JP6624831B2 - Olefin resin, method for producing the resin, pellet, 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 obtained by adding ethylene / α-olefin rubber which is a copolymer of ethylene and α-olefin (propylene) to: A polyene such as a small amount of ethylidene norbornene (ENB), 1,4-hexadiene (1,4-HD), or dicyclopentadiene (DCP) is introduced as a third component to have a double bond. .

  EPDM, which is a typical copolymer, has excellent processability, weather resistance, ozone resistance, heat resistance, cold resistance, chemical resistance, and electrical properties. Used for strips, various sealing materials, bellows, etc.), civil engineering and construction materials, electric cables, industrial chemicals, belts, tires, tubes, hoses, gaskets, electric wires, waterproof materials, resin blends, etc.

  The thermoplastic elastomer (Thermoplastic Vulcanizates; TPV) obtained by dynamically cross-linking EPDM and crystalline polyolefin resin (mainly polypropylene) is a material that can simplify the molding process, consumes less energy, and is recyclable. In addition, since scrap and defective products can be reused, they have been widely used as high-performance materials in the vulcanized rubber field. TPV is a multiphase 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 domains give the function of the vulcanized rubber to the TPV, and at high temperatures, the matrix flows and plastic deformation becomes possible. Therefore, a molded product can be easily obtained by a molding machine similar to thermoplastic plastic.

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

  There are only a few examples of such EPDM reports. For example, EPDMs having a linear block structure of crystalline polyethylene and an amorphous elastomer are disclosed in Patent Documents 1 and 2. In these documents, in order to synthesize a crystal-amorphous block copolymer in which a diene is introduced, a production method of sequentially synthesizing each segment using a vanadium catalyst composed of a reaction mixture of a vanadium compound and an organoaluminum compound is described. Used. Although the production ratio of the block copolymer in the produced polymer is not known, low temperature polymerization of about 10 ° C. is required in order to maintain the living polymerizability due to the performance of the catalyst, and the productivity is low because a large amount of catalyst is required. In addition, these documents do not show an effect of improving physical properties as TPV in a polypropylene resin.

JP-T-09-511776 Japanese Patent Publication No. Hei 10-504581

  The problem 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.

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above problems can be solved by using 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) satisfying the following requirements (I) to (IV).
(I) including 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 molecular chain of the main chain polymer. (III) In a measurement by differential scanning calorimetry (DSC), the temperature is in the range of 60 to 130 ° C. The melting temperature (Tm) is shown, 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 graft-type olefin polymer [R1] is in the range of 500 to 10,000.

[3] The method for producing an olefin resin (β) according to [1] or [2], comprising the following (a) or (b).
(A) a step [a-1] of polymerizing ethylene in the presence of a catalyst containing the following compounds (B) and (C);
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, a polyene, and a step [a-1] (B) in the presence of an olefin polymerization catalyst containing the following compounds (A) to (C) in the presence of an olefin polymerization catalyst containing the compounds of the following (A) to (C): A method comprising a step of copolymerizing a component containing at least one α-olefin selected from α-20 to α-20 and a polyene (A) a crosslinked metallocene compound represented by the following formula (I) (B) Transition metal compound represented by formula [B] (C) (C-1) organometallic compound, (C-2) organoaluminum oxy compound, and (C-3) bridged metallocene compound (A) or transition metal compound Reacts with (B) Compound to form an ion pair, at least one compound selected from

