JP6814272B2 - Olefin-based resin, method for producing the resin, pellets, thermoplastic elastomer and crosslinked rubber - Google Patents

Description

The present invention relates to an olefin resin, a method for producing the resin, pellets containing the resin, a thermoplastic elastomer, and a crosslinked rubber.

Ethylene / α-olefin / polyene copolymer, typically ethylene-propylene-diene rubber (EPDM or EPT), is a copolymer of ethylene and α-olefin (propylene) in ethylene / α-olefin rubber. A small amount of polyenes such as ethylidene norbornene (ENB), 1,4-hexadiene (1,4-HD), or dicyclopentadiene (DCP) is introduced as a third component to give a double bond. ..

EPDM, which is a typical copolymer, has excellent workability, weather resistance, ozone resistance, heat resistance, cold resistance, chemical resistance, and electrical characteristics, as well as automobile parts (hoses, weather) due to its functionality and economy. Used for strips, various sealing materials, bellows, etc.), civil engineering and construction materials, electric wires and cables, industrial chemicals, belts, tires, tubes, hoses, gaskets, electric wires, waterproof materials, resin blends, etc.

Thermoplastic Vulcanizates (TPV), which is obtained by dynamically cross-linking EPDM with a crystalline polyolefin resin (mainly polypropylene), is a material that can simplify the molding process, consume less energy, and is recyclable. Since scraps and defective products can be reused, they have come to be widely used as high-performance materials in the field of vulcanized rubber. TPV is a polymorphic polymer material characterized by a sea-island structure in which crosslinked rubber particles are finely dispersed as domains (island phases) in a thermoplastic resin which is a matrix (sea phase). At room temperature, the domain gives TPV the function of vulcanized rubber, and at high temperature, the matrix flows and plastic deformation becomes possible, so that a molded product can be easily obtained by a molding machine similar to that of thermoplastic.

The TPV structure that gives EPDM a crystal structure is an unexplored region, but in view of the generally well-proven rubber properties of block copolymers in which crystalline and amorphous segments are chemically bonded. It is considered that there is a possibility of improving various physical properties such as rubber elasticity and mechanical properties of TPV.

Although there are few examples of reporting such EPDM, for example, EPDM having a linear block structure of crystalline polyethylene and an amorphous elastomer is disclosed in Patent Document 1 and Patent Document 2. In these documents, a manufacturing method in which each segment is sequentially synthesized using a vanadium catalyst consisting of a reaction mixture of a vanadium compound and an organic aluminum compound in order to synthesize a crystal-crystal block copolymer in which a diene is introduced is used. It is used. The production ratio of block copolymers in the produced polymer is not clear, but due to the performance of the catalyst, low temperature polymerization of about 10 ° C. is forced to maintain the living polymerizable property, and a large amount of catalyst is required, resulting in low productivity. Further, these documents do not show the effect of improving the physical characteristics of the polypropylene resin as TPV.

Special Table No. 09-511767 Special Table No. 10-504581

An object to be solved by the present invention is to provide a thermoplastic elastomer having excellent rubber elasticity and mechanical properties, and an olefin resin capable of producing the thermoplastic elastomer.

As a result of diligent studies, the present inventors have found that the above-mentioned problems can be solved by a specific olefin-based resin containing a graft-type olefin-based polymer having an ethylene polymer as a side chain.
Configuration examples of the present invention are the following [1] to [8].

[1] An olefin resin (β) that satisfies the following requirements (I) to (IV).
(I) A graft-type olefin polymer [R1] having a main chain composed of an ethylene / α-olefin / polyene copolymer and a side chain composed of an ethylene polymer (II) a graft-type olefin polymer [ R1] has an average of 0.5 to 20 side chains per 1000 carbon atoms in the main chain polymer molecular chain. (III) In the range of 60 to 130 ° C. as measured by differential scanning calorimetry (DSC). Indicates the melting temperature (Tm), and the heat of fusion ΔH is in the range of 5 to 150 J / g. (IV) The glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) is in the range of -80 to -30 ° C. is there

[2] The olefin resin (β) according to [1], wherein the weight average molecular weight of the side chain of the grafted olefin polymer [R1] is in the range of 500 to 10000.

[3] The method for producing an olefin resin (β) according to [1] or [2], which comprises the following (a) or (b).
(A) A step of polymerizing ethylene in the presence of a catalyst containing the following compounds (B) and (C) [a-1].
In the presence of a catalyst containing the following compounds (A) and (C), ethylene, at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms, polyene, and step [a-1]. Method including step [a-2] of copolymerizing with the reaction product of (b) In the presence of an olefin polymerization catalyst containing each of the following compounds (A) to (C), ethylene and 3 carbon atoms A method including a step of copolymerizing a component containing polyene with at least one α-olefin selected from ~ 20 α-olefins (A) a crosslinked metallocene compound represented by the following formula (I) (B) below. Transition metal compound represented by the formula [B] (C) (C-1) Organic metal compound, (C-2) Organic aluminum oxy compound, and (C-3) Crosslinked metallocene compound (A) or transition metal compound. At least one compound selected from a compound that reacts with (B) to form an ion pair.

（式（Ｉ）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁸、Ｒ⁹およびＲ¹²はそれぞれ独立に、水素原子、炭化水素基、ケイ素含有基またはケイ素含有基以外のヘテロ原子含有基を示し、Ｒ¹〜Ｒ⁴のうち隣接する二つの基同士は互いに結合して環を形成していてもよい。
Ｒ⁶およびＲ¹¹は水素原子、炭化水素基、ケイ素含有基およびケイ素含有基以外のヘテロ原子含有基から選ばれる同一の原子または同一の基であり、Ｒ⁷およびＲ¹⁰は水素原子、炭化水素基、ケイ素含有基およびケイ素含有基以外のヘテロ原子含有基から選ばれる同一の原子または同一の基であり、Ｒ⁶およびＲ⁷は互いに結合して環を形成していてもよく、Ｒ¹⁰およびＲ¹¹は互いに結合して環を形成していてもよく；ただし、Ｒ⁶、Ｒ⁷、Ｒ¹⁰およびＲ¹¹が全て水素原子であることはない。
Ｒ¹³およびＲ¹⁴はそれぞれ独立にアリール基を示す。
Ｍはチタン原子、ジルコニウム原子またはハフニウム原子を示す。
Ｙ¹は炭素原子またはケイ素原子を示す。
Ｑはハロゲン原子、炭化水素基、ハロゲン化炭化水素基、炭素数４〜１０の中性の共役もしくは非共役ジエン、アニオン配位子または孤立電子対で配位可能な中性配位子を示し、ｊは１〜４の整数を示し、ｊが２以上の整数の場合は複数あるＱはそれぞれ同一でも異なっていてもよい。）

(In formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² are independently other than hydrogen atom, hydrocarbon group, silicon-containing group or silicon-containing group, respectively. the indicated heteroatom-containing group, two groups adjacent to each other among R ¹ to R ⁴ may be bonded to each other to form a ring.
R ⁶ and R ¹¹ are the same atom or the same group selected from heteroatom-containing groups other than hydrogen atom, hydrocarbon group, silicon-containing group and silicon-containing group, and R ⁷ and R ¹⁰ are hydrogen atom and hydrocarbon. It is the same atom or the same group selected from a group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group, and R ⁶ and R ⁷ may be bonded to each other to form a ring, and R ¹⁰ and R ¹¹ may be bonded to each other to form a ring; however, R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.
R ¹³ and R ¹⁴ each independently represent an aryl group.
M represents a titanium atom, a zirconium atom or a hafnium atom.
Y ¹ represents a carbon atom or a silicon atom.
Q indicates a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or unconjugated diene having 4 to 10 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair. , J indicates an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Qs may be the same or different. )

（式［Ｂ］中、Ｍは周期表第４または５族の遷移金属原子を示す。ｍは１〜４の整数を示す。Ｒ¹は、炭素原子数１〜４の非環式炭化水素基（Ｃ_n'Ｈ_2n'+1；ｎ’＝１〜４）を示す。Ｒ²〜Ｒ⁵は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭化水素基、ハロゲン化炭化水素基、ヘテロ環式化合物残基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基またはスズ含有基を示し、これらのうちの２個以上が互いに連結して環を形成していてもよい。Ｒ⁶〜Ｒ⁸は独立に、炭化水素基またはハロゲン化炭化水素基であって、そのうち少なくとも一つは芳香族炭化水素基またはハロゲン化芳香族炭化水素基であり、また、ｍが２以上の場合にはＲ²〜Ｒ⁸のうち２個の基が連結されていてもよい。ｎは、Ｍの価数を満たす数であり、Ｘは、水素原子、ハロゲン原子、炭化水素基、酸素含有基、イオウ含有基、窒素含有基、ホウ素含有基、アルミニウム含有基、リン含有基、ハロゲン含有基、ヘテロ環式化合物残基、ケイ素含有基、ゲルマニウム含有基またはスズ含有基を示し、ｎが２以上の場合には、互いに同一であっても、異なっていてもよく、また、Ｘで示される複数の基は互いに結合して環を形成してもよい。）

(In the formula [B], M represents a transition metal atom of Group 4 or 5 of the periodic table. M represents an integer of 1 to 4. R ¹ is an acyclic hydrocarbon group having 1 to 4 carbon atoms. _{(C n 'H 2n' +} 1; n '= 1~4) .R 2 ~R 5 showing a may be the same or different from each other, a hydrogen atom, a halogen atom, a hydrocarbon group, halogenated hydrocarbon Group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group or tin-containing group, and two or more of them. May be linked to each other to form a ring. R ^{6 to} R ⁸ are independently hydrocarbon groups or halogenated hydrocarbon groups, at least one of which is an aromatic hydrocarbon group or halogenated aromatic. It is a group hydrocarbon group, and when m is 2 or more, two groups of R ^{2 to} R ⁸ may be linked. N is a number satisfying the valence of M, and X is Is 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, and a silicon-containing group. , Germanium-containing group or tin-containing group, and when n is 2 or more, they may be the same or different from each other, and a plurality of groups represented by X are bonded to each other to form a ring. May be.)

[4] The method for producing an olefin resin (β) according to [3], wherein the copolymerization is carried out by a solution polymerization method in a temperature range of 80 to 300 ° C.

[5] Pellets containing the olefin resin (β) according to [1] or [2].

[6] A thermoplastic elastomer which is a crosslinked product of a composition containing the olefin resin (β), the crystalline polyolefin resin (α), and the crosslinking agent (γ) according to [1] or [2].
[7] A thermoplastic elastomer which is a crosslinked product using the pellets according to [5].

[8] A crosslinked rubber which is a crosslinked product of a composition containing the olefin resin (β) and the crosslinking agent (γ) according to [1] or [2].

According to the olefin-based resin according to the present invention, a thermoplastic elastomer having an excellent balance between rubber elasticity and mechanical properties in the room temperature to low temperature range, for example, hardness, modulus, breaking strength and breaking elongation, and excellent molding processability and fluidity. Can be easily obtained.

≪Olefin resin (β) ≫
The olefin resin (β) may be composed of only one type of olefin polymer, or may be composed of two or more types of olefin polymers, but the following requirements (I) to (IV) are satisfied. It is characterized by satisfying all.
(I) A graft-type olefin polymer [R1] having a main chain composed of an ethylene / α-olefin / polyene copolymer and a side chain composed of an ethylene polymer (II) a graft-type olefin polymer [ R1] has an average of 0.5 to 20 side chains per 1000 carbon atoms in the main chain polymer molecular chain. (III) In the range of 60 to 130 ° C. as measured by differential scanning calorimetry (DSC). Indicates the melting temperature (Tm), and the heat of fusion ΔH is in the range of 5 to 150 J / g. (IV) The glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) is in the range of -80 to -30 ° C. In the following, these requirements (I) to (IV) will be specifically described.

In the present invention, the olefin resin (β) means a component obtained during the synthesis of the polymer [R1]. That is, the olefin resin (β) contains an ethylene / α-olefin / polyene copolymer that is not a graft copolymer, the following macromonomer, and an antioxidant as a component obtained during the synthesis of the polymer [R1]. Can include additives such as.
However, the olefin resin (β) contains the polymer [R1] as a main component, and specifically, for example, preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more. Include in the amount of.

[Requirement (I)]
The olefin resin (β) contains an olefin polymer [R1] as an essential component. The polymer [R1] is a graft copolymer having a main chain and a side chain, and can be synthesized, for example, by a polymerization method described later.

The "graft copolymer" in the present invention refers to a T-type polymer or comb-shaped polymer in which one or more side chains are bonded to the main chain. The polymer [R1] is not particularly limited as long as it has a side chain made of an ethylene polymer, and the side chain may contain a repeating unit other than ethylene-derived as long as it does not deviate from the gist of the present invention.

Since the polymer [R1] has a crystalline side chain structure even though the main chain structure is an amorphous (or low crystalline) ethylene / α-olefin / polyene copolymer. The olefin resin (β) of the present invention is less sticky than a general ethylene / α-olefin / polyene copolymer (for example, ethylene / propylene / diene copolymer), and the resin (β) can be used. When the pellet containing the pellet is prepared, the blocking resistance of the pellet becomes good.

The main chain and side chains of the polymer [R1] preferably satisfy the following requirements (i) to (v).
(I) The main chain is composed of a copolymer of ethylene, at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms, and polyene, and a repeating unit derived from the ethylene. It contains 60 to 97 mol% with respect to all the repeating units constituting the main chain.
(Ii) The main chain contains 0.1 to 10.0 mol% of repeating units derived from the polyene.
(Iii) The weight average molecular weight of the main chain is 20000-400000.
(Iv) The side chain consists of repeating units derived from ethylene.
(V) The weight average molecular weight of the side chain is in the range of 500 to 10,000.
Hereinafter, these requirements (i) to (v) will be specifically described.

[Requirement (i)]
The main chain of the polymer [R1] is composed of ethylene, at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms, and a copolymer of polyene, and is flexible as a rubber property. It is a site that provides properties and good low temperature characteristics.

Here, specific examples of α-olefin having 3 to 20 carbon atoms that copolymerize with ethylene include propylene, 1-butene, 1-pentene, 2-methyl-1-propene, and 2-methyl-1-butene. 3-Methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl- 1-Pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1 -Octen, ethyl-1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, 1-nonene, Examples thereof include 1-decene, 1-undecene, and 1-dodecene.

More preferably, it is an α-olefin having 3 to 10 carbon atoms, and particularly preferably, it is an α-olefin having 3 to 8 carbon atoms. Specifically, linear olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene, 4-methyl-1-pentene and 3-methyl-1-pentene, Branched olefins such as 3-methyl-1-butene can be mentioned, with propylene, 1-butene, 1-pentene, 1-hexene and 1-octene being preferred.

The ratio of the repeating unit derived from ethylene in the main chain of the polymer [R1] is 60 to 97 mol%, preferably 60 to 95 mol%, more preferably 65 to 90 mol% with respect to all the repeating units contained in the main chain. Is the range of.
When the molar ratio of the repeating unit derived from ethylene in the main chain is within the above range, the olefin resin (β) has high flexibility and excellent low temperature characteristics. Therefore, the olefin resin (β) was used. The thermoplastic elastomer obtained by dynamic cross-linking also has excellent flexibility and low temperature characteristics. On the other hand, if the amount of repeating units derived from ethylene exceeds the above range, the resin tends to be inferior in flexibility and low temperature characteristics. Therefore, the thermoplastic elastomer obtained by dynamic crosslinking using the resin also has flexibility and low temperature. It tends to be inferior in characteristics.

The molar ratio of the repeating unit derived from ethylene in the main chain of the polymer [R1] is the concentration of ethylene and the concentration of α-olefin and polyene present in the polymerization reaction system in the step of producing the main chain. It can be adjusted by controlling the ratio.

[Requirements (ii)]
The main chain of the polymer [R1] contains 0.1 to 10.0 mol%, preferably 0.2 to 7.5 mol%, more preferably 0.3 to 5 mol% of the repeating unit derived from the polyene.

As the polyene, conjugated polyenes and non-conjugated polyenes can be used. These polyenes may be used alone or in combination of two or more.

