduced pressure at 130°C for 10 hours. As a result, olefin resin (β-3) was obtained at a production rate of approximately 288 g / hr. Gel permeation chromatography confirmed that terminally unsaturated polyethylene was consumed, and that the graft-type olefin polymer [R1-3] was formed. The glass transition temperature (Tg) of the olefin resin (β-3) was -33.9°C, and the heat of fusion ΔH was 50.6 J / g. Other analytical results are shown in Table 8.

[0288] [Example 4] <Manufacturing of olefin resin (β-4)> Process (A): Production of terminally unsaturated polyethylene (M-4) A transition metal compound represented by the following formula (A-1-2) was synthesized according to a known method and used as a catalyst. In formula (A-1-2), Ph represents a phenyl group.

[0289] [ka]

[0290] In a 2.0 L glass reactor that had been thoroughly purged with nitrogen, 1500 mL of toluene was added. The reactor was then maintained at 25°C and stirred at 900 rpm while ethylene was continuously supplied at 120 L / hr to saturate both the liquid and gas phases. While continuing to supply ethylene continuously, 2.0 mL (2.0 mmol) of a toluene solution (1.00 mol / L) of modified methylaluminoxane (also written as MMAO) manufactured by Tosoh Fine Chemical Co., Ltd., and 1.0 mL (0.0003 mmol) of a toluene solution (0.0003 mol / L) of the above compound (A-1-2) were added. Polymerization was carried out at atmospheric pressure and 25°C for 30 minutes. Polymerization was stopped by adding a small amount of isobutanol. The resulting polymerization reaction solution was added to a large amount of methanol containing hydrochloric acid to precipitate terminally unsaturated polyethylene. The polymer obtained by filtration was dried under reduced pressure at 80°C for 10 hours to obtain 40.7 g of terminally unsaturated polyethylene (M-4). The weight-average molecular weight of the obtained terminally unsaturated polyethylene (M-4) was 42,700 in polystyrene equivalent. This was used as the side chain composition and molecular weight of the graft-type olefin polymer [R1-4] contained in the resin (β-4) described later. Furthermore, the number of terminal vinyl groups in the obtained terminally unsaturated polyethylene was 1.3 per 1000 carbon atoms, and the terminal vinyl content was 99%.

[0291] Process (B): Dimethylsilylbis(2-methyl-4-phenylindenyl)zirconiumdimethyl, used as a catalyst, was synthesized according to a known method. A 1 L stainless steel autoclave, thoroughly purged with nitrogen, was opened, and 24.0 g of the terminally unsaturated polyethylene (M-4) synthesized above was placed into the autoclave reaction vessel. The autoclave flange was closed, and nitrogen was flowed at room temperature for 15 hours. Under nitrogen flow, 500 mL of toluene and 4.0 mL (4.0 mmol) of a toluene solution of triisobutylaluminum (1.00 mol / L) were added, and the autoclave was closed. The temperature was raised to 97°C and stirred for 5 minutes, then the temperature was lowered to 90°C. The propylene partial pressure was increased to 0.60 MPaG, then the propylene supply was stopped, and then the ethylene partial pressure was increased to 0.80 MPaG inside the autoclave by 0.11 MPaG. To this, 5.0 mL of toluene, 0.50 mL (0.50 mmol) of a toluene solution of triisobutylaluminum (1.0 mol / L), and 7.0 mL (0.00070 mmol) of a toluene solution of dimethylsilylbis(2-methyl-4-phenylindenyl)zirconiumdimethyl (0.00010 mol / L) were added under pressure. Next, 2.8 mL (0.0028 mmol) of a toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl)borate (0.0010 mmol / L) was added under pressure to start polymerization. The pressure was maintained while continuously supplying ethylene gas, and polymerization was carried out at 90°C for 17 minutes, after which polymerization was stopped by adding 5 mL of methanol under pressure. The obtained polymerization reaction solution was added to 3.0 L of methanol containing a small amount of hydrochloric acid to precipitate the polymer. The precipitate obtained by filtration was dried under reduced pressure at 130°C for 10 hours to obtain 33.6 g of olefin resin (β-4). Gel permeation chromatography confirmed the consumption of terminally unsaturated polyethylene and the formation of graft-type olefin polymers [R1-4]. The analytical results of the obtained polymers are shown in Table 8.