（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 the formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a group other than a silicon-containing group. And two adjacent groups among R ^{1 to} R ⁴ may be bonded to each other to form a ring.
R ⁶ and R ¹¹ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a hetero atom-containing group other than the silicon-containing group, and R ⁷ and R ¹⁰ are a hydrogen atom, a hydrocarbon group, are the same atoms or the same group selected from heteroatom-containing groups other than silicon-containing group and a silicon-containing group, R ⁶ and R ⁷ may bond to each other to form a ring, R ¹⁰ and R ¹¹ may combine with each other to form a ring; provided that R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.
R ¹³ and R ¹⁴ each independently represent an aryl group.
M represents a titanium atom, a zirconium atom or a hafnium atom.
Y ¹ represents a carbon atom or a silicon atom.
Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or non-conjugated diene having 4 to 10 carbon atoms, an anionic ligand or a neutral ligand capable of coordinating with a lone electron pair. , J represents an integer of 1 to 4, and when j is an integer of 2 or 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 belonging to Group 4 or 5 of the periodic table. M represents an integer of 1 to 4. R ¹ represents an acyclic hydrocarbon group having 1 to 4 carbon atoms. (C _{n ′} H _{2n ′ + 1} ; n ′ = 1 to 4.) R ^{2 to} R ⁵ may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, or a halogenated hydrocarbon. A group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. May be linked to each other to form a ring, and R ^{6 to} R ⁸ are independently a hydrocarbon group or a halogenated hydrocarbon group, at least one of which is an aromatic hydrocarbon group or a halogenated aromatic group. a family hydrocarbon group, and when m is 2 or more two groups of R ² to R ⁸ N is a number that satisfies the valence of M, and X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum Represents a containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. And a plurality of groups represented by X may be bonded to each other to form a ring.)

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

  [5] A pellet 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-based 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 the composition containing the olefin resin (β) according to [1] or [2] and a crosslinking agent (γ).

  According to the olefin resin according to the present invention, a thermoplastic elastomer excellent in rubber elasticity and mechanical properties in a range from room temperature to low temperature, for example, excellent in hardness, modulus, breaking strength and breaking elongation, and excellent in moldability and flowability. Can be easily obtained.

≪Olefin resin (β) ≫
The olefin resin (β) may be composed of only one olefin polymer or may be composed of two or more olefin polymers, but the following requirements (I) to (IV) are satisfied. It is characterized by satisfying all.
(I) including 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 molecular chain of the main chain polymer. (III) In the measurement by differential scanning calorimetry (DSC), the temperature is in the range of 60 to 130 ° C. The melting temperature (Tm) is shown, 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-based resin (β) means a component obtained at the time of synthesizing the polymer [R1]. That is, the olefin-based resin (β) is an ethylene / α-olefin / polyene copolymer that is not a graft copolymer, a macromonomer described below, or an antioxidant as a component obtained in the synthesis of the polymer [R1]. And the like.
However, the olefin-based 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, and still more preferably 90% by mass or more. Include in quantity.

[Requirements (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.

  In the present invention, the term "graft copolymer" refers to a T-type polymer or a comb-type polymer in which one or more side chains are bonded to a main chain. The polymer [R1] is not particularly limited as long as it has a side chain composed of an ethylene polymer, and the side chain can include a repeating unit other than ethylene-derived units without departing from the gist of the present invention.

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

The main chain and the side chain in 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 or more α-olefins selected from α-olefins having 3 to 20 carbon atoms, and a polyene, and the repeating unit derived from the ethylene is It is contained in an amount of 60 to 97 mol% based on all repeating units constituting the main chain.
(Ii) The main chain contains 0.1 to 10.0 mol% of a repeating unit derived from the polyene.
(Iii) The weight average molecular weight of the main chain is 20,000 to 400,000.
(Iv) The side chain is composed of a repeating unit 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 a copolymer of ethylene, at least one or more α-olefins selected from α to olefins having 3 to 20 carbon atoms, and a polyene, and has flexibility as a rubber property. It is a site that gives good properties and good low-temperature properties.

  Here, specific examples of the α-olefin having 3 to 20 carbon atoms to be copolymerized with ethylene include propylene, 1-butene, 1-pentene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl- 1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1 -Octene, ethyl-1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, die -1-butene, 1-nonene, 1-decene, 1-undecene, 1-dodecene.

  More preferred are α-olefins having 3 to 10 carbon atoms, and particularly preferred are α-olefins having 3 to 8 carbon atoms. Specifically, linear olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, 3-methyl-1-pentene, Examples include branched olefins such as 3-methyl-1-butene, and among them, propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene are preferred.