Specific examples of the conjugated polyene include 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadien, 1-phenyl-1, 3-butadiene, 1-phenyl-2,4-pentadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-butyl-1,3-butadiene, 2-pentyl- Examples thereof include 1,3-butadiene, 2-hexyl-1,3-butadiene, 2-heptyl-1,3-butadiene, 2-octyl-1,3-butadiene, and 2-phenyl-1,3-butadiene. Among these, 1,3-butadiene and isoprene are particularly preferable because they have excellent copolymerizability.

Specific examples of the non-conjugated polyene include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and 4 , 5-Dimethyl-1,4-hexadien, 7-methyl-1,6-octadien, 8-methyl-4-ethylidene-1,7-norbornene and 4-ethylidene-1,7-undecadien, etc. Diene; methyltetrahydroinden, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropyriden-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2 -Cyclic non-conjugated diene such as -norbornene, 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclopentadiene and norbornene; 2,3-diisopropyridene-5-norbornene , 2-Etylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornene, 4-ethylidene-8-methyl-1,7-nonadien and the like. Of these, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene are preferable.

Although it is difficult to directly measure the composition ratio of ethylene / α-olefin / polyene only in the main chain of the polymer [R1], it can be calculated by, for example, the following method.
In light of the production conditions of the olefin resin (β) to be measured, an ethylene / α-olefin / polyene copolymer containing only the main chain moiety of the polymer [R1] was separately synthesized under reasonable conditions to obtain the obtained product. By analyzing the composition ratio of the copolymer, the composition ratio of the main chain of the polymer [R1] can be indirectly obtained. Reasonable conditions include the concentrations of ethylene, α-olefin and polyene in the polymerization system, the molecular abundance ratio of ethylene and hydrogen, and the like, in principle, a polymer equivalent to the main chain moiety of the polymer [R1] is produced. It is a condition. Specifically, as a method for producing an olefin resin (β), an ethylene polymer (macromonomer) corresponding to the side chain of the polymer [R1] is synthesized in advance, and the macromonomer, ethylene, and α-olefin are used. When a method of copolymerizing with polyene is adopted, polymerization under the same conditions except that a macromonomer is not used can be mentioned.
It can also be evaluated by discounting the composition ratio corresponding to the macromonomer or the side chain from the total composition ratio of the resin (β).

[Requirements (iii)]
The weight average molecular weight of the main chain of the polymer [R1] is 20000 to 400000, preferably 30,000 to 300,000, and more preferably 50,000 to 200,000.
When the weight average molecular weight of the main chain of the polymer [R1] is within the above range, the fluidity, breaking strength, and the like when the olefin resin (β) and the crystalline polyolefin resin (α) are dynamically crosslinked are used. A thermoplastic elastomer having excellent basic physical properties such as elongation at break and rubber elasticity can be easily obtained. On the other hand, when the weight average molecular weight is less than the above range, the rubber elasticity of the obtained thermoplastic elastomer tends to decrease, and when it exceeds the above range, the desired physical properties are well-balanced due to poor dispersion of the olefin resin (β). It tends to be difficult to obtain the thermoplastic elastomer having.

The weight average molecular weight of the main chain of the polymer [R1] can be adjusted by controlling the ethylene concentration in the polymerization system in the production process described later. Examples of the ethylene concentration control method include ethylene partial pressure adjustment and polymerization temperature adjustment. Further, the weight average molecular weight of the main chain of the polymer [R1] can be adjusted by supplying hydrogen into the polymerization system.

The weight average molecular weight of the main chain of the polymer [R1] is the same as that of ethylene / α-olefin / polyene according to the method for calculating the composition ratio of ethylene / α-olefin / polyene in the main chain of the polymer [R1]. A polymer may be synthesized and the weight average molecular weight of the polymer may be determined by a conventional method, for example, gel permeation chromatography (GPC), or a macromonomer or macromonomer may be obtained from the molecular weight of the resin (β). It can also be evaluated by discounting the influence of the side chain.

[Requirements (iv)]
The side chain of the polymer [R1] is substantially an ethylene polymer composed of repeating units derived from ethylene, and is preferably composed of a crystalline ethylene polymer chain.
An ethylene polymer composed of repeating units substantially derived from ethylene has a molar ratio of repeating units derived from ethylene of preferably 95.0 to 100 mol% with respect to all the repeating units contained in the ethylene polymer. It is a polymer consisting of 98.0 to 100 mol%, more preferably 99.5 to 100 mol%. That is, it may contain an α-olefin other than ethylene as long as its role and characteristics are not impaired.

The reason why the thermoplastic elastomer obtained by dynamic cross-linking using an olefin resin (β) exhibits excellent rubber elasticity is that the side chain of the polymer [R1] acts as a pseudo-crosslink point of the rubber phase and the surface. It is presumed that this is because it plays a role of improving hardness and increasing rigidity, and also has an effect of exhibiting excellent rubber elasticity from high temperature to low temperature near the melting point of the polymer [R1].

The fact that the side chain of the polymer [R1] is composed of a crystalline ethylene polymer has a melting peak in the range of 60 to 130 ° C. in the differential scanning calorimetry (DSC) of the olefin resin (β) according to the present invention. Is observed, that is, it can be confirmed by having a melting temperature (Tm) in the range of 60 to 130 ° C.

[Requirement (v)]
The weight average molecular weight of the side chain of the polymer [R1] is in the range of 500 to 10000, preferably in the range of 500 to 5000, and more preferably in the range of 500 to 3000.

When the weight average molecular weight of the side chain of the polymer [R1] is within the above range, the thermoplastic elastomer obtained by dynamic cross-linking using an olefin resin (β) is a polymer while having high hardness and high rigidity. It has excellent rubber elasticity from high temperature to low temperature near the melting point of [R1].

When the weight average molecular weight of the side chain of the polymer [R1] is less than the above range, the thermoplastic elastomer obtained by using the olefin resin (β) tends to have a decrease in surface hardness and rigidity, and a decrease in rubber elasticity. is there. It is speculated that this may be because the role of the side chain component as a pseudo-crosslink point is reduced. On the other hand, when the weight average molecular weight exceeds the above range, the mechanical properties such as the rigidity, surface hardness, and rubber elasticity of the obtained thermoplastic elastomer are lowered due to the decrease in the number of side chains with respect to the main chain, or the polymer [R1]. ], Since the relative amount of the main chain portion decreases, the rubber elasticity may decrease significantly.

The polymer [R1] can be obtained by copolymerizing a macromonomer, which is an ethylene polymer, with ethylene, α-olefin, and polyene. In this case, the weight average molecular weight of the macromonomer corresponds to the weight average molecular weight of the side chain of the polymer [R1]. Therefore, the weight average molecular weight of the side chain of the polymer [R1] is determined by analyzing the molecular weight of the macromonomer separated as the elution component on the low weight side by GPC measurement of the olefin resin (β), or by pre-synthesizing it. It can be obtained by performing GPC measurement of the macromonomer.

As a method for adjusting the weight average molecular weight of the side chain of the polymer [R1], when a transition metal compound is used as a catalyst for synthesizing a macromonomer described later, a method of changing the type of the transition metal compound or , A method of adjusting the polymerization conditions can be mentioned.

The polymer [R1] contained in the olefin resin (β) satisfies the above-mentioned requirements (i) to (v), and thus is a thermoplastic elastomer obtained by dynamic crosslinking using the olefin resin (β). Is characterized by satisfying all the properties of fluidity, hardness, modulus, breaking strength, breaking elongation and rubber elasticity at a high level. The polymer [R1] more preferably further satisfies the following requirements (vi).

[Requirements (vi)]
The number of methyl branches in the side chain of the polymer [R1] is less than 0.1 per 1000 carbons contained in the side chain.
When the number of methyl branches in the side chain is within the above range, the crystallinity of the ethylene polymer in the side chain is further enhanced, and the thermoplastic elastomer obtained by dynamic cross-linking using an olefin resin (β) has hardness and modulus. Is high and has excellent rubber elasticity.

The number of methyl branches is a known method using isotope carbon nuclear magnetic resonance analysis ( ¹³ C-NMR) using a macromonomer obtained by the same method as described in the above-mentioned “Requirement (v)”. For example, it can be measured by the method published in JP-A-2006-233207.

As a method for adjusting the number of methyl branches in the side chain of the polymer [R1], when a transition metal compound is used as a catalyst for synthesizing a macromonomer described later, a method of changing the type of the transition metal compound is used. Can be mentioned.

[Requirement (II)]
As described above, the olefin resin (β) contains the polymer [R1], and the side chains of the polymer [R1] average 0.5 to 20 per 1000 carbon atoms in the main chain polymer molecular chain. There are (books), preferably 0.5 to 15 on average, and more preferably 0.5 to 10 on average.

Since the side chain is introduced into the main chain in the above range, the thermoplastic elastomer obtained by dynamic cross-linking using an olefin resin (β) has high hardness and high modulus, and is of the polymer [R1]. Excellent rubber elasticity from high temperature to low temperature near the melting point.

On the other hand, when the number of side chains is less than the above range, the effect of the physical cross-linking point by the side chains is reduced, so that the thermoplastic elastomer obtained by dynamic cross-linking with the olefin resin (β) has rigidity. Hardness or rubber elasticity may decrease. Further, when the number of side chains exceeds the above range, the relative amount of the crystal component composed of the ethylene polymer in the olefin resin (β) increases, so that the thermoplastic elastomer obtained by dynamic crosslinking using the resin is , Rubber elasticity may be significantly reduced.

As a method for calculating the number of side chains, for example, a method using [a] isotope carbon nuclear magnetic resonance spectrum ( ¹³ C-NMR) or a method using [b] GPC can be used.
Hereinafter, [a] and [b] will be described.

[A] In the measurement by isotope carbon nuclear magnetic resonance spectrum ( ¹³ C-NMR), in the range of 37.8 to 38.1 ppm, ethylene, α-olefin and poerin constituting the main chain of the polymer [R1] were added. Apart from the derived methine carbon, a signal that can be attributed to the methine carbon at the junction of the side chain and the main chain may be observed.
When the signal is observed, the number of side chains can be calculated by the following equation.
[Number of side chains] = 1000 x [I _PE-methine ] / {[I _all-C ] x (100- [M]) / 10
0};
[I _PE-methine ]: Integral value of methine carbon at the junction of side chain and main chain [I _all-C ]: Integral value of total carbon [M]: _Polymer [R1] Of macromonomer added or produced during production Weight ratio (wt%) to olefin resin (β)

[B] As described above, the peak on the low molecular weight side obtained when the olefin resin (β) is analyzed by GPC is derived from the macromonomer remaining without copolymerization during the copolymerization reaction. Therefore, the weight ratio of the remaining macromonomer contained in the olefin resin (β) can be obtained from the area ratio of the peak on the low molecular weight side to the other peak. When the weight composition of the macromonomer added or produced during the production of the polymer [R1] is clear, the number of side chains can be determined from the difference between the weight composition and the weight ratio of the remaining macromonomer. Specifically, it can be calculated by the following equation.

[Number of side chains] = ([M]-[M']) / (100- [M']) x (1 / [Mn _-M ]) x 14 / {1-([M]-[M']] ) / (100- [M'])} × (1/1000);
[M]: Weight ratio (wt%) of the macromonomer added or produced during the production of the polymer [R1] to the total amount [R'] of the resin obtained during the production of the polymer [R1].
[M']: Weight ratio (wt%) of the remaining macromonomer obtained from GPC to the total amount of resin [R'] obtained during the production of the polymer [R1].
[Mn _-M ]: Number average molecular weight of macromonomer

The average frequency determined by the methods [a] and [b] is, when an ethylene / α-olefin / polyene copolymer produced as a by-product during the production of the olefin resin (β) is present, the polymer. It is a value when the number of side chains of is 0.

The number of side chains can be adjusted, for example, by controlling the molar concentration of macromonomers in the polymerization system.
For example, under certain polymerization conditions, when the side chain molecular weight is constant, increasing the charged mass (or produced mass) of the macromonomer increases the molar concentration of the macromonomer, and the number of side chains in the produced graft polymer. Will increase. Further, when the charged mass (or the produced mass) of the macromonomer is constant, the molar concentration of the macromonomer becomes high by reducing the side chain molecular weight, and the number of side chains in the produced graft polymer can be increased. it can.
The number of side chains can also be adjusted by selecting the type of crosslinked metallocene compound (A) described later. For example, crosslinks that exhibit high copolymerizability at high temperatures and can produce a high amount of polymer. The number of side chains can be increased by selecting a catalyst for olefin polymerization containing a metallocene compound.

[Requirement (III)]
The olefin resin (β) exhibits an endothermic peak, that is, a melting peak when the temperature rise of the DSC is measured, and the melting temperature (Tm) is 60 to 130 ° C., preferably 80 to 125 ° C., more preferably 90 to 120 ° C. Exists in range.
The heat of fusion (ΔH) calculated from the melting peak area is in the range of 5 to 150 J / g, preferably 5 to 120 J / g, more preferably 5 to 100 J / g, and further preferably 8 to 60 J / g. ..

Tm and ΔH are crystallized by a cooling step up to 30 ° C. after the sample is melted once through a heating step by DSC, and endothermic peaks appearing in the second heating step (heating rate 10 ° C./min) are obtained. It is an analysis.

The Tm and ΔH observed in the above range are mainly derived from the side chain ethylene polymer of the polymer [R1] constituting the olefin resin (β), and Tm and ΔH are in the above range. The thermoplastic elastomer obtained by dynamic cross-linking using the olefin resin (β) of the present invention has high hardness and high rigidity, and is particularly excellent in rubber elasticity from high temperature to low temperature near the melting point of the polymer [R1]. .. On the other hand, if Tm or ΔH is below the range, the rigidity, hardness or rubber elasticity may decrease.

Examples of the method for adjusting Tm within the above range include a method for appropriately selecting the type of transition metal compound used in the synthesis of macromonomers, which will be described later.
Further, as a method of adjusting ΔH within the above range, for example, a method of controlling the abundance ratio of the macromonomer in the manufacturing process of the olefin resin (β) described later can be mentioned. Specific examples thereof include a method of controlling the feed amount of the macromonomer or controlling the feed ratio of the crosslinked metallocene compound (A) and the transition metal compound (B) described later.

[Requirements (IV)]
The olefin resin (β) has a glass transition temperature (Tg) measured by DSC at −80 to −30 ° C., preferably −80 to −40 ° C., and more preferably −80 to −50 ° C.
This Tg is based on the ethylene / α-olefin / polyene copolymer of the main chain of the polymer [R1]. When the Tg is in the range of −80 to −30 ° C., the thermoplastic elastomer obtained by dynamically cross-linking with an olefin resin (β) has flexibility as a rubber and rubber elasticity.

The olefin resin (β) having Tg in the above range can be obtained by controlling the type and composition of α-olefin, which is a comonomer, in the synthesis of the polymer [R1].

The olefin resin (β) preferably satisfies the following requirements (V), (VI), or both of the above requirements (I) to (IV).

[Requirement (V)]
The olefin resin (β) has an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.1 to 12 dl / g, preferably 0.2 to 10 dl / g, and more preferably 0.5. ~ 5 dl / g. Within this range, the thermoplastic elastomer obtained by dynamically cross-linking with an olefin resin (β) exhibits good mechanical properties and also has good molding processability.

[Requirements (VI)]
In the olefin resin (β), the ratio (E value) of the orthodichlorobenzene-soluble component at 20 ° C. or lower measured by a cross-separation chromatograph (CFC) is 45 wt% or less, preferably 35 wt% or less, and more. It is preferably 30 wt% or less.

Generally, a commercially available ethylene / α-olefin / polyene copolymer resin (for example, ethylene / propylene / diene copolymer) is a polymer adjusted so that the composition of ethylene is about 90 to 50 mol%, and is not. It exhibits crystallinity (or low crystallinity) and dissolves well in specific organic solvents even at temperatures below room temperature. For example, most of the commercially available ethylene / propylene / diene copolymer resins are soluble in orthodichlorobenzene at 20 ° C. or lower, and the E value is usually 93 wt% or more.

On the other hand, in the polymer [R1] constituting the olefin resin (β) according to the present invention, the main chain is the above-mentioned ethylene / α-olefin / polyene copolymer, but the side chain is crystalline ethylene weight. Since it is a coalescence, it is sparingly soluble in orthodichlorobenzene below room temperature. Therefore, the olefin resin (β) has a characteristic that the E value is small.