[0292] [Example 5] <Manufacturing of olefin resin (β-5)> Process (A): Production of unsaturated ethylene propylene copolymer (M-5) A transition metal compound represented by the following formula (A-1-3) was synthesized according to a known method and used as a catalyst.

[0293] [ka] In a 1 L autoclave with a sufficiently nitrogen-purged internal volume, 500 mL of toluene and 0.60 mL (0.60 mmol) of a toluene solution of methylaluminoxane (1.00 mol / L) were added under nitrogen flow, the autoclave was closed, and the temperature was raised to 85°C. After increasing the propylene partial pressure by 0.25 MPaG, the supply of propylene was stopped, and then the ethylene partial pressure was increased by 0.47 MPaG to 0.80 MPaG inside the autoclave. To this, 5.0 mL of toluene, 0.15 mL (0.15 mmol) of a toluene solution of methylaluminoxane (1.0 mol / L), and 3.0 mL (0.00030 mmol) of a toluene solution of the transition metal compound represented by formula (A-1-3) (0.00010 mol / L) were injected under pressure to start polymerization. The pressure was maintained while continuously supplying ethylene gas, and polymerization was carried out at 85°C for 5 minutes, after which polymerization was stopped by injecting 5 mL of methanol under pressure. The resulting polymerization reaction solution was added to 3 L of methanol containing hydrochloric acid to precipitate the ethylene propylene copolymer. The copolymer obtained by filtration was dried under reduced pressure at 130°C for 10 hours to obtain 35.8 g of terminally unsaturated ethylene propylene copolymer (M-5). The weight-average molecular weight of the obtained terminally unsaturated ethylene propylene copolymer (M-5) was 38,600 in polystyrene terms. This was used as the side chain composition and molecular weight of the graft-type olefin polymer [R1-5] contained in the resin (β-5) described later. Furthermore, the number of terminal vinyl groups in the obtained terminally unsaturated ethylene propylene copolymer was 1.1 per 1000 carbon atoms, and the terminal vinyl content was 73%.

[0294] Process (B): A 1 L stainless steel autoclave, thoroughly purged with nitrogen, was opened, and 9.0 g of the terminally unsaturated ethylene propylene copolymer (M-5) synthesized above was placed into the autoclave reaction vessel. The autoclave flange was closed, and nitrogen was flowed at room temperature for 15 hours. Under nitrogen flow, 500 mL of toluene and 2.7 mL (2.7 mmol) of a toluene solution of triisobutylaluminum (1.00 mol / L) were added, and the autoclave was closed. The temperature was raised to 85°C and stirred for 5 minutes, then the temperature was lowered to 80°C. After increasing the propylene partial pressure by 0.53 MPaG, the supply of propylene was stopped, and then the ethylene partial pressure was increased by 0.20 MPaG to 0.80 MPaG inside the autoclave. To this, 5.0 mL of toluene, 0.30 mL (0.30 mmol) of a toluene solution of triisobutylaluminum (1.0 mol / L), and 4.0 mL (0.00040 mmol) of a toluene solution of dimethylsilylbis(2-methyl-4-phenylindenyl)zirconiumdimethyl (0.00010 mol / L) were added under pressure. Next, 1.6 mL (0.0016 mmol) of a toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl)borate (0.0010 mmol / L) was added under pressure to start polymerization. The pressure was maintained while continuously supplying ethylene gas, and polymerization was carried out at 80°C for 15 minutes, after which polymerization was stopped by adding 5 mL of methanol under pressure. The obtained polymerization reaction solution was added to 3.0 L of methanol containing a small amount of hydrochloric acid to precipitate the polymer. The precipitate obtained by filtration was dried under reduced pressure at 130°C for 10 hours to obtain 14.3 g of olefin resin (β-5). Gel permeation chromatography confirmed the consumption of terminally unsaturated ethylene propylene polymers and the formation of graft-type olefin polymers [R1-5]. The analytical results of the obtained polymers are shown in Table 8.