The proportion 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%, based on all repeating units contained in the main chain. Range.
When the molar ratio of the repeating units derived from ethylene in the main chain is within the above range, the olefin resin (β) has excellent flexibility and excellent low-temperature properties. Thermoplastic elastomers obtained by dynamic crosslinking also have excellent flexibility and low-temperature properties. On the other hand, if the repeating unit amount 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 or low temperature. It tends to have poor properties.

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

[Requirement (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 a repeating unit derived from the polyene.

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

  As the conjugated polyene, specifically, for example, 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 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 preferred because of their excellent copolymerizability.

  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, Non-conjugated such as 1,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 8-methyl-4-ethylidene-1,7-nonadiene and 4-ethylidene-1,7-undecadiene Diene; methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2 -Norbornene, 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2- Cyclic non-conjugated dienes such as rubornene, cyclopentadiene and norbornadiene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, 4- And trienes such as ethylidene-8-methyl-1,7-nonadiene. Among them, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene are preferred.

Although it is difficult to directly measure the composition ratio of ethylene / α-olefin / polyene in the main chain of the polymer [R1], it can be calculated, for example, by the following method.
In the light of the production conditions of the olefin resin (β) to be measured, an ethylene / α-olefin / polyene copolymer having only the main chain portion of the polymer [R1] is separately synthesized under reasonable conditions, and obtained. By analyzing the composition ratio of the copolymer thus obtained, the composition ratio of the main chain of the polymer [R1] can be obtained indirectly. Reasonable conditions are that a polymer equivalent to the main chain site of the polymer [R1] is formed in principle, such as the concentrations of ethylene, α-olefin and polyene in the polymerization system, and the molecular abundance ratio of ethylene and hydrogen. Condition. Specifically, as a method for producing the olefin-based 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 synthesized. When a method of copolymerizing with a polyene is employed, polymerization may be performed under the same conditions except that no macromonomer is used.
The evaluation can also be made by subtracting the composition ratio corresponding to the macromonomer or the side chain from the entire composition ratio of the resin (β).

[Requirements (iii)]
The weight average molecular weight of the main chain of the polymer [R1] is 20,000 to 400,000, preferably 30,000 to 300,000, 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, when the polymer is dynamically crosslinked using the olefin resin (β) and the crystalline polyolefin resin (α), the fluidity, the breaking strength, A thermoplastic elastomer excellent in 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 below the above range, the obtained thermoplastic elastomer tends to have a low rubber elasticity, and when the weight average molecular weight 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 a thermoplastic elastomer having the same.

  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 method for controlling the ethylene concentration include adjustment of ethylene partial pressure and adjustment of polymerization temperature. 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 determined based on the method of 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, by gel permeation chromatography (GPC). It can also be evaluated by discounting the effects of side chains.

[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.
The ethylene polymer substantially consisting of a repeating unit derived from ethylene means that the molar ratio of the repeating unit derived from ethylene is preferably 95.0 to 100 mol% with respect to all the repeating units contained in the ethylene polymer. More preferably, it is a polymer composed of 98.0 to 100 mol%, and still 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 that a thermoplastic elastomer obtained by dynamic crosslinking using an olefin-based resin (β) exhibits excellent rubber elasticity is that the side chain of the polymer [R1] acts as a pseudo-crosslinking point of a rubber phase and has This is presumed to be because it has the effect of improving the hardness and increasing the rigidity, and has the effect of exhibiting excellent rubber elasticity from a high temperature near the melting point of the polymer [R1] to a low temperature.

  The fact that the side chain of the polymer [R1] is composed of a crystalline ethylene polymer indicates that the olefin resin (β) according to the present invention has a melting peak in the range of 60 to 130 ° C. in differential scanning calorimetry (DSC). Is observed, that is, the melting temperature (Tm) is 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 crosslinking using the olefin resin (β) has high hardness and high rigidity, It is excellent in rubber elasticity from a high temperature near the melting point of [R1] to a low temperature.