The low E value of the olefin resin (β) is an indirect evidence that the main chain structure and the side chain structure of the polymer [R1] are chemically bonded, and further, the olefin resin (β) It is shown that the polymer [R1] is contained in a considerable amount.

The olefin-based resin (β) of the present invention is a crystalline polyolefin such as polypropylene, like a commercially available ethylene / α-olefin / polyene copolymer resin used as a raw material for a general dynamically crosslinked olefin-based thermoplastic elastomer. It forms a domain phase by compounding with a resin, and plays a role in exhibiting flexibility and rubber elasticity in the obtained thermoplastic elastomer. Here, when a commercially available ethylene / α-olefin / polyene copolymer resin is used, the obtained thermoplastic elastomer exhibits flexibility and rubber elasticity as rubber, but on the other hand, surface hardness, modulus, breaking strength, and breaking elongation are exhibited. Decreases. On the other hand, when the olefin resin (β) of the present invention is used, the obtained thermoplastic elastomer is excellent in hardness, modulus, breaking strength, breaking elongation and rubber elasticity in a well-balanced manner. This is because, in the domain phase formed by the ethylene / α-olefin / polyene copolymer, the polyethylene polymer which is the side chain of the polymer [R1] forms a pseudo-crosslink point, and the domain itself has high rigidity. It is presumed that this is because high hardness and excellent rubber elasticity are produced.
Therefore, the inclusion of the polymer [R1] in the olefin resin (β) is an important factor in obtaining a thermoplastic elastomer showing good physical properties in a well-balanced manner.

Further, in order to maintain a good mechanical property balance of the thermoplastic elastomer according to the present invention, the ΔH and E values of the olefin resin (β) must satisfy any of the following relationships a), b) and c). preferable.
a) When ΔH is 5 J / g or more and less than 15 J / g, E is 45 wt% or less, preferably 40 wt% or less, and more preferably 10 to 35 wt%.
b) When ΔH is 15 J / g or more and less than 30 J / g, E is 40 wt% or less, preferably 35 wt% or less, and more preferably 5 to 30 wt%.
c) When ΔH is 30 J / g or more, E is 30 wt% or less, preferably 25 wt% or less.

The fact that the olefin resin (β) satisfies the relationship of a), b) or c) means that the amount of the polymer [R1] contained in the olefin resin (β) according to the present invention is excellent in mechanical properties. It is shown that it is sufficiently abundant to obtain a thermoplastic elastomer.
When the olefin resin (β) does not satisfy the relationship of a), b) or c), that is, when the E value becomes large, the content of the graft polymer is not sufficient and the ethylene / α-olefin / polyene copolymer weight is insufficient. It may have properties similar to those of a polymer blend of a coalescence and an ethylene polymer, making it difficult to exhibit the good physical properties described above.

For example, when the amount of side chains is small, such as when ΔH is 5 J / g or more and less than 15 J / g, and the E value exceeds 45 wt%, the existing ethylene / α-olefin / polyene copolymer resin is used. It tends to be difficult to obtain a thermoplastic elastomer that is close to the performance of the case and has a good balance of hardness, rigidity and rubber elasticity. Further, when the amount of side chains such as ΔH is 30 J / g or more and the amount of side chains is relatively large and the E value exceeds 30 wt%, the components of the ethylene polymer alone not incorporated into the main chain increase, and the rubber is used as rubber. Not only is the flexibility impaired, but rubber elasticity and rigidity may be significantly reduced.

As described above, the olefin resin (β) contains a considerable amount of a component (polymer [R1]) in which a crystalline ethylene polymer is chemically bonded to an ethylene / α-olefin / polyene copolymer. For example, it is preferably contained in an amount of 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more. Therefore, the above-mentioned preferable relationship between ΔH and E value can be satisfied. When olefin resin (β) is synthesized by copolymerizing ethylene with α-olefin, polyene, and polyethylene macromonomer, it is considered important to select a catalyst to be used in the copolymerization step, and crosslinked metallocene described later. By using the compound (A), a resin satisfying the above-mentioned preferable relationship between ΔH and E value can be obtained.

[Other physical characteristics of olefin resin (β)]
-Elastic modulus The olefin resin (β) preferably has an elastic modulus in the range of 2 to 120 MPa, more preferably 3 to 100 MPa, and further preferably 5 to 90 MPa. When the elastic modulus is within the above range, the thermoplastic elastomer obtained by dynamically cross-linking with an olefin resin (β) is excellent in flexibility as rubber and rubber elasticity.
It is desirable that the elastic modulus is a tensile elastic modulus according to ASTM D638.

-Phase separation structure In the olefin resin (β), it is preferable that the phase showing the crystalline component observed by the transmission electron microscope is a discontinuous phase on the order of micrometer. In addition, the observation of whether or not it has the above-mentioned phase structure is carried out, for example, as follows.

First, the olefin resin (β) is molded by heating it for 5 minutes using a hydraulic hot press molding machine set at 170 ° C. and then pressurizing it at 10 MPa for 1 minute, and then molding it at 20 ° C. and 10 MPa for 3 minutes. A test piece is obtained by producing a sheet having a predetermined thickness by cooling.

The obtained test piece is made into small pieces of 0.5 mm square and stained with ruthenium acid (RuO ₄ ). Further, in an ultramicrotome equipped with a diamond knife, the obtained small pieces are made into ultrathin sections having a film thickness of about 100 nm. Carbon is vapor-deposited on this ultrathin section and observed with a transmission electron microscope (acceleration voltage 100 kV).
According to this observation method, the side chain ethylene polymer of the polymer [R1] is observed as having a higher contrast because the intercrystal amorphous portion of the lamellar structure formed by the side chain is selectively stained with ruthenic acid. Will be done.

In the olefin resin (β), it is preferable that the phase corresponding to the side chain portion of the polymer [R1] observed in this manner composed of the ethylene polymer is a discontinuous phase on the order of micrometers.

As described above, the olefin resin (β) contains a polymer [R1] in which an amorphous (or low crystalline) main chain and a crystalline side chain are covalently linked as a main component, and thus is a non-crystalline component. It is considered that the compatibility effect of the crystal components is high and the above-mentioned microphase-separated structure is formed.

The discontinuous phase observed in the olefin resin (β) is a physical cross-linking point composed of a side chain ethylene polymer, and is formed in the thermoplastic elastomer obtained by using the olefin resin (β). It is considered that the physical cross-linking point is also formed in the domain phase composed of the ethylene / α-olefin / polyene copolymer. Therefore, it is considered that the thermoplastic elastomer according to the present invention has an excellent balance of mechanical properties between rigidity, hardness and rubber elasticity.

On the other hand, when a polymer blend of an ethylene / α-olefin / polyene copolymer and an ethylene polymer is used in the production of the thermoplastic elastomer without using the olefin resin (β), the microphase as described above is used. No separated structure is formed, but a coarse crystalline phase is formed. Therefore, when the polymer blend is used, no physical cross-linking point is formed in the ethylene / α-olefin / polyene copolymer domain, and a dynamically cross-linked thermoplastic elastomer showing good physical properties cannot be obtained. ..

<Manufacturing method of olefin resin (β)>
As a method for producing the olefin resin (β) of the present invention, for example, it can be produced by a method including the following (a) or (b).
(A) A step of polymerizing ethylene in the presence of a catalyst containing the following compounds (B) and (C) [a-1].
In the presence of a catalyst containing the following compounds (A) and (C), ethylene, at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms, polyene, and step [a-1]. Method including step [a-2] of copolymerizing with the reaction product of (b) In the presence of an olefin polymerization catalyst containing each of the following compounds (A) to (C), ethylene and 3 carbon atoms A method including a step of copolymerizing a component containing polyene with at least one α-olefin selected from ~ 20 α-olefins (A) a crosslinked metallocene compound represented by the following formula (I) (B) below. Transition metal compound represented by the formula [B] (C) (C-1) Organic metal compound, (C-2) Organic aluminum oxy compound, and (C-3) Crosslinked metallocene compound (A) or transition metal compound. At least one compound selected from a compound that reacts with (B) to form an ion pair.

[Cross-linked metallocene compound (A)]
The crosslinked metallocene compound (A) is represented by the following formula (I) and functions as a catalyst for olefin polymerization in the presence of the compound (C) described later.

（式（Ｉ）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁸、Ｒ⁹およびＲ¹²はそれぞれ独立に、水素原子、炭化水素基、ケイ素含有基またはケイ素含有基以外のヘテロ原子含有基を示し、Ｒ¹〜Ｒ⁴のうち隣接する二つの基同士は互いに結合して環を形成していてもよい。
Ｒ⁶およびＲ¹¹は水素原子、炭化水素基、ケイ素含有基およびケイ素含有基以外のヘテロ原子含有基から選ばれる同一の原子または同一の基であり、Ｒ⁷およびＲ¹⁰は水素原子、炭化水素基、ケイ素含有基およびケイ素含有基以外のヘテロ原子含有基から選ばれる同一の原子または同一の基であり、Ｒ⁶およびＲ⁷は互いに結合して環を形成していてもよく、Ｒ¹⁰およびＲ¹¹は互いに結合して環を形成していてもよく；ただし、Ｒ⁶、Ｒ⁷、Ｒ¹⁰およびＲ¹¹が全て水素原子であることはない。
Ｒ¹³およびＲ¹⁴はそれぞれ独立にアリール基を示す。
Ｍはチタン原子、ジルコニウム原子またはハフニウム原子を示す。
Ｙ¹は炭素原子またはケイ素原子を示す。
Ｑはハロゲン原子、炭化水素基、ハロゲン化炭化水素基、炭素数４〜１０の中性の共役もしくは非共役ジエン、アニオン配位子または孤立電子対で配位可能な中性配位子を示し、ｊは１〜４の整数を示し、ｊが２以上の整数の場合は複数あるＱはそれぞれ同一でも異なっていてもよい。）

(In formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² are independently other than hydrogen atom, hydrocarbon group, silicon-containing group or silicon-containing group, respectively. the indicated heteroatom-containing group, two groups adjacent to each other among R ¹ to R ⁴ may be bonded to each other to form a ring.
R ⁶ and R ¹¹ are the same atom or the same group selected from heteroatom-containing groups other than hydrogen atom, hydrocarbon group, silicon-containing group and silicon-containing group, and R ⁷ and R ¹⁰ are hydrogen atom and hydrocarbon. It is the same atom or the same group selected from a group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group, and R ⁶ and R ⁷ may be bonded to each other to form a ring, and R ¹⁰ and R ¹¹ may be bonded to each other to form a ring; however, R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.
R ¹³ and R ¹⁴ each independently represent an aryl group.
M represents a titanium atom, a zirconium atom or a hafnium atom.
Y ¹ represents a carbon atom or a silicon atom.
Q indicates a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or unconjugated diene having 4 to 10 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair. , J indicates an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Qs may be the same or different. )

The olefin polymerization catalyst containing the crosslinked metallocene compound (A) is a copolymer of ethylene, at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms, polyene, and a macromonomer. And plays a role in producing the polymer [R1].

That is, the catalyst for olefin polymerization containing the crosslinked metallocene compound (A) contributes to the copolymerization of ethylene, α-olefin, polyene, and macromonomer, and has a characteristic of exhibiting particularly high copolymerizability with respect to the macromonomer. Further, the catalyst for olefin polymerization containing the crosslinked metallocene compound (A) exhibits sufficiently high olefin polymerization activity even under relatively high temperature conditions such that the macromonomer which is an ethylene polymer chain is dissolved, and has a sufficiently high molecular weight for practical use. It has the characteristic of being able to synthesize a polymer of.

Since the catalyst for olefin polymerization containing the crosslinked metallocene compound (A) has the above-mentioned characteristics, it is possible to produce an olefin resin (β) containing a large amount of the polymer [R1], and the above-mentioned requirement (I) ) To (IV) can be produced as an olefin resin (β). The thermoplastic elastomer obtained by dynamically cross-linking with the olefin resin (β) thus obtained has high hardness and high rigidity, and further has excellent mechanical properties and rubber elasticity.
Hereinafter, the chemical structural features of the crosslinked metallocene compound (A) used in the present invention will be described.

The crosslinked metallocene compound (A) structurally has the following features [m1] to [m3].
[M1] Of the two ligands, one is a cyclopentadienyl group which may have a substituent, and the other one is a fluorenyl group having a substituent (hereinafter, also referred to as "substituted fluorenyl group"). It says.).
[M2] Two ligands are bonded by an aryl group-containing covalent bond cross-linking portion (hereinafter, also referred to as “cross-linking portion”) consisting of a carbon atom or a silicon atom having an aryl group.
[M3] The transition metal (M) constituting the metallocene compound is an atom of Group 4 of the periodic table, specifically, a titanium atom, a zirconium atom or a hafnium atom.

Hereinafter, the cyclopentadienyl group which may have a substituent, the substituted fluorenyl group, the crosslinked portion and other features of the crosslinked metallocene compound (A) will be sequentially described.

(Cyclopentadienyl group which may have a substituent)
In formula (I), R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a hetero atom-containing group other than a silicon-containing group, and represent a hydrogen atom and a hydrocarbon. A group or a silicon-containing group is preferable, and two adjacent groups may be bonded to each other to form a ring.
For example, R ¹ , R ² , R ³ and R ⁴ are all hydrogen atoms, or one or more of R ¹ , R ² , R ³ and R ⁴ are hydrocarbon groups (hereinafter “hydrocarbon groups”). (F1) ”), preferably a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing group (hereinafter, also referred to as“ silicon-containing group (f2) ”), preferably silicon having 1 to 20 carbon atoms. It is a containing group. In addition, examples of R ¹ , R ² , R ³ and R ⁴ include heteroatom-containing groups (excluding silicon-containing groups (f2)) such as halogenated hydrocarbon groups, oxygen-containing groups and nitrogen-containing groups. ..

The hydrocarbon group (f1) is preferably a hydrocarbon group having 1 to 20 carbon atoms, for example, a linear or branched hydrocarbon group (eg, alkyl group, alkenyl group, alkynyl group), cyclic group. Examples thereof include saturated hydrocarbon groups (eg, cycloalkyl groups) and cyclic unsaturated hydrocarbon groups (eg, aryl groups). The hydrocarbon group (f1) also includes a group in which any two hydrogen atoms bonded to carbon atoms adjacent to each other are simultaneously substituted to form an alicyclic ring or an aromatic ring.

Specific examples of the hydrocarbon group (f1) include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group and n-octyl group. Linear hydrocarbon groups such as n-nonyl group, n-decanyl group, allyl group; isopropyl group, isobutyl group, sec-butyl group, t-butyl group, amyl group, 3-methylpentyl group, neopentyl group. Group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1- Branched hydrocarbon groups such as methyl-1-isopropyl-2-methylpropyl group; cyclic saturated hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group; phenyl group, naphthyl Cyclic unsaturated hydrocarbon groups such as groups, biphenyl groups, phenanthryl groups, anthracenyl groups and their nuclear alkyl substituents; at least one hydrogen atom of saturated hydrocarbon groups such as benzyl group and cumyl group is substituted with aryl group. Butyl groups and the like.

The silicon-containing group (f2) is preferably a silicon-containing group having 1 to 20 carbon atoms. For example, the silicon atom is directly covalently bonded to the ring carbon of the cyclopentadienyl group in the formula (I). Groups are mentioned, and specific examples thereof include an alkylsilyl group (eg, trimethylsilyl group) and an arylsilyl group (eg, triphenylsilyl group).

Specific examples of the hetero atom-containing group (excluding the silicon-containing group (f2)) include a methoxy group, an ethoxy group, a phenoxy group, an N-methylamino group, a trifluoromethyl group, a tribromomethyl group, and a pentafluoroethyl group. Examples include a group and a pentafluorophenyl group.

When two or more of R ¹ , R ² , R ³ and R ⁴ are substituents other than hydrogen atoms, the substituents may be the same or different from each other, and R ¹ , R ² , R ³ And two adjacent groups of R ⁴ may be bonded to each other to form an alicyclic or aromatic ring.