[0295] [Comparative Example 1] <Manufacturing of olefin resin (β'-1)> In Example 2, the procedure was carried out similarly except that the toluene solution of dimethylsilylbis(2-methyl-4-phenylindenyl)zirconiumdimethyl (0.00010 mol / L) was changed to 2.0 mL (0.00020 mmol) and the toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl)borate (0.00010 mmol / L) was changed to 8.0 mL (0.00080 mmol), yielding 13.5 g of olefin resin (β'-1). The analysis results of the obtained polymer are shown in Table 8.

[0296] [Comparative Example 2] <Manufacturing of olefin resin (β'-2)> The procedure was carried out in the same manner as in Step (A) of Example 3 to obtain 40.7 g of olefin resin (β'-2). The analysis results of the obtained polymer are shown in Table 8.

[0297] [Comparative Example 3] <Manufacturing of olefin resin (β'-3)> The procedure was carried out in the same manner as in Step (A) of Example 4 to obtain 35.8 g of olefin resin (β'-3). The analysis results of the obtained polymer are shown in Table 8.

[0298] [Comparative Example 4] <Manufacturing of olefin resin (β'-4)> The procedure was carried out similarly to Example 2, except that the propylene partial pressure was increased by 0.33 MPaG and the ethylene partial pressure by 0.17 MPaG, resulting in a total pressure of 0.59 MPaG inside the autoclave. 19.3 g of resin (β'-4) containing the graft-type olefin polymer [R1'-4] was obtained. The analysis results of the obtained polymer are shown in Table 8.

[0299] [Comparative Example 5] <Manufacturing of olefin resin (β'-5)> Process (A): Production of unsaturated ethylene propylene copolymer (M'-5) In the production of the terminally unsaturated ethylene propylene copolymer (M-5) in Example 5 (Step A), the procedure was carried out similarly except that the propylene partial pressure was changed to 0.47 MPaG, the ethylene partial pressure to 0.25 MPaG, and the toluene solution of the above compound (A-1-3) (0.00010 mol / L) was changed to 8.0 mL (0.00080 mmol). 31.6 g of terminally unsaturated ethylene propylene copolymer (M'-5) was obtained. The weight-average molecular weight of the obtained terminally unsaturated ethylene propylene copolymer (M'-5) was 15,600 in polystyrene terms. This was used as the side chain composition and molecular weight of the graft-type olefin polymer [R1'-5] contained in the resin (β'-5) described later. Furthermore, the number of terminal vinyl groups in the obtained terminally unsaturated ethylene propylene copolymer was 1.2 per 1000 carbon atoms, and the terminal vinyl content was 32%. Process (B): The procedure was carried out similarly to Example 5, except that the terminally unsaturated ethylene propylene copolymer was replaced with 25.0 g of the terminally unsaturated ethylene propylene copolymer (M'-5) synthesized above. 29.1 g of resin (β'-5) containing the graft-type olefin polymer [R1'-5] was obtained. The analysis results of the obtained polymer are shown in Table 8.

[0300] [Table 8]

[0301] [Examples 6-12 and Comparative Examples 6-17] Preparation of olefin resin compositions An olefin-based resin composition was prepared by placing the raw materials listed in Tables 9 and 10 into a Laboplast Mill manufactured by Toyo Seiki Seisakusho Co., Ltd., in the mixing ratios (parts by mass) listed in Tables 9 and 10, and melt-kneading them for approximately 5 minutes at 200°C and 60 rpm. The raw materials, olefin resins (β-1) to (β-5) and (β'-1) to (β'-5), were obtained in Examples 1 to 5 and Comparative Examples 1 to 5, respectively. The following propylene-based resins (α1) and ethylene-based resins (α2) were used as raw materials.

[0302] [Propylene resin (α1)] Commercially available homopropylene (manufactured by Prime Polymer Co., Ltd., product name: Prime PolyPro F113G, MFR (230℃, 2.16kg load) = 3.0g / 10min) was used. [Ethylene-based resin (α2)] Commercially available metallocene linear low-density polyethylene (manufactured by Prime Polymer Co., Ltd., product name: Evolu SP2540, MFR (190℃, 2.16kg load) = 3.8g / 10min) was used.