  When the weight average molecular weight of the side chain of the polymer [R1] is below the above range, the thermoplastic elastomer obtained by using the olefin resin (β) tends to have reduced surface hardness and rigidity and reduced rubber elasticity. is there. This is presumed that the role of the side chain component as a pseudo-crosslinking point is reduced. On the other hand, when the weight average molecular weight exceeds the above range, the mechanical properties such as rigidity, surface hardness, and rubber elasticity of the obtained thermoplastic elastomer decrease due to the decrease in the number of side chains with respect to the main chain, or the polymer [R1 ), The rubber elasticity may be significantly reduced.

  The polymer [R1] can be obtained by copolymerizing a macromonomer that 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] was determined by analyzing the molecular weight of the macromonomer separated as a low-molecular-weight elution component by GPC measurement of the olefin-based resin (β), or synthesized in advance. It can be determined 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 below, a method of changing the type of the transition metal compound, And a method of adjusting polymerization conditions.

  The polymer [R1] contained in the olefin-based resin (β) satisfies the requirements (i) to (v) described above, whereby the thermoplastic elastomer obtained by dynamic crosslinking using the olefin-based resin (β) Is characterized by satisfying all 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 requirement (vi).

[Requirements (vi)]
The number of methyl branches in the side chain of the polymer [R1] is less than 0.1 per 1,000 carbon atoms contained in the side chain.
When the number of side chain methyl branches is in the above range, the crystallinity of the side chain ethylene polymer is further increased, and the thermoplastic elastomer obtained by dynamic crosslinking using the olefin resin (β) has a hardness and a modulus. And high rubber elasticity.

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

  As a method of 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 below, a method of changing the type of the transition metal compound is used. No.

[Requirement (II)]
The olefin resin (β) contains the polymer [R1] as described above, and the side chain of the polymer [R1] has an average of 0.5 to 20 per 1000 carbon atoms in the main chain polymer molecular chain. (Books), preferably 0.5 to 15 on average, 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 crosslinking using the olefin-based resin (β) has high hardness and high modulus, and the polymer [R1] has a high hardness and a high modulus. Excellent rubber elasticity from high to low temperatures around the melting point.

  On the other hand, when the number of side chains is less than the above range, the effect of the physical crosslinking point due to the side chains is reduced, so that the thermoplastic elastomer obtained by dynamic crosslinking using 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 crystalline component composed of the ethylene polymer in the olefin-based resin (β) increases, so that the thermoplastic elastomer obtained by dynamic crosslinking using the resin is In some cases, rubber elasticity is significantly reduced.

The number of side chains can be calculated by, for example, [a] a method using isotope carbon nuclear magnetic resonance spectrum (< ¹³ > C-NMR) or [b] a method using GPC.
Hereinafter, [a] and [b] will be described.

[A] In the measurement by the isotope carbon nuclear magnetic resonance spectrum (< ¹³ > C-NMR), the ethylene, [alpha] -olefin and poeline constituting the main chain of the polymer [R1] fall within the range of 37.8 to 38.1 ppm. Apart from the derived methine carbon, a signal that can be assigned to the methine carbon at the junction between the side chain and the main chain may be observed.
When the signal is observed, the number of side chains can be determined by the following equation.
[Number of side chains] = 1000 × [I _PE-methine ] / {[I _all-C ] × (100− [M]) / 100};
[I _PE-methine ]: integrated value of methine carbon at the junction between the side chain and the main chain [I _all-C ]: total carbon integrated value [M]: of macromonomer added or generated at the time of production of polymer [R1] Weight ratio to olefin resin (β) (wt%)

  [B] As described above, the peak on the low molecular weight side obtained when the olefin-based 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-based resin (β) can be determined from the area ratio between the low molecular weight peak and the other peaks. When the weight composition of the macromonomer to be 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 obtained by the following equation.