(Substituted fluorenyl group)
In formula (I), R ⁵ , R ⁸ , R ⁹ and R ¹² independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a hetero atom-containing group other than a silicon-containing group, and represent a hydrogen atom and a hydrocarbon. Groups or silicon-containing groups are preferred. R ⁶ and R ¹¹ are the same atom or the same group selected from heteroatomic groups other than hydrogen atom, hydrocarbon group, silicon-containing group and silicon-containing group, and the hydrogen atom, hydrocarbon group and silicon-containing group are Preferably; R ⁷ and R ¹⁰ are the same atom or the same group selected from heteroatomic groups other than hydrogen atoms, hydrocarbon groups, silicon-containing groups and silicon-containing groups, and contain hydrogen atoms, hydrocarbon groups and silicon. Groups are preferred; R ⁶ and R ⁷ may be bonded to each other to form a ring, and R ¹⁰ and R ¹¹ may be bonded to each other to form a ring; however, "R ⁶ , R ^7". , R ¹⁰ and R ¹¹ are not all hydrogen atoms.

From the viewpoint of polymerization activity, it is preferable that neither R ⁶ nor R ¹¹ is a hydrogen atom; it is more preferable that none of R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ is a hydrogen atom; R ⁶ and R ¹¹ Is the same group selected from the hydrocarbon group and the silicon-containing group, and it is particularly preferable that R ⁷ and R ¹⁰ are the same group selected from the hydrocarbon group and the silicon-containing group. It is also preferable that R ⁶ and R ⁷ are bonded to each other to form an alicyclic or aromatic ring, and R ¹⁰ and R ¹¹ are bonded to each other to form an alicyclic or aromatic ring.

Examples of the hydrocarbon group in R ^{5 to} R ¹² and a preferable group include a group similar to the group exemplified as the hydrocarbon group (f1). Examples of the silicon-containing groups in R ^{5 to} R ¹² and preferred groups include groups similar to the groups exemplified as the silicon-containing group (f2). Examples of the heteroatom-containing group in R ^{5 to} R ¹² include groups similar to those exemplified as the heteroatom-containing group.

The substituted fluorenyl group when R ⁶ and R ⁷ (R ¹⁰ and R ¹¹ ) are bonded to each other to form an alicyclic or aromatic ring is derived from a compound represented by the formulas [II] to [VI] described later. A suitable example is the group to be used.

(Bridge)
In formula (I), R ¹³ and R ¹⁴ each independently represent an aryl group, and Y ¹ represents a carbon atom or a silicon atom. An important point in the process for producing an olefin-based resin (beta) is a bridging atom Y ¹ of the bridge, that are bonded also aryl (aryl) group [R ¹³ and R ^14] be the same or different from each other Is. It is preferable that R ¹³ and R ¹⁴ are the same as each other because of ease of manufacture.

Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a group in which one or more of the aromatic hydrogens (sp2-type hydrogens) contained therein are substituted with a substituent. Examples of the substituent include the hydrocarbon group (f1) and the silicon-containing group (f2), and a halogen atom and a halogenated hydrocarbon group.

Specific examples of the aryl group include an unsubstituted aryl group having 6 to 14, preferably 6 to 10 carbon atoms such as a phenyl group, a naphthyl group, an anthracenyl group, and a biphenyl group; a trill group, an isopropylphenyl group, and an n-butylphenyl group. Alkyl group-substituted aryl groups such as groups, t-butylphenyl groups and dimethylphenyl groups; cycloalkyl group-substituted aryl groups such as cyclohexylphenyl groups; aryl halide groups such as chlorophenyl groups, bromophenyl groups, dichlorophenyl groups and dibromophenyl groups ; (Trifluoromethyl) phenyl group, bis (trifluoromethyl) phenyl group and other alkyl halide substituted aryl groups can be mentioned.
The positions of the substituents in these groups are preferably meta-position and / or para-position. Of these, substituted phenyl groups in which the substituents are located at the meta and / or para positions are more preferable.

(Other features of crosslinked metallocene compound (A))
In formula (I), Q can be coordinated with a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or unconjugated diene with 4 to 10 carbon atoms, an anionic ligand or a lone electron pair. It indicates a neutral ligand, j indicates an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Qs may be the same or different.

Specific examples of the halogen atom are fluorine, chlorine, bromine and iodine, and the hydrocarbon group includes, for example, a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms and 3 carbon atoms. Examples include 10 to 10 aliphatic hydrocarbon groups. Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, 2-methylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group and 1,1-. Diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylbutyl group, 1,1,3 -Methylbutyl group, neopentyl group and examples. Examples of the alicyclic hydrocarbon group include a cyclohexyl group, a cyclohexylmethyl group, and a 1-methyl-1-cyclohexyl group.

Examples of the halogenated hydrocarbon group in Q include a group in which at least one hydrogen atom of the hydrocarbon group mentioned as an example of Q is substituted with a halogen atom.

Specific examples of neutral conjugated or non-conjugated diene having 4 to 10 carbon atoms include s-cis- or s-trans-η4-1,3-butadiene, s-cis or s-trans-η4-1, 4-Diphenyl-1,3-butadiene, s-cis or s-trans-η-4-3-methyl-1,3-pentadiene, s-cis or s-trans-η4-2,4-hexadiene, s-cis or s-trans-η4-1,3-pentadiene, s-cis or s-trans-η4-1,4-ditril-1,3-butadiene, s-cis or s-trans-η4-1,4-bis ( Trimethylsilyl) -1,3-butadiene and the like.

Specific examples of the anion ligand include an alkoxy group such as methoxy, tert-butoxy and phenoxy, a carboxylate group such as acetate and benzoate, and a sulfonate group such as mesylate and tosylate.

Specific examples of the neutral ligand capable of coordinating with a lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine, or tetrahydrofuran, diethyl ether, dioxane, 1, 2 -Ethers such as dimethoxyethane can be mentioned.

In the formula (I), M represents a titanium atom, a zirconium atom or a hafnium atom, and the zirconium atom or the hafnium atom can copolymerize a macromonomer with high efficiency and can produce a high molecular weight olefin resin (β). preferable.

In particular, in an industrial process in which polymerization is carried out under high temperature and high pressure conditions in order to ensure high productivity, it is preferable that M is a hafnium atom because of the above-mentioned characteristics. This is because the abundance ratio of ethylene and α-olefin is higher than that of the macromonomer under high pressure conditions, and the molecular weight generally decreases under high temperature conditions. Therefore, as described above, the macromonomer is efficiently copolymerized and is high. This is because it is preferable to use a catalyst having the ability to produce an olefin resin (β) having a molecular weight.

Such characteristics due to the fact that M is a hafnium atom include (1) the Lewis acidity of the hafnium atom is smaller and the reactivity is lower than that of the zirconium atom and the titanium atom, and (2) the zirconium atom and the like. The fact that the bond energy between the hafnium atom and the carbon atom is larger than that of the titanium atom is a chain that includes the β-hydrogen elimination reaction of the polymerization active species that is bonded to the product polymer chain, which is one of the molecular weight determinants. It is considered that this is due to the suppression of the migration reaction.

(Example of preferred crosslinked metallocene compound (A))
A suitable specific example of the crosslinked metallocene compound (A) is shown below. In the exemplified compounds, octamethyloctahydrodibenzofluorenyl refers to a group derived from a compound having a structure represented by the formula [II], and octamethyltetrahydrodicyclopentafluorenyl is represented by the formula [III]. Dibenzofluorenyl refers to a group derived from a compound having a structure represented by the formula [IV], and is 1,1', 3,6,8,8'-hexamethyl-. 2,7-Dihydrodicyclopentafluorenyl refers to a group derived from a compound having a structure represented by the formula [V], and is 1,3,3', 6,6', 8-hexamethyl-2,7-. Dihydrodicyclopentafluorenyl refers to a group derived from a compound having a structure represented by the formula [VI].

Examples of the crosslinked metallocene compound (A) include
Diphenylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (Cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) ( Dibenzofluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (1,1', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, diphenylmethylene (Cyclopentadienyl) (1,3,3', 6,6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7) -Diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (Cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3 , 6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride.

Examples of the crosslinked metallocene compound (A) include
Di (p-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (1,1) ', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (1,3,3', 6 , 6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert- Butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (Cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-( Dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,3,6,7-tetramethylfluorenyl) zirconium dichloride, Di (p-tolyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride.

Examples of the crosslinked metallocene compound (A) include
Di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (1,1 ', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (1,3,3', 6 , 6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert- Butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (Cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-( Dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium Dichloride is mentioned.

Examples of the crosslinked metallocene compound (A) include
Di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (1,1 ', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (1,3,3', 6 , 6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert- Butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (Cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-( Dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium Dichloride is mentioned.

Examples of the crosslinked metallocene compound (A) include
Di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (3,6-dienyl) tert-Butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) ) (Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadi) Enyl) (1,1', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (1) , 3,3', 6,6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-diphenyl) -3,6-ditert-butylfluorenyl) zirconium Dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium Dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene ( Cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,3,6) , 7-Tetratert-butylfluorenyl) zirconium dichloride.

Examples of the crosslinked metallocene compound (A) include
Di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (m-) Trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Zyroxide dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (1,1', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium Dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (1,3,3', 6,6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride , Di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) Methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7) -(Trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3, 6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride Can be mentioned.

Examples of the crosslinked metallocene compound (A) include
Di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-) Trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Zyroxide dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (1,1', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium Dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (1,3,3', 6,6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride , Di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) Methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7) -(Trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3, 6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride Can be mentioned.

Examples of the crosslinked metallocene compound (A) include
Di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-) tert-Butyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Zyroxide dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (1,1', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium Dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (1,3,3', 6,6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride , Di (p-tert-butyl-phenyl) Methyl (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) Zyroxide dichloride, di (p-tert-butyl-phenyl) Methyl (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,7) -(Trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3, 6-Ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride Can be mentioned.

Examples of the crosslinked metallocene compound (A) include
Di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-) n-Butyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Zyroxide dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (1,1', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium Dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (1,3,3', 6,6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride , Di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (pn-butyl-phenyl) Methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,7) -(Trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3, 6-ditert-butylfluorenyl) zirconium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride Can be mentioned.

Examples of the crosslinked metallocene compound (A) include
Di (p-biphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (1,1 ', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (1,3,3', 6 , 6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert- Butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (Cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2,7-( Dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconide, di (p-biphenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium Dichloride is mentioned.

Examples of the crosslinked metallocene compound (A) include
Di (1-naphthyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (1,1 ', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (1,3,3', 6 , 6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert- Butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (Cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,7-( Dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium Dichloride is mentioned.

Examples of the crosslinked metallocene compound (A) include
Di (2-naphthyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (1,1 ', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (1,3,3', 6 , 6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert- Butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (Cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,7-( Dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium Dichloride is mentioned.

Examples of the crosslinked metallocene compound (A) include
Di (m-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (2,7-dimethylfluore) Nyl) zirconium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride.

Examples of the crosslinked metallocene compound (A) include
Di (p-isopropylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluore) Nyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) ( 3,6-ditert-butylfluorenyl) zirconium dichloride.

Examples of the crosslinked metallocene compound (A) include
Diphenylcilylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylcilylene (Cyclopentadienyl) (Octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) ( Dibenzofluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (1,1', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, diphenylcilylene (Cyclopentadienyl) (1,3,3', 6,6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2,7) -Diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylcilylene (Cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3 , 6-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride.

Examples of the crosslinked metallocene compound (A) include a compound obtained by changing the above-exemplified compound "zyrosine" to "hafnium" or "titanium", and "dichloride" to "difluoride", "dibromid", "diaiodide", "dimethyl", and ". Compounds changed to "methylethyl" or "dibenzyl", "cyclopentadienyl" changed to "3-tert-butyl-5-methyl-cyclopentadienyl", "3,5-dimethyl-cyclopentadienyl", Compounds changed to "3-tert-butyl-cyclopentadienyl" or "3-methyl-cyclopentadienyl" can also be mentioned.

The above metallocene compounds can be produced by a known method, and the production method is not particularly limited. Known methods include, for example, the methods described in International Publication No. 01/27124 and International Publication No. 04/029062.

As the crosslinked metallocene compound (A) as described above, one kind alone or two or more kinds can be used.

[Transition metal compound (B)]
The transition metal compound (B) is a specific compound having a structure represented by the following formula [B], and functions as a catalyst for olefin polymerization in the presence of the compound (C) described later.

（式［Ｂ］中、Ｍは周期表第４または５族の遷移金属原子を示す。
ｍは１〜４の整数を示す。
Ｒ¹は、式Ｃ_n'Ｈ_2n'+1（ｎ’は１〜４の整数である）で表される炭素原子数１〜４の非環式炭化水素基を示す。
Ｒ²〜Ｒ⁵は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭化水素基、ハロゲン化炭化水素基、ヘテロ環式化合物残基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、これらのうちの２個以上が互いに連結して環を形成していてもよい。
Ｒ⁶〜Ｒ⁸は独立に炭化水素基またはハロゲン化炭化水素基であって、そのうち少なくとも一つは芳香族炭化水素基またはハロゲン化芳香族炭化水素基であり、また、ｍが２以上の場合には、式［Ｂ］の構造単位相互間においてＲ²〜Ｒ⁸で示される基のうち２個の基が連結されていてもよい。
ｎは、Ｍの価数を満たす数であり、Ｘは、水素原子、ハロゲン原子、炭化水素基、酸素含有基、イオウ含有基、窒素含有基、ホウ素含有基、アルミニウム含有基、リン含有基、ハロゲン含有基、ヘテロ環式化合物残基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、ｎが２以上の整数である場合には、複数のＸは互いに同一であっても、異なっていてもよく、また、Ｘで示される複数の基は互いに結合して環を形成してもよい。）

(In formula [B], M represents a transition metal atom of Group 4 or 5 of the Periodic Table.
m represents an integer of 1 to 4.
R ¹ represents a formula _{C n 'H 2n' + 1} (n ' is a is an integer of 1-4) acyclic hydrocarbon group having 1 to 4 carbon atoms as represented by.
R ^{2 to} R ⁵ may be the same or different from each other, and are hydrogen atom, halogen atom, hydrocarbon group, halogenated hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group. , Sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group, and two or more of these may be linked to each other to form a ring.
R ^{6 to} R ⁸ are independently hydrocarbon groups or halogenated hydrocarbon groups, at least one of which is an aromatic hydrocarbon group or a halogenated aromatic hydrocarbon group, and when m is 2 or more. In, ^two groups among the groups represented by R ^{2 to} R ⁸ may be linked between the structural units of the formula [B].
n is a number satisfying the valence of M, and X is 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, When n indicates a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and n is an integer of 2 or more, a plurality of Xs are different even if they are the same as each other. Or, the plurality of groups represented by X may be bonded to each other to form a ring. )

The catalyst for olefin polymerization containing the transition metal compound (B) is used for the synthesis of the macromonomer which is an ethylene polymer, and also contributes to the formation of the side chain of the polymer [R1].

That is, the olefin polymerization catalyst containing the transition metal compound (B) mainly contributes to the polymerization of ethylene, and by using the compound (B), an ethylene polymer having a one-terminal vinyl group is synthesized with a high selectivity. can do. Further, by using a catalyst for olefin polymerization containing a transition metal compound (B), an ethylene polymer having a relatively low molecular weight (with a weight average molecular weight in the range of 500 to 10,000) can be synthesized. Since the olefin polymerization catalyst containing the transition metal compound (B) has the above-mentioned characteristics, the polymer [R1] in which the side chain is efficiently introduced can be easily obtained, and the olefin system of the present invention can be easily obtained. The thermoplastic elastomer obtained by dynamically cross-linking with a resin (β) has high hardness and high rigidity, and further has excellent mechanical properties and rubber elasticity.

Further, the olefin polymerization catalyst containing the transition metal compound (B) has a characteristic that ethylene can be highly selectively polymerized even in the coexistence of ethylene, α-olefin, polyene and macromonomer, and therefore, it can be used as an ethylene polymer. A polymer [R1] having a side chain having good mechanical properties and thermal properties can be easily obtained. Therefore, the thermoplastic elastomer obtained by dynamically cross-linking with the olefin resin (β) obtained by using the olefin polymerization catalyst containing the transition metal compound (B) has high hardness and high rigidity, and further. It has excellent mechanical properties and rubber elasticity. Further, the above-mentioned feature is also a preferable feature in adopting the polymerization method [b] among the methods for producing the olefin resin (β) described later.