[0303] Measurement of molded material properties The physical properties of the molded articles of the prepared olefin resin compositions were measured by the following method. The results are shown in Tables 9 and 10. [Izod impact strength] An olefin resin composition was heated for 6 minutes using a hydraulic hot press molding machine set to 200°C, and then molded for 2 minutes under a pressure of 10 MPa. Afterward, a 3 mm thick sheet was produced by cooling for 2 minutes at 20°C under a pressure of 10 MPa. After 72 hours at room temperature following molding, the Izod impact strength was measured from the prepared sheets under the following conditions, in accordance with ASTM D256. <Test Conditions> Hammer capacity: 3.92J Swing angle: 149.0°C A notch is a machined part. Temperature: 23℃

[0304] [Transmission electron microscope observation] An olefin resin composition was heated for 6 minutes using a hydraulic hot press molding machine set to 200°C, and then molded for 2 minutes under a pressure of 10 MPa. Afterward, a 3 mm thick sheet was produced by cooling for 2 minutes at 20°C under a pressure of 10 MPa. The obtained molded bodies were cut into 0.5 mm square pieces and stained with ruthenic acid (RuO4). Further, using an ultramicrotome equipped with a diamond knife, these pieces were prepared as ultrathin sections with a film thickness of approximately 100 nm. Carbon was deposited onto these ultrathin sections, and the phase structure was observed using a transmission electron microscope (Hitachi High-Tech H-7650).

[0305] [Table 9]

[0306] [Table 10]

[0307] As shown in Tables 9 and 10, the olefin resin compositions of the examples were found to have higher Izod impact strength and superior impact resistance compared to the olefin resin compositions of the comparative examples.

[0308] Figures 1, 2, and 3 show the results of observing the phase structures of the olefin resin compositions obtained in Example 11 and Comparative Examples 12 and 13 using a transmission electron microscope. All of them have a phase separation structure consisting of a phase formed by a propylene resin component (bright field) and a phase formed by an ethylene resin component (dark field). However, in Example 11, the dispersed particle size of the phase formed by the propylene resin component is smaller and better dispersed than in Comparative Examples 12 and 13. From these results, it was confirmed that the presence of graft-type olefin polymer [R1-4] improves compatibility and enhances the impact resistance of the olefin resin composition.

Claims

1. An olefin resin composition containing a propylene resin (α1), an ethylene resin (α2), and an olefin resin (β), The olefin resin (β) is The main chain is composed of a copolymer of propylene and ethylene, with a content of 78 to 99 mol% of structural units derived from propylene and a content of 1 to 22 mol% of structural units derived from ethylene, and Side chains composed of ethylene homopolymers or copolymers of ethylene and propylene, with a content of 80-100 mol% of structural units derived from ethylene and 0-20 mol% of structural units derived from propylene. A graft-type olefin polymer [R1] having the following Olefin-based resin composition.

2. The olefin resin composition according to claim 1, wherein the olefin resin (β) contains 10 to 93% by weight of structural units derived from propylene.

3. The olefin resin composition according to claim 1, wherein the weight-average molecular weight of the copolymer constituting the main chain of the graft-type olefin polymer [R1], as determined by gel permeation chromatography (GPC) as a styrene equivalent, is in the range of 50,000 to 1,000,000.

4. The olefin resin composition according to claim 1, wherein the weight-average molecular weight of the polymer or copolymer constituting the side chain of the graft-type olefin polymer [R1], as determined by gel permeation chromatography (GPC) as a styrene equivalent, is in the range of 5,000 to 200,000.

5. The olefin resin composition according to claim 1, wherein the total weight-average molecular weight, which is the product of the weight-average molecular weight per side chain, determined as a styrene equivalent value by gel permeation chromatography (GPC), and the number of side chains per main chain, is in the range of 15,000 to 500,000.

6. A molded article of an olefin resin composition according to any one of claims 1 to 5.

Images