[Number of side chains] = ([M] − [M ′]) / (100− [M ′]) × (1 / [Mn _−M ]) × 14 / ｛1-([M] − [M ′] ) / (100− [M ′])｝ × (1/1000);
[M]: Weight ratio (wt%) of the macromonomer added or generated at the time of producing the polymer [R1] to the total amount of the resin [R '] obtained at the time of producing the polymer [R1].
[M ′]: weight ratio (wt%) of the remaining macromonomer determined by GPC to the total amount of resin [R ′] obtained at the time of producing the polymer [R1]
[Mn- _M ]: Number average molecular weight of macromonomer

  In addition, the average frequency obtained by the methods [a] and [b] is such that when an ethylene / α-olefin / polyene copolymer by-produced during the production of the olefin-based resin (β) is present, the polymer is used. Is a value when the number of side chains is 0.

The number of side chains can be adjusted, for example, by controlling the molar concentration of the macromonomer in the polymerization system.
For example, when the molecular weight of the side chain is constant under a certain polymerization condition, if the charged mass (or generated mass) of the macromonomer is increased, the molar concentration of the macromonomer is increased, and the number of side chains in the generated graft polymer is increased. Will increase. In addition, when the charged mass (or generated mass) of the macromonomer is constant, the molar concentration of the macromonomer is increased by reducing the side chain molecular weight, and the number of side chains in the generated graft polymer may be increased. it can.
The number of side chains can also be adjusted by selecting the type of a crosslinked metallocene compound (A) described later. For example, a crosslinkable polymer that exhibits high copolymerizability at a high temperature and can produce a large amount of polymer can be obtained. The number of side chains can be increased by selecting an olefin polymerization catalyst containing a metallocene compound.

[Requirement (III)]
The olefin-based resin (β) shows an endothermic peak, that is, a melting peak when measuring the temperature rise of the DSC, and has a melting temperature (Tm) of 60 to 130 ° C, preferably 80 to 125 ° C, more preferably 90 to 120 ° C. Exist 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 still more preferably 8 to 60 J / g. .

  Tm and ΔH are measured by DSC after the sample is once melted through a heating step, then crystallized by a cooling step to 30 ° C., and an endothermic peak appearing in a second heating step (heating rate 10 ° C./min) is measured. 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-based resin (β). The thermoplastic elastomer obtained by dynamic crosslinking using the olefin resin (β) of the present invention has high hardness and high rigidity, and particularly has excellent rubber elasticity from a high temperature to a low temperature near the melting point of the polymer [R1]. . On the other hand, when Tm or ΔH is below the range, rigidity, hardness, or rubber elasticity may decrease.

As a method of adjusting Tm to the above range, a method of appropriately selecting the type of a transition metal compound to be used in the synthesis of a macromonomer described below can be mentioned.
Examples of a method of adjusting ΔH to the above range include a method of controlling the abundance ratio of a macromonomer in a production process of an olefin-based resin (β) described later. Specifically, there is 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-based resin (β) has a glass transition temperature (Tg) measured by DSC of −80 to −30 ° C., preferably −80 to −40 ° C., and more preferably −80 to −50 ° C.
This Tg is based on the main chain ethylene / α-olefin / polyene copolymer of the polymer [R1]. When the Tg is in the range of −80 to −30 ° C., the thermoplastic elastomer obtained by dynamic crosslinking using the olefin resin (β) has flexibility as a rubber and rubber elasticity.

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

  The olefin resin (β) preferably satisfies the following requirements (V) and / or (VI) in addition to the requirements (I) to (IV).

[Requirements (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, more preferably 0.5 to 10 dl / g. ５5 dl / g. Within this range, the thermoplastic elastomer obtained by dynamic crosslinking using the olefin-based resin (β) shows good mechanical properties and also has good moldability.

[Requirements (VI)]
In the olefin resin (β), the ratio (E value) of an orthodichlorobenzene-soluble component at 20 ° C. or lower measured by cross fractionation chromatography (CFC) is 45 wt% or lower, preferably 35 wt% or lower. Preferably it is 30 wt% or less.

  Normally, commercially available ethylene / α-olefin / polyene copolymer resins (for example, ethylene / propylene / diene copolymer) are polymers adjusted to have a composition of ethylene of about 90 to 50 mol%. Shows crystallinity (or low crystallinity) and dissolves well in specific organic solvents even at temperatures below room temperature. For example, most of commercially available ethylene / propylene / diene copolymer resins are soluble in orthodichlorobenzene at a temperature of 20 ° C. or less, and the E value is usually 93% by weight or more.