The olefin polymerization catalyst containing the transition metal compound (B) can be obtained to have the ability to substantially not generate an olefin structure (so-called internal olefin) inside the polymer chain, and the olefin resin (β) and the olefin can be obtained. It is preferable from the viewpoint of light resistance and color resistance of the thermoplastic elastomer obtained by dynamically cross-linking with the based resin (β).

Hereinafter, the chemical structural features of the transition metal compound (B) used in the present invention will be described.

In the formula [B], N ... M generally indicate that they are coordinated, but in the present invention, they may or may not be coordinated.

In the formula [B], M represents a transition metal atom of Group 4 or Group 5 of the Periodic Table, specifically titanium, zirconium, hafnium, vanadium, niobium, tantalum, etc., preferably a metal of Group 4 of the Periodic Table. It is an atom, specifically titanium, zirconium, hafnium, and more preferably zirconium.

m represents an integer of 1 to 4, preferably 1 to 2, and particularly preferably 2.

R ¹ has the formula _{C n 'H 2n' + 1} (n ' is a is an integer of 1 to 4) indicates the non-cyclic hydrocarbon group having 1 to 4 carbon atoms as represented by, specifically methyl Group, ethyl group, n-propyl group, n-butyl group, iso-propyl group, iso-butyl group, tert-butyl group. It is preferably a linear hydrocarbon group, specifically a methyl group, an ethyl group, an n-propyl group, or an n-butyl group. Of these, a methyl group, an ethyl group and an n-propyl group are preferable. More preferably, it is a methyl group or an ethyl group. Since R ¹ is these hydrocarbon groups, an ethylene polymer having a relatively low molecular weight (for example, a weight average molecular weight in the range of 500 to 10000) can be synthesized, and as described above, the present invention has an excellent balance of physical properties. It is preferable to obtain the thermoplastic elastomer of.

R ^{2 to} R ⁵ may be the same or different from each other, and may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, or a boron-containing group. , Sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group or tin-containing group, and two or more of these may be linked to each other to form a ring.

When m is 2 or more, two of the groups represented by R ^{2 to} R ⁸ may be linked between the structural units of the formula [B].

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, n-hexyl group and the like. A linear or branched alkyl group having 1 to 30 carbon atoms, preferably 1 to 20; a direct group having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms such as a vinyl group, an allyl group, and an isopropenyl group. Chain or branched alkenyl group; linear or branched alkynyl group having 2 to 30 carbon atoms, preferably 2 to 20, such as ethynyl group and propargyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl Cyclic saturated hydrocarbon groups having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms such as groups and adamantyl groups; cyclic unsaturated carbides having 5 to 30 carbon atoms such as cyclopentadienyl group, indenyl group and fluorenyl group. Hydrogen group; aryl group having 6 to 30, preferably 6 to 20 carbon atoms such as phenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group, anthrasenyl group; tolyl group, isopropylphenyl group, t-butyl Examples thereof include alkyl-substituted aryl groups such as a phenyl group, a dimethylphenyl group and a di-t-butylphenyl group.
Further, the hydrocarbon group may be substituted with another hydrocarbon group, and examples thereof include an aryl group-substituted alkyl group such as a benzyl group and a cumyl group.

Examples of the halogenated hydrocarbon group include a group in which at least one hydrogen atom of the hydrocarbon group is substituted with a halogen, and examples thereof include a trifluoromethyl group, a pentafluorophenyl group, a chlorophenyl group and the like having 1 carbon atom. Examples thereof include ~ 30, preferably 1 to 20 halogenated hydrocarbon groups.

Examples of the above-mentioned hydrocarbon group and halogenated hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group and neopentyl group. A linear or branched alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as an n-hexyl group; a carbon such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group and an anthrasenyl group. An aryl group having 6 to 30 atoms, preferably 6 to 20 atoms; these aryl groups include a halogen atom, an alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 atoms, and 6 to 30 carbon atoms, preferably 6 atoms. A substituted aryl group in which 1 to 5 substituents such as an aryl group of ~ 20 are substituted is preferable.

Examples of the oxygen-containing group include a group containing an alcoholic group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, a carboxylic acid anhydride group and the like, and specific examples thereof. , A group in which the above-mentioned hydrocarbon group is substituted with these groups and the like can be mentioned. Of these, the aryl group is substituted with 1 to 5 substituents such as an alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 atoms, and an aryloxy group having 6 to 30 carbon atoms, preferably 6 to 20 atoms. Substituent aryl groups and the like are preferable.

Examples of the nitrogen-containing group include an amino group, an imino group, an amide group, an imide group, a hydrazino group, a hydrazono group, a nitro group, a nitroso group, a cyano group, an isocyano group, a cyanate ester group, an amidino group, a diazo group and an ammonium base. Examples thereof include groups containing the above, and specific examples thereof include groups in which the above hydrocarbon groups are substituted with these groups.

Examples of the boron-containing group include groups containing a bolangyl group, a bolantriyl group, a diboranyl group and the like, and specific examples thereof include a group in which the hydrocarbon group is substituted with these groups.

Examples of the sulfur-containing group include a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group, a thioether group, a thiosian acid ester group, an isothian acid ester group, a sulfone ester group, a sulfonamide group and a thiocarboxyl group. Examples thereof include a group containing a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, a sulfenyl group and the like, and specific examples thereof include a group in which the hydrocarbon group is substituted with these groups.

Examples of the phosphorus-containing group include a group containing a phosphide group, a phosphoryl group, a thiophosphoryl group, a phosphat group and the like, and specific examples thereof include a group in which the hydrocarbon group is substituted with these groups.

Heterocyclic compound residues include nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine, oxygen-containing compounds such as furan and pyran, and sulfur-containing compounds such as thiophene, and heterocyclic compounds thereof. Examples of the compound residue include an alkyl group having 1 to 30 carbon atoms, preferably 1 to 20, and a group further substituted with a substituent such as an alkoxy group.

Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, and the like, specifically, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, and a triethylsilyl group. , Diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group, dimethyl (pentafluorophenyl) silyl group and the like. Among these, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a triphenylsilyl group and the like are preferable. Particularly, a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group and a dimethylphenylsilyl group are preferable. Specific examples of the hydrocarbon-substituted siloxy group include a trimethylsiloxy group.

Examples of the germanium-containing group and the tin-containing group include a group in which the silicon of the silicon-containing group is replaced with germanium and tin.

Next, the examples of R ^{2 to} R ⁶ described above will be described more specifically. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a t-butoxy group and the like.

Specific examples of the alkylthio group include a methylthio group and an ethylthio group.

Specifically, the allyloxy group includes a phenoxy group, a 2,6-dimethylphenoxy group, and 2
, 4,6-trimethylphenoxy group and the like.

Specific examples of the arylthio group include a phenylthio group, a methylphenylthio group, and a naphthylthio group.

Specific examples of the acyl group include a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, and a p-methoxybenzoyl group.

Specific examples of the ester group include an acetyloxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, a p-chlorophenoxycarbonyl group and the like.

Specific examples of the thioester group include an acetylthio group, a benzoylthio group, a methylthiocarbonyl group, and a phenylthiocarbonyl group.

Specific examples of the amide group include an acetamide group, an N-methylacetamide group, and an N-methylbenzamide group.

Specific examples of the imide group include an acetoimide group and a benzimide group.

Specific examples of the amino group include a dimethylamino group, an ethylmethylamino group, and a diphenylamino group.

Specific examples of the imino group include a methylimino group, an ethylimino group, a propylimino group, a butylimino group, a phenylimino group and the like.

Specific examples of the sulfonic acid ester group include a methyl sulfonate group, an ethyl sulfonate group, and a phenyl sulfonic acid group.

Specific examples of the sulfonamide group include a phenylsulfonamide group, an N-methylsulfonamide group, and an N-methyl-p-toluenesulfonamide group.

In R ^{2 to} R ⁵ , two or more of these groups, preferably adjacent groups, may be linked to each other to form an alicyclic ring, an aromatic ring, or a ring containing a hetero atom such as a nitrogen atom. , These rings may further have a substituent.

n is a number that satisfies the valence of M, and is specifically an integer of 0 to 5, preferably 1 to 4, and more preferably 1 to 3.

X is 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, and a silicon-containing group. Indicates a 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.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Examples of the hydrocarbon group include groups similar to the groups exemplified in R ^{2 to} R ⁵ above. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, nonyl group, dodecyl group and icosyl group; carbon such as cyclopentyl group, cyclohexyl group, norbornyl group and adamantyl group. Cycloalkyl group with 3 to 30 atoms; alkenyl group such as vinyl group, propenyl group, cyclohexenyl group; arylalkyl group such as benzyl group, phenylethyl group, phenylpropyl group; phenyl group, tolyl group, dimethylphenyl group , Trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group, antolyl group, aryl group such as phenanthryl group and the like, but are not limited thereto. Of these, groups having 1 to 20 carbon atoms are preferable.

Examples of the heterocyclic compound residue include groups similar to the groups exemplified in R ^{2 to} R ⁵ above.

Examples of the oxygen-containing group include the same groups as those exemplified in R ^{2 to} R ⁵ , specifically, a hydroxy group; an alcoholic group such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; a phenoxy group. , Methylphenoxy group, dimethylphenoxy group, naphthoxy group and other allyloxy groups; phenylmethoxy group, phenylethoxy group and other arylalkoxy groups; acetoxy group; carbonyl group and the like, but are not limited thereto.

Examples of the sulfur-containing group include the same groups as those exemplified in R ^{2 to} R ⁵ , and specifically, a methyl sulphonate group, a trifluoromethane sulphonate group, a phenyl sulphonate group, and a benzyl sulphonate group. Sulfonate groups such as phonate group, p-toluene sulfonate group, trimethylbenzene sulphonate group, triisobutylbenzene sulphonate group, p-chlorobenzene sulphonate group, pentafluorobenzene sulphonate group; methyls Sulfinate groups such as ruffinate group, phenylsulfinate group, benzylsulfinate group, p-toluenesulfinate group, trimethylbenzenesulfinate group, pentafluorobenzenesulfinate group; alkylthio group; arylthio group etc. These are, but are not limited to.

Specific examples of the nitrogen-containing group include the same groups as those exemplified in R ^{2 to} R ⁵ , and specifically, amino group; methylamino group, dimethylamino group, diethylamino group, dipropyl. Alkylamino groups such as amino group, dibutylamino group and dicyclohexylamino group; arylamino group such as phenylamino group, diphenylamino group, ditrilamino group, dinaphthylamino group and methylphenylamino group or alkylarylamino group and the like. However, it is not limited to these.

Specific examples of the boron-containing group include BR ₄ (R indicates a hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

Specific examples of the phosphorus-containing group include a trialkylphosphin group such as a trimethylphosphine group, a tributylphosphin group and a tricyclohexylphosphin group; a triarylphosphin group such as a triphenylphosphine group and a tritrylphosphin group; a methylphosphite group. , Ethylphosphite group, phosphite group such as phenylphosphite group (phosphide group); phosphonic acid group; phosphinic acid group and the like, but the present invention is not limited thereto.

Specific examples of the silicon-containing group include groups similar to those exemplified in R ^{2 to} R ⁵ , and specific examples thereof include a phenylsilyl group, a diphenylsilyl group, a trimethylsilyl group, a triethylsilyl group, and a tri. Hydrocarbon-substituted silyl groups such as propylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, methyldiphenylsilyl group, tritrylsilyl group, trinaphthylsilyl group; hydrocarbon-substituted silyl ether group such as trimethylsilyl ether group; trimethylsilylmethyl Silicon-substituted alkyl groups such as groups; silicon-substituted aryl groups such as trimethylsilylphenyl groups and the like can be mentioned.

Specific examples of the germanium-containing group and the tin-containing group include groups similar to the groups exemplified in R ^{2 to} R ⁵ , respectively. Specifically, the silicon of the silicon-containing group is germanium or tin. Examples include groups substituted with.

Specifically, the halogen-containing group includes a fluorine-containing group such as PF ₆ and BF ₄ , a chlorine-containing group such as ClO ₄ and SbC _{l 6} , an iodine-containing group such as IO _4, and a hydrocarbon group having 1 to 20 carbon atoms. Examples thereof include, but are not limited to, a group in which at least one hydrogen is substituted with a halogen.

Specific examples of the aluminum-containing group include, but are not limited to, AlR ₄ (R indicates a hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.).

R ^{6 to} R ⁸ are independently hydrocarbon groups or halogenated hydrocarbon groups, at least one of which is an aromatic hydrocarbon group.

Specifically, the hydrocarbon group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a neopentyl group, an n-hexyl group and the like. A linear or branched alkyl group having 1 to 30 carbon atoms, preferably 1 to 20; a vinyl group, an allyl group, an isopropenyl group, etc. having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms. Linear or branched alkenyl group; linear or branched alkynyl group having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms such as ethynyl group and propargyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, Cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20 carbon atoms such as cyclohexyl group and adamantyl group; cyclic unsaturated group having 5 to 30 carbon atoms such as cyclopentadienyl group, indenyl group and fluorenyl group. Hydrocarbon group; aryl group having 6 to 30, preferably 6 to 20 carbon atoms such as phenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group, anthracenyl group; tolyl group, isopropylphenyl group, t- Examples thereof include alkyl-substituted aryl groups such as a butylphenyl group, a dimethylphenyl group and a di-t-butylphenyl group.
Further, the hydrocarbon group may be substituted with another hydrocarbon group, and examples thereof include an aryl group-substituted alkyl group such as a benzyl group and a cumyl group.

Examples of the halogenated hydrocarbon group include a group in which at least one hydrogen atom of the hydrocarbon group is substituted with a halogen, and examples thereof include a trifluoromethyl group, a pentafluorophenyl group, a chlorophenyl group and the like having 1 carbon atom. Examples thereof include ~ 30, preferably 1 to 20 halogenated hydrocarbon groups.

Specific examples of the aromatic hydrocarbon group include an aryl group having 6 to 30, preferably 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group and an anthrasenyl group. Examples include alkyl-substituted aryl groups such as trill group, isopropylphenyl group, t-butylphenyl group, dimethylphenyl group and di-t-butylphenyl group. The aromatic hydrocarbon group may be substituted with another hydrocarbon group.
Examples of the halogenated aromatic hydrocarbon group include a group in which at least one hydrogen atom of the aromatic hydrocarbon group is substituted with halogen.

Since at least one of the hydrocarbon groups of R ^{6 to} R ⁸ is an aromatic hydrocarbon group, the polymerization catalyst containing the transition metal compound (B) has good activity even under high temperature polymerization conditions. , Suitable for the production of the olefin resin (β) according to the present invention, and the thermoplastic elastomer obtained by using the produced olefin resin (β) exhibits good performance.

When m is 2 or more, two of the groups represented by R ^{2 to} R ⁸ may be linked between the structural units of the formula [B]. Furthermore, R ¹ each other when m is 2 or more, R ² together, R ³ together, R ⁴ together, R ⁵ each other, R ⁶ together, R ⁷ together, each other R ⁸ may be the same or different from each other ..

When n is an integer of 2 or more, the plurality of groups represented by X may be the same or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring.

Further, as the transition metal compound (B) as described above, one kind alone or two or more kinds can be used.

[Compound (C)]
The compound (C) is a compound other than the compound (A) and the compound (B), reacts with the compound (A) and the compound (B), and functions as a catalyst for olefin polymerization. Is
(C-1) Organometallic compound,
(C-2) Organoaluminium oxy compound and
(C-3) At least one compound selected from the compound (A) or the compound which reacts with the compound (B) to form an ion pair.
Hereinafter, the compounds (C-1) to (C-3) will be described in order.

((C-1) Organometallic compound)
Specific examples of the (C-1) organometallic compound include an organoaluminum compound represented by the following formula (C-1a), a group 1 metal of the periodic table represented by the formula (C-1b), and aluminum. Examples thereof include a complex alkylated product of the above, and a dialkyl compound of a metal of Group 2 or Group 12 of the periodic table represented by the formula (C-1c). The (C-1) organometallic compound does not include the (C-2) organoaluminum oxy compound described later.

R ^a _p Al (OR ^b ) _q H _r Y _s (C-1a)
(In the formula (C-1a), ^Ra and ^Rb may be the same or different from each other, and represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and Y represents a halogen atom. Shown, 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).

M ³ AlR ^c ₄ (C-1b)
(In the formula (C-1b), 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.)

R ^d R ^e M ⁴ (C-1c)
(In the formula (C-1c), R ^d and R ^e may be the same or different from each other, and represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 hydrocarbon groups or halogenated hydrocarbon groups. , M ⁴ is Mg, Zn or Cd.)

Examples of the organoaluminum compound represented by the formula (C-1a) include compounds represented by the following formulas (C-1a-1) to (C-1a-4).

R ^a _p Al (OR ^b ) _3-p (C-1a-1)
(In the formula, R ^a and R ^b may be the same or different from each other, and represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably 1.5 ≦ p ≦. It is a number of 3.

R ^a _p AlY _3-p (C-1a-2)
(In the formula, Ra represents ^a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4, Y represents a halogen atom, and p is preferably a number of 0 <p <3.)

^{_{R a p AlH 3-p (}} C-1a-3)
(In the formula, Ra represents ^a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and p is preferably a number of 2 ≦ p <3.)

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

More specifically, as the organic aluminum compound represented by the formula (C-1a), trimethylaluminum, triethylaluminum, trin-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, and tridecyl Tri-n-alkylaluminum such as aluminum;
Triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, tri4 -Tri-branched alkyl aluminum such as methylpentylaluminum, tri2-methylhexylaluminum, tri3-methylhexylaluminum, tri2-ethylhexylaluminum;
Tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum;
Triarylaluminum such as triphenylaluminum and tritrylaluminum;
Dialkylaluminum hydrides such as diisobutylaluminum hydride;
Trialkenyl aluminum such as triisoprenyl aluminum;
Dialkylaluminum alkoxides such as dimethylaluminum methoxyde, diethylaluminum ethoxide, dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxydo and butylaluminum sesquibutoxide;
Partially alkoxylated aluminum hydrocarbons with an average composition of R ^a _2.5 Al (OR ^b ) _0.5 (in the formula, R ^a and R ^b may be the same or different from each other and have a number of carbon atoms. Shows 1 to 15, preferably 1 to 4 hydrocarbon groups);
Diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-- Dialkylaluminum aryloxides such as 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, diisobutylaluminum chloride;
Alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromid;
Partially halogenated alkylaluminum such as alkylaluminum dihalide such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromid;
Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride;
Partially hydrogenated alkylaluminum, such as alkylaluminum dihydrides such as ethylaluminum dihydrides and propylaluminum dihydrides;
Examples thereof include partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxychloride, butylaluminum butokicyclolide, and ethylaluminum ethoxybromid.

Further, in the present invention, a compound similar to (C-1a) can also be used, and as such a compound, for example, an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom, specifically, an organoaluminum compound. , (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) _{2 and the} like.

Examples of the compound represented by the formula (C-1b) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

Examples of the compound represented by the formula (C-1c) include dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium, dimethyl zinc, diethyl zinc, diphenyl zinc, di-n-propyl zinc, diisopropyl zinc, and di-n. -Butyl zinc, diisobutyl zinc, bis (pentafluorophenyl) zinc, dimethyl cadmium, diethyl cadmium and the like can be mentioned.

In addition to the above compounds, the (C-1) organometallic compound includes methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, and propylmagnesium bromide. , Propylmagnesium chloride, butylmagnesium bromide, butylmagnesium chloride and the like can also be used.

Further, a compound such that the organoaluminum compound is formed in the polymerization system, for example, a combination of aluminum halide and alkyllithium, a combination of aluminum halide and alkylmagnesium, and the like can be used as the (C-1) organometallic metal. It can also be used as a compound.

As the organometallic compound (C-1), one kind alone or two or more kinds can be used.

((C-2) Organoaluminium oxy compound)
The (C-2) organoaluminum oxy compound may be a conventionally known aluminoxane, and may be, for example, a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. .. Specific examples of the (C-2) organoaluminum oxy compound include methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane.

Conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent.
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method in which an organic aluminum compound such as trialkylaluminum is added to the hydrocarbon medium suspension of the above, and adsorbed water or water of crystallization is reacted with the organic aluminum compound.
(2) A method in which water, ice or water vapor is allowed to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organometallic component.
Further, after removing the solvent or the unreacted organoaluminum compound from the obtained solution of aluminoxane by distillation, the obtained aluminoxane may be redissolved in a solvent or suspended in a poor solvent of aluminoxane.

Specific examples of the organoaluminum compound used when preparing alminoxane include organoaluminum compounds similar to those exemplified as the organoaluminum compound belonging to the above formula (C-1a).
Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.

As the organoaluminum compound, one kind alone or two or more kinds can be used.

Examples of the solvent used for preparing alminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and simen, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane, and cyclopentane. , Cyclohexane, cyclooctane, methylcyclopentane and other alicyclic hydrocarbons, petroleum distillates such as gasoline, kerosene and light oil, or halides of the aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons. In particular, halogenated hydrocarbon solvents such as chlorinated compounds and brominated compounds can be mentioned. Further, ethers such as ethyl ether and tetrahydrofuran can be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.

The benzene-insoluble organoaluminum oxy compound is a compound in which the Al component dissolved in benzene at 60 ° C. is usually 10% by mass or less, preferably 5% by mass or less, and particularly preferably 2% by mass or less in terms of Al atoms. It is preferable to have.

As the organoaluminum oxy compound (C-2), an organoaluminum oxy compound containing boron represented by the following formula (III) can also be mentioned.

（式（ＩＩＩ）中、Ｒ¹⁷は炭素原子数が１〜１０の炭化水素基またはハロゲン化炭化水素基を示し、４つのＲ¹⁸は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数が１〜１０の炭化水素基を示す。）

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

The organoaluminum oxy compound containing boron represented by the formula (III) is prepared by, for example, using an alkylboronic acid represented by the following formula (IV) and an organoaluminum compound in an inert solvent under an inert gas atmosphere. It can be produced by reacting at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours.

R ^19- B (OH) ₂ (IV)
(In formula (IV), R ¹⁹ represents the same group as R ¹⁷ in formula (III).)

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

Specific examples of the organoaluminum compound to be reacted with such alkylboronic acid include organoaluminum compounds similar to those exemplified as the organoaluminum compound belonging to the above formula (C-1a).
As the organoaluminum compound, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These can be used alone or in combination of two or more.

As the (C-2) organoaluminum oxy compound, one kind alone or two or more kinds can be used.

((C-3) A compound that reacts with a crosslinked metallocene compound (A) or a transition metal compound (B) to form an ion pair)
Examples of the compound (C-3) (hereinafter, referred to as “ionized ionic compound”) that reacts with the crosslinked metallocene compound (A) or the transition metal compound (B) to form an ion pair include JP-A No. 1-501950. Japanese Patent Application Laid-Open No. 1-502036, Japanese Patent Application Laid-Open No. 3-179005, Japanese Patent Application Laid-Open No. 3-179006, Japanese Patent Application Laid-Open No. 3-207703, Japanese Patent Application Laid-Open No. 3-207704, US Pat. No. 5,321106, etc. Examples thereof include Lewis acid, ionic compounds, borane compounds and carborane compounds described in. In addition, heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, the Lewis acid is represented by BR ₃ (R is a phenyl group or a fluorine atom which may have a substituent such as a fluorine atom, a methyl group or a trifluoromethyl group). Examples thereof include trifluoroborone, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl). Examples thereof include boron, tris (p-tolyl) boron, tris (o-tolyl) boron, and tris (3,5-dimethylphenyl) boron.

Examples of the ionic compound include compounds represented by the following formula (V).

（式（Ｖ）中、Ｒ²⁰はＨ⁺、カルボニウムカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオンまたは遷移金属を有するフェロセニウムカチオンであり、Ｒ²¹〜Ｒ²⁴は、互いに同一でも異なっていてもよく、有機基、好ましくはアリール基または置換アリール基である。）。

(In formula (V), R ²⁰ is a ferrosenium cation having H ⁺ , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptiltyrienyl cation or a transition metal, and R ^{21 to} R ²⁴ are , They may be the same or different from each other and are organic groups, preferably aryl groups or substituted aryl groups).

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

Specifically, the ammonium cations include trialkylammonary cations such as trimethylammonium cation, triethylammonary cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation; N, N-dimethylanilinium cation, N, N-dialkylanilinium cations such as N, N-diethylanilinium cations, N, N, 2,4,6-pentamethylanilinium cations; dialkylammonium cations such as di (isopropyl) ammonium cations, dicyclohexylammonium cations And so on.

Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

As R ²⁰ , carbonium cations and ammonium cations are preferable, and triphenylcarbonium cations, N, N-dimethylanilinium cations, and N, N-diethylanilinium cations are particularly preferable.

Moreover, as an ionic compound, a trialkyl-substituted ammonium salt, an N, N-dialkylanilinium salt, a dialkylammonium salt, a triarylphosphonium salt and the like can also be mentioned.

Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, and 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, tri ( Examples thereof include n-butyl) ammonium tetra (o-tolyl) boron.

Specifically, as the N, N-dialkylanilinium salt, for example, N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N, 2, 4, Examples thereof include 6-pentamethylanilinium tetra (phenyl) boron.

Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

Furthermore, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrosenium tetra (pentafluorophenyl) borate, triphenylcarbenium penta Phenylcyclopentadienyl complex, N, N-diethylanilinium pentaphenylcyclopentadienyl complex, boron compound represented by the following formula (VI) or (VII) and the like can also be mentioned.

（式（ＶＩ）中、Ｅｔはエチル基を示す。）

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

（式（ＶＩＩ）中、Ｅｔはエチル基を示す。）

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

Specifically, as the borane compound, for example, decaborane;
Bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate , Anion salts such as bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachloro dodecaborate;
Metal borane anions such as tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III) Salt is mentioned.

Specifically, as the carborane compound, for example, 4-carbanonaborane, 1,3-dicarbanoborane, 6,9-dicarbadecaborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodeca Hydlide-1-methyl-1,3-dicarbanonaborane, Undeca Hydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2,7-dicarbaundeca Boranes, undecahydride-7,8-dimethyl-7,8-dicarbundecaborane, dodecahydride-11-methyl-2,7-dicarbaundecaborane, tri (n-butyl) ammonium 1-carbadecabolate, Tri (n-butyl) ammonium 1-carbundecaborate, 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-carbundecaborate, tri (n-butyl) ammonium 7-carbaundecaborate, Tri (n-butyl) ammonium 7,8-dicarbundecaborate, tri (n-butyl) ammonium 2,9-dicarbundecaborate, tri (n-butyl) ammonium dodecahydride-8-methyl-7,9- Dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaun Decaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate , Anion salts such as tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbundecaborate;
Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonabolate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) Telate (III), Tri (n-Butyl) Ammonium Bis (Undeca Hydlide-7,8-Dicarba Undecaborate) Cobalate (III), Tri (n-Butyl) Ammonium Bis (Undeca Hydride-7) , 8-dicarbundecaborate) Niklate (III), Tri (n-butyl) Ammonium Bis (Undeca Hydlide-7,8-dicarbundecaborate) Copper Acidate (III), Tri (n-butyl) Ammonium Bis (Undeca Hydlide-7,8-Dicarba Undecaborate) Hydrochloride (III), Tri (n-Butyl) Ammonium Bis (Nona Hydride-7,8-Dimethyl-7,8-Dicarba Undecaborate) Tetrate (III), Tri (n-Butyl) Ammonium Bis (Nona Hydride-7,8-Dimethyl-7,8-Dicarbundecaborate) Chromate (III), Tri (n-Butyl) Ammonium Bis (N-butyl) Tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate (III) , Bis [Tri (n-butyl) Ammonium] Bis (Undeca Hydlide-7-Carbaundecaborate) Manganate (IV), Bis [Tri (n-Butyl) Ammonium] Bis (Undeca Hydride-7-Cal) Examples include salts of metal carborane anions such as bound carbolarate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbundecaborate) nickelate (IV). ..

The heteropoly compound is a compound 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, limbanadic acid, germanovanadic acid, arsenic vanadic acid, linniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, tungstic acid, germanomolybdic acid, arsenic molybdic acid, tungstic acid, phosphorus. Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdate vanadic acid, phosphombdate vanadic acid, germanotangstvanadic acid, phosphomolybdate tongue tungstic acid, germanomolybdate tongue tungstic acid, phosphomolybdate tungstic acid , Phospholybdoniobic acid, and salts of these acids, but not limited to. The salt is a salt of the acid, for example, a metal of Group 1 or Group 2 of the periodic table, specifically, a salt of lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium or the like. , Organic salts such as triphenylethyl salt and the like.

The isopoly compound is a compound composed of a metal ion of one atom selected from vanadium, niobium, molybdenum and tungsten, and can be regarded as a molecular ion species of a metal oxide. Specific examples include, but are not limited to, vanadate, niobic acid, molybdic acid, tungstic acid, and salts of these acids. Examples of the salt include metals of Group 1 or Group 2 of the periodic table, specifically salts of lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and the like. Examples thereof include organic salts such as triphenylethyl salt.

As the pre-ionized ionic compound (C-3), one kind alone or two or more kinds can be used.

When a (C-2) organoaluminum oxy compound such as methylaluminoxane as a co-catalyst component is used in combination with the crosslinked metallocene compound (A), it exhibits extremely high polymerization activity with respect to the olefin compound.

[Polymerization method of olefin]
Hereinafter, a method including the above-mentioned (a) or (b) will be described.
The polymerization of the olefin can be carried out by any of a solution polymerization method, a bulk polymerization method, a liquid phase polymerization method such as suspension polymerization, and a gas phase polymerization method, but the subsequent steps [a-2] of the polymerization method [a] described later and The polymerization method [b] is preferably a liquid phase polymerization method.

In the liquid phase polymerization method, an inert hydrocarbon medium can be used, and specifically, the medium is an aliphatic hydrocarbon such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene. Aliphatic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane or mixtures thereof. , Olefin itself can also be used as a solvent.

When the above-mentioned catalyst for olefin polymerization is used in the production of the olefin resin (β), the crosslinked metallocene compound (A) is usually 10 ^-8 to 1 mol, preferably 10 ^{-7 to} 0, per liter of the reaction volume. Used in an amount of 5 mol, the transition metal compound (B) is usually in an amount of 10 ^-12 to ^10-2 mol, preferably 10 ^-10 to 10 ^-3 mol, per liter of reaction volume. Used in.

The crosslinked metallocene compound (A) and the transition metal compound (B) usually have a molar ratio (B / A) of the transition metal compound (B) to the crosslinked metallocene compound (A) of 0.00001 to 100, preferably 0.00001 to 100. It is used in an amount of 0.0005-10, more preferably 0.0001-5.

The organic metal compound (C-1) is the organic metal compound (C-1) and the transition metal atom (M) in the crosslinked metallocene compound (A) and the transition metal compound (B) (in the crosslinked metallocene compound (A)). It is used in an amount such that the molar ratio (C-1 / M) with titanium atom, zirconium atom or hafnium atom is usually 0.01 to 100,000, preferably 0.05 to 50,000.

The organic aluminum oxy compound (C-2) includes an aluminum atom in the organic aluminum oxy compound (C-2) and a transition metal atom (M) (crosslinked metallocene) in the crosslinked metallocene compound (A) and the transition metal compound (B). In compound (A), the molar ratio (C-2 / M) with titanium atom, zirconium atom or hafnium atom) is usually 10 to 500,000, preferably 20 to 100,000.

The ionized ionic compound (C-3) is the ionized ionic compound (C-3) and the transition metal atom (M) in the crosslinked metallocene compound (A) and the transition metal compound (B) (crosslinked metallocene compound (A)). In the above, the molar ratio (C-3 / M) with titanium atom, zirconium atom or hafnium atom) is usually 1 to 10, preferably 1 to 5.

The polymerization temperature of the olefin using such an olefin polymerization catalyst is usually in the range of −50 to + 300 ° C., preferably 0 to 170 ° C. The polymerization pressure is usually from normal pressure to 9.8 MPa (100 kg / cm ² ), preferably from normal pressure to 4.9 MPa (50 kg / cm ² ), and the polymerization reaction is batch type, semi-continuous type or continuous type. Either method can be used.