  On the other hand, the polymer [R1] constituting the olefin-based resin (β) according to the present invention has a main chain of the above-described ethylene / α-olefin / polyene copolymer and a side chain of a crystalline ethylene polymer. Because it is coalesced, it becomes sparingly soluble in orthodichlorobenzene at room temperature or lower. Therefore, the olefin-based resin (β) has a feature that the E value is small.

  The fact that the olefin resin (β) has a low E value is indirect evidence that the main chain structure and the side chain structure of the polymer [R1] are chemically bonded. Contains a considerable amount of the polymer [R1].

The olefin resin (β) of the present invention is a crystalline polyolefin such as polypropylene, similar to a commercially available ethylene / α-olefin / polyene copolymer resin used as a raw material for a general dynamically crosslinked olefin thermoplastic elastomer. A domain phase is formed by complexing with a resin, and plays a role of expressing flexibility and rubber elasticity in the obtained thermoplastic elastomer. When a commercially available ethylene / α-olefin / polyene copolymer resin is used, the resulting thermoplastic elastomer exhibits flexibility and rubber elasticity as a rubber, but has a surface hardness and modulus, a breaking strength, and a breaking elongation. Decrease. On the other hand, when the olefin resin (β) of the present invention is used, the thermoplastic elastomer obtained 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-crosslinking point, and has high rigidity in the domain itself. It is presumed that high hardness and excellent rubber elasticity are produced.
Therefore, the fact that the polymer [R1] is contained in the olefin resin (β) is an important factor in obtaining a thermoplastic elastomer exhibiting good physical properties in a well-balanced manner.

In order to maintain a good balance of the mechanical properties of the thermoplastic elastomer according to the present invention, the ΔH and E values of the olefin resin (β) must satisfy any one of the following 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, 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 the above 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. This indicates that the amount is sufficient to obtain a thermoplastic elastomer.
When the olefin-based resin (β) does not satisfy the relationship of the above a), b) or c), that is, when the E value is large, the content of the graft type polymer is not sufficient and the ethylene / α-olefin / polyene copolymer Properties such as a polymer blend of a coalesced polymer and an ethylene polymer may be obtained, and it may be difficult to exhibit the good physical properties described above.

  For example, when the E value exceeds 45 wt% when the amount of side chains is small, such as ΔH of 5 J / g or more and less than 15 J / g, an existing ethylene / α-olefin / polyene copolymer resin is used. It tends to be close to the performance in such a case, and it is difficult to obtain a thermoplastic elastomer having a good balance of hardness, rigidity and rubber elasticity. Further, when the side chain amount is relatively large such that ΔH is 30 J / g or more, and when the E value exceeds 30 wt%, the component of the ethylene polymer alone not incorporated into the main chain increases, and the Not only the flexibility is impaired, but also the rubber elasticity and the 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, the content is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. Therefore, the above-described preferable relationship between ΔH and E value can be satisfied. In the case of synthesizing an olefin resin (β) by copolymerizing ethylene with an α-olefin, a polyene, or a polyethylene macromonomer, selection of a catalyst used in the copolymerization step is considered to be important. By using the compound (A), a resin satisfying the above-mentioned preferable relationship between ΔH and E value can be obtained.

[Other physical properties 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 still more preferably 5 to 90 MPa. When the elastic modulus is in the above range, the thermoplastic elastomer obtained by dynamic crosslinking using the olefin resin (β) is excellent in flexibility and rubber elasticity as a rubber.
The elastic modulus is desirably a tensile elastic modulus based on ASTM D638.

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

  First, the olefin resin (β) is heated by using a hydraulic hot press molding machine set at 170 ° C. for 5 minutes, and then molded by pressing at 10 MPa for 1 minute, and then at 20 ° C. and under 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 a small piece of 0.5 mm square and stained with ruthenic acid (RuO ₄ ). Further, the obtained small piece is made into an ultrathin section having a thickness of about 100 nm by an ultramicrotome equipped with a diamond knife. 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 a higher contrast because the intercrystalline amorphous portion of the lamellar structure formed by the side chain is selectively dyed with ruthenic acid. Is done.