The molecular weight of the resulting olefin resin (β) can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature, and further, the compounds (A), (B) and (C) to be used. ) Can be adjusted by selecting any of the compounds or by selecting a combination.

Examples of the olefin used for the polymerization include ethylene and the above-mentioned α-olefin having 3 to 20 carbon atoms and a polyene. For these olefins, ethylene can be used as an essential monomer, and one or more other monomers can be used in combination.

In the present invention, the olefin resin (β) can be produced by either the following polymerization method [a] or the polymerization method [b].

-Polymerization method [a]
A pre-step [a-1] of polymerizing ethylene to obtain a macromonomer in the presence of the transition metal compound (B) and the compound (C), and then using the crosslinked metallocene compound (A) and the compound (C) to obtain ethylene. And the post-step [a-2] of copolymerizing at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms, polyene, and the reaction product of the pre-step [a-1]. How to include.

Pre-process [a-1]
The previous step [a-1] is a step of polymerizing mainly ethylene using the transition metal compound (B) and the compound (C) to obtain a macromonomer which is substantially an ethylene polymer, and the polymerization method is The method is not particularly limited, and examples thereof include the above-mentioned methods. In this pre-step [a-1], a vinyl-terminated macromonomer can be obtained. In the case of liquid phase polymerization, the obtained reaction solution may be introduced into the subsequent step as it is, or after the macromonomer is taken out, the macromonomer may be introduced into the subsequent step as a lump or as a powder, or taken out. A slurry or solution may be prepared using the macromonomer, and the obtained slurry or solution may be introduced into a subsequent step.

Post-process [a-2]
The post-step [a-2] involves ethylene, at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms, and a polyene in the presence of the crosslinked metallocene compound (A) and compound (C). This is a step of copolymerizing with the macromonomer obtained in the previous step [a-1]. The polymerization method is not particularly limited, and examples thereof include the above-mentioned methods, but the liquid phase polymerization method is particularly preferable because it produces an amorphous or low crystallinity ethylene / α-olefin / polyene copolymer moiety. Solution polymerization is preferable in order to control the concentration of each monomer and obtain an olefin resin (β) having a desired structure.

In the polymerization reaction, the pre-step [a-1] may be carried out in a batch manner and the post-step [a-2] may also be carried out in a batch formula, or the pre-step [a-1] may be carried out in a batch formula and the macromonomer taken out. The subsequent step [a-2] may be continuously performed using the above. Further, by performing the pre-step [a-1] in a continuous manner and using the product as it is in the post-step [a-2], the post-step [a-2] can also be carried out in a continuous manner. Further, the pre-step [a-1] can be performed continuously and the post-step [a-2] can be performed in batches.

-Polymerization method [b]
Ethylene in the presence of crosslinked metallocene compound (A), transition metal compound (B), compound (C), at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms, and polyene. It is a method of polymerizing in a single stage, and can be performed by one polymerizer. By using the transition metal compound (B) and the compound (C), ethylene tends to be highly selectively polymerized even if an olefin other than ethylene is present in the polymerization system. Further, by using the transition metal compound (B) and the compound (C), there is a tendency that an ethylene polymer (macromonomer) having a vinyl terminal and having a relatively small molecular weight can be produced. Then, by using the crosslinked metallocene compound (A) and the compound (C), a polymer [R1] having a large molecular weight can be produced. In this way, the olefin resin (β) can be synthesized under one polymerization reaction condition.

In the method for producing the olefin resin (β), the subsequent steps [a-2] and the polymerization method [b] of the polymerization method [a] are preferably carried out by a solution polymerization method in a temperature range of 80 to 300 ° C. ..

The "solution polymerization" is a general term for a method of polymerizing in a state where the polymer is dissolved in an inert hydrocarbon solvent described later. The polymerization temperature of solution polymerization is preferably 80 to 300 ° C, more preferably 90 to 250 ° C. In solution polymerization, if the polymerization temperature is less than 80 ° C., the macromonomer may not be sufficiently dissolved and the polymer [R1] may not be efficiently produced. Further, when the polymerization temperature is less than 80 ° C., the polymerization activity is extremely lowered, so that it tends to be impractical in terms of productivity. Further, in the polymerization temperature region of 80 ° C. or higher, as the temperature increases, the solution viscosity at the time of polymerization decreases, the heat of polymerization can be easily removed, and the obtained polymer [R1] can be made higher in molecular weight. However, if the polymerization temperature exceeds 300 ° C., the obtained polymer may be deteriorated, which is not preferable.

The polymerization pressure is usually under the conditions of normal pressure to 10 MPa gauge pressure, preferably normal pressure to 8 MPa gauge pressure, and the polymerization reaction can be carried out by any method of batch type, semi-continuous type and continuous type. Further, it is also possible to carry out the polymerization in two or more stages having different reaction conditions. The weight average molecular weight of the obtained polymer [R1] can be adjusted by changing the hydrogen concentration and the polymerization temperature in the polymerization system, and further can be adjusted by the amount of the compound (C) used. .. When hydrogen is added, the amount thereof is appropriately about 0.001 to 5,000 NL per 1 kg of the produced polymer [R1].

The solvent used in the solution polymerization is usually an inert hydrocarbon solvent, preferably a saturated hydrocarbon having a boiling point of 50 to 200 ° C. under normal pressure. Specific examples thereof include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane and kerosene; and 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 are also included in the category of inert hydrocarbon solvents, and their use is not restricted.

In the production of olefin resin (β), rubber, inorganic filler, weather resistance stabilizer, heat stabilizer, antistatic agent, anti-slip agent, anti-blocking, as long as the object of the present invention is not impaired. Additives such as agents, antifogging agents, lubricants, pigments, dyes, plasticizers, antioxidants, hydrochloric acid absorbers, antioxidants, and crystal nucleating agents may be used. When such an additive is used, the obtained component may contain these additives, but in the present invention, the olefin resin (β) is also referred to when such an additive is contained.

The olefin resin (β) can be used for the following pellets, thermoplastic elastomers, etc., but in this case, it contains various additives and resins other than the polymer [R1] as described above. It can be used for these as a composition.
The amount of the additive or other resin added is not particularly limited as long as it does not impair the object of the present invention, but for example, the total amount of the olefin resin (β) and the additive or other resin is 100% by weight. On the other hand, an embodiment in which the polymer [R1] is contained in an amount of 5 to 100% by weight, preferably 25 to 100% by weight, more preferably 50 to 100% by weight, still more preferably 70 to 100% by weight. It can be exemplified.

≪Pellets≫
The pellet of the present invention may contain the olefin resin (β) of the present invention, and may further contain various additives and resins other than the polymer [R1] as described above.
An additive for preventing powder or the like from adhering to the surface of the pellet of the present invention may be present.

The pellet of the present invention can be used as it is, but it is preferable to use it as a raw material for a thermoplastic elastomer by mixing it with another resin and cross-linking it, if necessary.

The pellets of the present invention can be obtained by kneading and granulating using an extruder equipped with a pelletizer.

The pellet of the present invention is not particularly limited, and examples thereof include a spherical shape, a columnar shape, a prismatic shape, a sponge shape, and the like, and the aspect ratio is preferably 5 or less, more preferably 3 or less, and further preferably 1 to 2. , Particularly preferably 1 to 1.5. The size is not particularly limited, but is usually about 0.1 to 50 mm, preferably 0.5 to 30 mm, more preferably 1 to 10 mm, and particularly preferably 3 to 8 mm.

For the pellet size, the maximum length Lmax1 to 10 and the minimum length Lmin1 to 10 of each of 10 arbitrarily selected pellets (pellets 1 to 10) were measured using a caliper, and the average value was measured as the pellet. Expressed as the size of.
Pellet size = (Lmax1 + Lmax2 + Lmax3 + Lmax4 + Lmax5 + Lmax6 + Lmax7 + Lmax8 + Lmax9 + Lmax10 + Lmin1 + Lmin2 + Lmin3 + Lmin4 + Lmin5 + Lmin6 + Lmin7 + Lmin8 + Lmin9 + Lmin10) / 20

≪Thermoplastic elastomer≫
The thermoplastic elastomer of the present invention is prepared by using a composition containing the olefin resin (β), the crystalline polyolefin resin (α) and the cross-linking agent (γ) (hereinafter, also referred to as “polymer composition”). , Preferably a crosslinked product of the elastomer composition, or prepared using the pellets, preferably a crosslinked product using the pellets, and more preferably the polymer composition dynamically. It is a dynamic heat-treated product obtained by heat treatment.

[Crystalline polyolefin resin (α)]
The crystalline polyolefin resin (α) is preferably a crystalline high molecular weight solid product obtained by polymerizing one or more monoolefins. Examples of such polyolefins include isotactic or syndiotactic monoolefin polymer resins. These resins are commercially available.
The crystalline polyolefin resin (α) has a role of improving the fluidity and heat resistance of the thermoplastic elastomer.
The crystalline polyolefin resin (α) may be used alone, or two or more kinds may be used.

Specific examples of the raw material olefin of the crystalline polyolefin resin (α) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, and 2-methyl-1-propene. , 3-Methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and the like, α-olefins having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms. As these α-olefins, one kind alone or two or more kinds can be used.
The polymerization mode may be a random type or a block type, and any polymerization mode may be adopted as long as a resinous substance can be obtained.

As the crystalline polyolefin resin (α), a propylene-based polymer is preferable, and specifically, a propylene homopolymer, a propylene / ethylene block copolymer, a propylene / ethylene random copolymer, a propylene / ethylene / butene random copolymer, and the like are preferable.

The crystalline polyolefin resin (α) has a melt flow rate (MFR: ASTM D1238-65T, 230 ° C., 2.16 kg load), usually 0.01 to 100 g / 10 minutes, preferably 0.05 to 50 g / 10. It is desirable to be in the range of minutes.

The ratio of the crystalline polyolefin resin (α) and the olefin resin (β) of the present invention to the total of the crystalline polyolefin resin (α) and the olefin resin (β) is that the crystalline polyolefin resin (α) is used. It is preferably 10 to 80% by weight, more preferably 15 to 60% by weight, and the olefin resin (β) is preferably 20 to 90% by weight, more preferably 40 to 85% by weight in terms of processability. ..

[Crosslinking agent (γ)]
Examples of the cross-linking agent (γ) include phenolic vulcanizers such as organic peroxides, sulfur, sulfur compounds, and phenol resins, and among them, organic peroxides are preferably used.
The cross-linking agent (γ) may be used alone, or two or more kinds may be used.

Specific examples of the organic peroxide include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, and 2,5-dimethyl-2. , 5-Di (tert-butylperoxy) hexin-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n -Butyl-4,4-bis (tert-butylperoxy) peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperbenzoate, tert-butylperoxyisopropyl Examples thereof include carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butylcumyl peroxide.

Among them, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane and 2,5-dimethyl-2,5-di (tert-butylperoxy) hexine in terms of odor and scorch stability. -3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane and n-butyl-4,4-bis (tert- Butylperoxy) Valerate is preferred.

The cross-linking agent (γ) is used in a proportion of 0.01 to 15 parts by weight, preferably 0.03 to 12 parts by weight, based on 100 parts by weight of the amount of the olefin resin (β). When the cross-linking agent is used in the above ratio, a thermoplastic elastomer in which the olefin resin (β) is cross-linked can be obtained, and a molded product having sufficient heat resistance, tensile properties and rubber elasticity can be obtained. Moreover, this thermoplastic elastomer is excellent in moldability.

[Crossing aid]
In the present invention, sulfur, p-quinone dioxime, p, p'-dibenzoylquinone dioxime, N-methyl-N, 4-dinitrosoaniline, nitrobenzene, diphenylguanidine are used for the cross-linking treatment with the cross-linking agent (γ). , Trimethylolpropane-N, N'-m-phenylenedi maleimide, eletin glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, polyfunctional methacrylate monomers such as allyl methacrylate, divinylbenzene, Polyfunctional vinyl monomers such as triallyl cyanurate, vinyl butyrate or vinyl stearate can be blended. By using such a compound, a uniform and mild cross-linking reaction can be expected. In particular, divinylbenzene is easy to handle, has good compatibility with an olefin resin (β), and has an organic peroxide solubilizing effect when an organic peroxide is used as a cross-linking agent (γ), and is organic. Since it acts as a dispersion aid for peroxides, it is most preferable because a thermoplastic elastomer having a uniform cross-linking effect due to heat treatment and a balance between fluidity and physical properties can be obtained.
The cross-linking aid may be used alone or in combination of two or more.

[Manufacturing method of thermoplastic elastomer]
The thermoplastic elastomer of the present invention is preferably obtained by dynamically cross-linking the polymer composition, and more preferably the olefin resin (β), the crystalline polyolefin resin (α), and the cross-linking agent ( γ), preferably a mixture of an organic peroxide and other components blended as needed, is obtained by dynamically heat-treating and cross-linking.

The thermoplastic elastomer of the present invention may be a partially crosslinked polymer composition or a completely crosslinked polymer composition.
In the present invention, "dynamically heat-treating" means kneading the polymer composition in a molten state.

The dynamic heat treatment is preferably performed in a non-open type apparatus, and is preferably performed in an atmosphere of an inert gas such as nitrogen or carbon dioxide. The temperature of the heat treatment is usually in the range of the melting point of the olefin resin (β) to 300 ° C., preferably 150 to 280 ° C., and more preferably 170 to 270 ° C. The kneading time is usually 1 to 20 minutes, preferably 1 to 10 minutes. Further, the shear force applied is typically 10～100,000Sec ^-1 at the highest shear rate, preferably 100～50,000Sec ^-1, more preferably 1,000～10,000Sec ^-1, more preferably 2,000 The range is ~ 7,000 sec ^-1 .

As the kneading device at the time of kneading, a mixing roll, an intensive mixer (eg, Banbury mixer, kneader), a single-screw or twin-screw extruder and the like can be used, but a non-open type device is preferable.

[Use of thermoplastic elastomer]
The thermoplastic elastomer of the present invention is appropriately molded and used according to the intended use. Examples of the molding method include commonly used molding methods such as an injection molding method, an extrusion molding method, a hollow molding method, and a compression molding method. Applications include automobile parts (weather strips, ceiling materials, interior seats, bumper moldings, side moldings, air spoilers, air duct hoses, cup holders, side brake grips, shift knob covers, seat adjustment knobs, flapper door seals, wire harness glomets, rack and Pinion boots, suspension cover boots, glass guides, inner belt line seals, roof guides, trunk lid seals, molded quarter wind gaskets, corner moldings, glass encapsulation, hood seals, glass run channels, secondary seals, various packings, etc. ), Civil and building material parts (water blocking material, joint material, building window frame, etc.), sports equipment (golf club, tennis racket grips, etc.), industrial parts (hose tube, gasket, etc.), home appliance parts (hose) , Packing, etc.), medical equipment parts, electric wires, miscellaneous goods, etc.

≪Crosslinked rubber≫
The crosslinked rubber of the present invention is prepared by using a composition containing the olefin resin (β) and / or pellets and a crosslinking agent (γ), and is preferably a crosslinked product of the composition.
The amount of the cross-linking agent (γ) used for the olefin resin (β) in the composition is the same as described above.

The crosslinked rubber can be obtained by a conventionally known method, and for example, the olefin resin (β) and / or pellets and a crosslinking agent (γ) are blended, if necessary, using the kneading apparatus. A composition with other components to be molded is prepared and molded into the intended shape by various molding methods using an extrusion molding machine, a calendar roll, a press, an injection molding machine, a transfer molding machine, etc., and at the same time as molding or molding. It can be obtained by introducing a product into a brewing tank and cross-linking the product.

The crosslinked rubber includes weather strips for automobiles; hoses for automobiles, water supply hoses, gas hoses, etc .; anti-vibration rubber for automobiles, anti-vibration rubber for railways, anti-vibration rubber for industrial machinery, anti-vibration rubber for construction, etc. Anti-vibration rubber; Belts such as transmission belts and transport belts; Sealing materials for automobile cups and sealing materials, sealing materials for industrial machinery, etc .; Weather strip sponges for automobiles, sealing sponges for construction, other hose protection sponges, cushions Foams such as sponges for use, heat insulating sponges, insulation pipes; coated electric wires, electric wire joints, electrically insulating parts, semi-conductive rubber parts; rolls for OA equipment, industrial rolls; rain gear, rubber rings, shoes, rubber gloves, latex products, Household products such as rubber balls; widely used for plastic modification, thermoplastic elastomer, engineering plastic modification, etc.

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

(1) Measurement of melting temperature (Tm) and heat of fusion ΔH The melting temperature (Tm) and heat of fusion ΔH of the olefin resin were measured by DSC measurement under the following conditions.
Using a differential scanning calorimeter [RDC220, manufactured by SII], a sample of about 10 mg was heated from 30 ° C. to 200 ° C. at a heating rate of 50 ° C./min under a nitrogen atmosphere, and held at that temperature for 10 minutes. Further, the temperature was cooled to 30 ° C. at a temperature lowering rate of 10 ° C./min, held at that temperature for 5 minutes, and then raised to 200 ° C. at a temperature rising rate of 10 ° C./min. The endothermic peak observed during this second temperature rise was defined as the melting peak, and the peak top temperature was determined as the melting temperature (Tm). Further, the heat of fusion ΔH was obtained by calculating the area of the melting peak. When the melting peak was multimodal, the area of the entire melting peak was calculated and calculated.

(2) Measurement of glass transition temperature (Tg) The glass transition temperature (Tg) of the olefin resin was measured by DSC measurement under the following conditions.
Using a differential scanning calorimeter [RDC220, manufactured by SII], a sample of about 10 mg was heated from 30 ° C. to 200 ° C. at a heating rate of 50 ° C./min under a nitrogen atmosphere, and held at that temperature for 10 minutes. Further, the temperature was cooled to −100 ° C. at a temperature lowering rate of 10 ° C./min, held at that temperature for 5 minutes, and then raised to 200 ° C. at a temperature rising rate of 10 ° C./min. At the time of the second temperature rise, the DSC curve bends due to the change in specific heat, and the temperature at the intersection of the tangent of the baseline at the lower temperature part than this bending and the tangent at the point where the inclination becomes maximum at the bent part is the glass. The transition temperature (Tg) was used.

(3) ¹³ C-NMR measurement For the purpose of composition analysis of ethylene, α-olefin and diene in olefin resin, graft structure, number of grafts (per 1000C) and structure of the following macromonomer (P-1), the following ¹³ C-NMR measurement was carried out under the conditions of.
Device: AVANCE III500 CryoProbe Product type nuclear magnetic resonance device manufactured by Bruker Biospin, measurement nucleus: ¹³ C (125 MHz), measurement mode: single pulse proton broadband decoupling, pulse width: 45 ° (5.00 μsec), number of points: 64 k , Measurement range: 250 ppm (-55 to 195 ppm), Repeat time: 5.5 seconds, Number of integrations: 512 times, Measurement solvent: Orthodichlorobenzene / benzene-d ₆ (4/1 v / v), Sample concentration: ca .. 60 mg / 0.6 mL, measurement temperature: 120 ° C., window function: exponential (BF: 1.0 Hz), chemical shift standard: benzene-d ₆ (128.0 ppm)

(4) GPC analysis In order to analyze the molecular weight of the olefin resin, analyze the molecular weight of the following macromonomer (P-1), and calculate the amount of residual macromonomer, GPC analysis was performed under the following conditions.
Equipment: Waters Alliance GPC 2000 type, Column: TSKgel GMH6-HT x 2 and TSKgel GMH6-HTL x 2 (both manufactured by Tosoh, inner diameter 7.5 mm x length 30 cm), column temperature: 140 ° C, mobile phase : Orthodichlorobenzene (containing 0.025% dibutylhydroxytoluene), detector: differential refractometer, flow rate: 1.0 mL / min, sample concentration: 0.15% (w / v), injection volume: 0.5 mL, Sampling time interval: 1 second, column calibration: monodisperse polystyrene (manufactured by Tosoh)

(5) Extreme viscosity ([η]: [dl / g])
The ultimate viscosity of the olefin resin was measured at 135 ° C. using a decalin solvent.

(6) Elution component at 20 ° C or lower ([wt%])
As for the elution component of the olefin resin at 20 ° C. or lower, the orthodichlorobenzene-soluble component at a temperature of 20 ° C. or lower was measured using a cross-separation chromatograph (CFC). Specifically, the procedure was carried out under the following conditions.
Equipment: Cross-separation chromatograph CFC2 (manufactured by Polymer ChAR), Detector (built-in): Infrared spectrophotometer IR ⁴ (manufactured by Polymer ChAR), Detection wavelength: 3.42 μm (2,920 cm ^-1 ) fixed, sample Concentration: 120 mg / 30 mL, injection volume: 0.5 mL, temperature lowering rate: 1.0 ° C / min, elution classification: 4.0 ° C interval (-20 ° C to 140 ° C), GPC column: Chromatography HT-806M x 3 (Showa Denko), GPC column temperature: 140 ° C, GPC column calibration: monodisperse polystyrene (manufactured by Toso), molecular weight calibration method: general-purpose calibration method (polystyrene conversion), mobile phase: o-dichlorobenzene (dibutylhydroxytoluene) Addition), flow rate: 1.0 mL / min

Hereinafter, a production example of the olefin resin will be described. In addition, in order to secure the sample amount required for evaluation, the production by the following method may be carried out multiple times.

[Example 1] Production of olefin resin (β-1) <Synthesis of macromonomer (P-1) (previous step [a-1])>
The compound (1) represented by the following formula used as a catalyst was synthesized according to [Synthesis Example 3] of International Publication No. 2006/0572229, and the macromonomer (P-1) was synthesized according to [Example 1] of the same publication. did. The product had a polyethylene equivalent of Mw of 1600, Mw / Mn of 2.32, and a one-end unsaturated rate of 99.0 mol% measured by ¹ H-NMR.

（式中、Ｐｈはベンゼン環を示す。）

(In the formula, Ph represents a benzene ring.)

<Graft copolymerization (post-process [a-2])>
Compound (2) represented by the following formula was synthesized by a known method.
5.0 g of macromonomer (P-1) and 500 ml of xylene were charged into a glass reactor having an internal volume of 1 L sufficiently substituted with nitrogen, and then the temperature was raised to 95 ° C. to dissolve the macromonomer. 180 liters / hr of ethylene and 50 liters / hr of propylene were continuously supplied thereto to saturate the liquid phase and the gas phase. 2. With continuous supply of ethylene and propylene, 1.5 mL (11.1 mmol) of 5-ethylidene-2-norbornene (also referred to as ENB) and a decan solution of triisobutylaluminum (1.0 mol / L) were added. Add 3.0 mL (0.030 mmol) of 0 mL (2.0 mmol), a toluene solution of compound (2) (0.010 mol / L), followed by triphenylcarbenium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (Ph ₃ CB). 15 mL (0.060 mmol) of a toluene solution (4.0 mmol / L) of C ₆ F ₅ ) ₄ ) was added, and polymerization was carried out at 95 ° C. for 30 minutes under normal pressure. The polymerization was stopped by adding a small amount of isobutanol. The obtained polymerization reaction solution was added to 1.5 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing the precipitate with methanol, a methanol solution containing an antioxidant Irganox1010 (manufactured by BASF) was added, and the mixture was dried under reduced pressure at 80 ° C. for 10 hours to obtain 22.4 g of an olefin resin (β-1). The analysis results of the obtained olefin resin (β-1) are shown in Table 1.

[Comparative Example 1] Production of Olefin Resin (β'-1) Polymerization was carried out in the same manner as in Example 1 except that the macromonomer (P-1) was not added in the subsequent step [a-2] of Example 1. This was carried out to obtain 18.8 g of an olefin resin (β'-1). The analysis results of the obtained olefin resin (β'-1) are shown in Table 1.

[Comparative Example 2] Production of Olefin Resin (β "-1) 17.4 g of Olefin Resin (β'-1) and macromonomer (P-1) were placed in a glass reactor with an internal volume of 1 L sufficiently substituted with nitrogen. ) 5.0 g and 500 ml of xylene were charged, and then the temperature was raised to 95 ° C. to dissolve the olefin resin (β'-1) and the macromonomer (P-1). A small amount of the obtained solution was used. The polymer was precipitated by adding it to 1.5 liters of methanol containing the hydrochloric acid of the above. After washing the precipitate with methanol, a methanol solution containing an antioxidant Irganox1010 (manufactured by BASF) was added, and the mixture was added at 80 ° C. for 10 hours. The mixture was dried under reduced pressure to obtain 22.4 g of an olefin resin (β "-1). The analysis results of the obtained olefin resin (β "-1) are shown in Table 1-1.

[Example 2]
Each component in Table 2 was weighed as shown in Table 2, and kneaded using a lab plast mill (capacity 100 cc) manufactured by Toyo Seiki Co., Ltd. at a rotation speed of 100 rpm for 1 minute and 25 seconds. Then, the rotation speed was lowered to 60 rpm, kneading was performed for 5 seconds, and the lab plast mill was stopped. The following cross-linking agent component was added thereto, and kneading by a laboplast mill (rotation speed: 60 rpm) was restarted (kneading time: 15 seconds), and then the rotation speed was increased to 100 rpm again and kneading was performed for 2 minutes and 15 seconds. A thermoplastic elastomer was obtained by the above steps (dynamic cross-linking). The obtained thermoplastic elastomer was taken out from the lab plast mill. The kneading temperature in the lab plast mill was 200 ° C.
<Crosslinking agent component>
Organic peroxide (PHSA): 0.28g
Divinylbenzene (DVB810): 0.19 g
Paraffin oil (PW-100): 0.47 g

[Comparative Examples Examples 3 and 4]
A thermoplastic elastomer was obtained by the same method as in Example 2 except that the components in Table 2 were used in the amounts shown in Table 2.

(1) MFR
The MFR of the obtained thermoplastic elastomer was measured at 230 ° C. with a load of 10 kg according to ASTM D 1238. The results are shown in Table 3.

(2) Hardness The obtained thermoplastic elastomer is pressed using a 50t press molding machine (KMF100-1E, manufactured by Kotaki Co., Ltd.) at a temperature of 190 ° C. for 10 minutes, and then at room temperature for 5 minutes. A 20 cm square, 2 mm thick sheet was obtained. The obtained sheets were stacked to make a thickness of 12 mm, and the hardness (JIS-A) was measured according to JIS K6253. The results are shown in Table 3.

(3) Tensile test Using a sheet obtained by the same method as in (2) above, a tensile test was performed under the conditions of a measurement temperature of 23 ° C. and a tensile speed of 500 mm / min according to JIS K6251, and modulus, breaking strength, and breaking were performed. The elongation was measured. The results are shown in Table 3.

(4) Compressed permanent strain (CS)
Using the sheet obtained by the same method as in (2) above, the compression set after 22 hours of treatment was measured at each temperature in Table 3 according to JIS K6250 6.5 and JIS K6262 (2013). .. The results are shown in Table 3.

From the results in Table 3, the thermoplastic elastomer of Example 2 had higher values in hardness, modulus and breaking strength than the thermoplastic elastomer of Comparative Example 3 and Comparative Example 4, and was compressed at -30 ° C to 23 ° C. The permanent strain (CS) is a small value. This is a thermoplastic elastomer obtained by using a resin (β-1) containing a graft-type olefin polymer, and a blend resin (β "-1) of an ethylene / propylene / diene copolymer and an ethylene polymer. Not only does it show that the mechanical properties such as hardness, rigidity and strength are significantly improved as compared with the obtained thermoplastic elastomer and the thermoplastic elastomer obtained by using the existing ethylene / propylene / diene copolymer. At the same time, it is shown that the compression set resistance, that is, the rubber elasticity is also significantly improved. This is because the ethylene polymer, which is a side chain of the graft-type olefin polymer contained in the resin (β-1), is used. It is considered that, at the same time as imparting high rigidity and strength to the elastomer, good rubber elasticity is also imparted by forming a physical cross-linking point in the elastomer component.

Claims (6)

An olefin resin (β) that satisfies the following requirements (I) to (IV).
(I) A graft-type olefin polymer [R1] having a main chain composed of an ethylene / α-olefin / polyene copolymer and a side chain composed of an ethylene polymer (II) a graft-type olefin polymer [ R1] has an average of 0.5 to 20 side chains per 1000 carbon atoms in the main chain polymer molecular chain. (III) In the range of 60 to 130 ° C. as measured by differential scanning calorimetry (DSC). Indicates the melting temperature (Tm), and the heat of fusion ΔH is in the range of 5 to 150 J / g. (IV) The glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) is in the range of -80 to -30 ° C. is there The olefin resin (β) according to claim 1, wherein the weight average molecular weight of the side chain of the grafted olefin polymer [R1] is in the range of 500 to 10,000. The olefin resin (β) according to claim 1 or 2, which satisfies the following requirement (VI).
(VI) The ratio (E value) of orthodichlorobenzene-soluble components at 20 ° C. or lower as measured by a cross-separation chromatograph (CFC) is 45 wt% or less. The method for producing an olefin resin (β) according to any one of claims 1 to 3 , which comprises the following (a) or (b).
(A) A step of polymerizing ethylene in the presence of a catalyst containing the following compounds (B) and (C) [a-1].
In the presence of a catalyst containing the following compounds (A) and (C), ethylene, at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms, polyene, and step [a-1]. Method including step [a-2] of copolymerizing with the reaction product of (b) In the presence of an olefin polymerization catalyst containing each of the following compounds (A) to (C), ethylene and 3 carbon atoms A method including a step of copolymerizing a component containing polyene with at least one α-olefin selected from ~ 20 α-olefins (A) a crosslinked metallocene compound represented by the following formula (I) (B) below. Transition metal compound represented by the formula [B] (C) (C-1) Organic metal compound, (C-2) Organic aluminum oxy compound, and (C-3) Crosslinked metallocene compound (A) or transition metal compound. At least one compound selected from a compound that reacts with (B) to form an ion pair.

(In formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² are independently other than hydrogen atom, hydrocarbon group, silicon-containing group or silicon-containing group, respectively. the indicated heteroatom-containing group, two groups adjacent to each other among R ¹ to R ⁴ may be bonded to each other to form a ring.
R ⁶ and R ¹¹ are the same atom or the same group selected from heteroatom-containing groups other than hydrogen atom, hydrocarbon group, silicon-containing group and silicon-containing group, and R ⁷ and R ¹⁰ are hydrogen atom and hydrocarbon. It is the same atom or the same group selected from a group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group, and R ⁶ and R ⁷ may be bonded to each other to form a ring, and R ¹⁰ and R ¹¹ may be bonded to each other to form a ring; however, R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.
R ¹³ and R ¹⁴ each independently represent an aryl group.
M represents a titanium atom, a zirconium atom or a hafnium atom.
Y ¹ represents a carbon atom or a silicon atom.
Q indicates a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or unconjugated diene having 4 to 10 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair. , J indicates an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Qs may be the same or different. )

(In the formula [B], M represents a transition metal atom of Group 4 or 5 of the periodic table. M represents an integer of 1 to 4. R ¹ is an acyclic hydrocarbon group having 1 to 4 carbon atoms. _{(C n 'H 2n' +} 1; n '= 1~4) .R 2 ~R 5 showing a may be the same or different from each other, a hydrogen atom, a halogen atom, a hydrocarbon group, halogenated hydrocarbon Group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group or tin-containing group, and two or more of them. May be linked to each other to form a ring. R ^{6 to} R ⁸ are independently hydrocarbon groups or halogenated hydrocarbon groups, at least one of which is an aromatic hydrocarbon group or halogenated aromatic. It is a group hydrocarbon group, and when m is 2 or more, two groups of R ^{2 to} R ⁸ may be linked. N is a number satisfying the valence of M, and X is Is 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, and a silicon-containing group. , Germanium-containing group or tin-containing group, and when n is 2 or more, they may be the same or different from each other, and a plurality of groups represented by X are bonded to each other to form a ring. May be.) The method for producing an olefin resin (β) according to claim 4 , wherein the copolymerization is carried out by a solution polymerization method in a temperature range of 80 to 300 ° C. A pellet containing the olefin resin (β) according to any one of claims 1 to 3 .