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

  As described above, the olefin-based resin (β) is mainly composed of a polymer [R1] in which an amorphous (or low-crystalline) main chain and a crystalline side chain are connected by a covalent bond. It is considered that the compatibilizing effect of the crystal component is high, and the microphase-separated structure as described above 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 using the olefin resin (β). It is considered that the physical cross-linking points are also formed in the domain phase composed of the ethylene / α-olefin / polyene copolymer. For this reason, it is considered that the thermoplastic elastomer according to the present invention has an excellent balance of mechanical properties of rigidity, hardness and rubber elasticity.

  On the other hand, in the case of using a polymer blend of an ethylene / α-olefin / polyene copolymer and an ethylene polymer without using the olefin resin (β) in the production of the thermoplastic elastomer, the microphase No separation structure is formed, and a coarse crystal 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 dynamic cross-linkable thermoplastic elastomer showing good physical properties cannot be obtained. .

<Method for producing olefin resin (β)>
As a method for producing the olefin-based resin (β) of the present invention, for example, it can be produced by a method comprising the following (a) or (b).
(A) a step [a-1] of polymerizing ethylene in the presence of a catalyst containing the following compounds (B) and (C);
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, a polyene, and a step [a-1] (B) in the presence of an olefin polymerization catalyst containing the following compounds (A) to (C) in the presence of an olefin polymerization catalyst containing the compounds of the following (A) to (C): A method comprising a step of copolymerizing a component containing at least one α-olefin selected from α-20 to α-20 and a polyene (A) a crosslinked metallocene compound represented by the following formula (I) (B) Transition metal compound represented by formula [B] (C) (C-1) organometallic compound, (C-2) organoaluminum oxy compound, and (C-3) bridged metallocene compound (A) or transition metal compound Reacts with (B) Compound to form an ion pair, at least one compound selected from

[Bridged 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 a compound (C) described below.

（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 the formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a group other than a silicon-containing group. And two adjacent groups among R ^{1 to} R ⁴ may be bonded to each other to form a ring.
R ⁶ and R ¹¹ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a hetero atom-containing group other than the silicon-containing group, and R ⁷ and R ¹⁰ are a hydrogen atom, a hydrocarbon group, are the same atoms or the same group selected from heteroatom-containing groups other than silicon-containing group and a silicon-containing group, R ⁶ and R ⁷ may bond to each other to form a ring, R ¹⁰ and R ¹¹ may combine with each other to form a ring; provided that R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.
R ¹³ and R ¹⁴ each independently represent an aryl group.
M represents a titanium atom, a zirconium atom or a hafnium atom.
Y ¹ represents a carbon atom or a silicon atom.
Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or non-conjugated diene having 4 to 10 carbon atoms, an anionic ligand or a neutral ligand capable of coordinating with a lone electron pair. , J represents an integer of 1 to 4, and when j is an integer of 2 or 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, a polyene, and a macromonomer. And plays the role of producing the polymer [R1].

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

Since the olefin polymerization catalyst containing the crosslinked metallocene compound (A) has the above characteristics, it is possible to produce an olefin resin (β) containing a large amount of the polymer [R1]. ) To (IV) can be produced. The thermoplastic elastomer obtained by dynamic crosslinking using the olefin resin (β) thus obtained has high hardness and high rigidity, and further has excellent mechanical properties and rubber elasticity.
Hereinafter, the features of the chemical structure of the bridged metallocene compound (A) used in the present invention will be described.

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

  Hereinafter, the optionally substituted cyclopentadienyl group, substituted fluorenyl group, crosslinked portion, and other features of the bridged metallocene compound (A) will be sequentially described.

(Cyclopentadienyl group which may have a substituent)
In the formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a hetero atom-containing group other than the silicon-containing group, and include a hydrogen atom, 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 at ^{least one} of R ¹ , R ² , R ³ and R ⁴ is a hydrocarbon group (hereinafter referred to as “hydrocarbon group”). (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. Other examples of R ¹ , R ² , R ³ and R ⁴ include heteroatom-containing groups (excluding silicon-containing group (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 Examples include a saturated hydrocarbon group (eg, a cycloalkyl group) and a cyclic unsaturated hydrocarbon group (eg, an aryl group). The hydrocarbon group (f1) also includes groups in which any two hydrogen atoms bonded to mutually adjacent carbon atoms are simultaneously substituted to form an alicyclic ring or an aromatic ring.

  Specific examples of the hydrocarbon group (f1) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an 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, 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; cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, and adamanti Cyclic saturated hydrocarbon groups such as phenyl group, naphthyl group, biphenyl group, phenanthryl group, anthracenyl group and the like, and their alkyl substituted alkyl groups; saturated hydrocarbons such as benzyl group and cumyl group And a group in which at least one hydrogen atom of the group is substituted with an aryl group.

  The silicon-containing group (f2) is preferably a silicon-containing group having 1 to 20 carbon atoms. For example, a silicon atom is directly and covalently bonded to a ring carbon of a cyclopentadienyl group in the formula (I). And an alkylsilyl group (eg, a trimethylsilyl group) and an arylsilyl group (eg, a 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. And a pentafluorophenyl group.

When two or more of R ¹ , R ² , R ³ and R ⁴ are substituents other than a hydrogen atom, 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 the formula (I), R ⁵ , R ⁸ , R ⁹ and R ¹² each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a hetero atom-containing group other than the silicon-containing group, and include a hydrogen atom, a hydrocarbon Groups or silicon-containing groups are preferred. R ⁶ and R ¹¹ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a hetero atom-containing group other than the silicon-containing group, and the hydrogen atom, the hydrocarbon group and the silicon-containing group are Preferably, R ⁷ and R ¹⁰ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a hetero atom-containing group other than the silicon-containing group, and are preferably a hydrogen atom, a hydrocarbon group and a silicon-containing group. R ⁶ and R ⁷ may be bonded to each other to form a ring, and R ¹⁰ and R ¹¹ may be bonded to each other to form a ring; provided that “R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms. "

From the viewpoint of polymerization activity, R ⁶ and R ¹¹ are preferably not hydrogen atoms; R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are more preferably not hydrogen atoms; R ⁶ and R ¹¹ Is preferably the same group selected from a hydrocarbon group and a silicon-containing group, and R ⁷ and R ¹⁰ are particularly preferably the same group selected from a hydrocarbon group and a 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 that R ¹⁰ and R ¹¹ are bonded to each other to form an alicyclic or aromatic ring.

Examples and preferred examples of the hydrocarbon group for R ^{5 to} R ¹² include the same groups as the groups exemplified as the hydrocarbon group (f1). Examples and preferred examples of the silicon-containing group for R ^{5 to} R ¹² include the same groups as the groups exemplified as the silicon-containing group (f2). Examples of the hetero atom-containing group in R ^{5 to} R ¹² include the same groups as the groups exemplified as the hetero atom-containing group.

When R ⁶ and R ⁷ (R ¹⁰ and R ¹¹ ) are bonded to each other to form an alicyclic or aromatic ring, the substituted fluorenyl group is derived from compounds represented by the following formulas [II] to [VI]. Suitable groups are mentioned as preferred examples.

(Bridge section)
In the 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 method for producing the olefin resin (β) is that the aryl (aryl) groups [R ¹³ and R ¹⁴ ] which may be the same or different from each other are bonded to the bridging atom Y ¹ of the bridging portion. It is. It is preferable that R ¹³ and R ¹⁴ be the same from the viewpoint of ease of production.

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

Specific examples of the aryl group include an unsubstituted aryl group having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, an anthracenyl group, and a biphenyl group; a tolyl group, an isopropylphenyl group, and an n-butylphenyl. Aryl groups such as cyclohexylphenyl group; halogenated aryl groups such as chlorophenyl group, bromophenyl group, dichlorophenyl group and dibromophenyl group. A halogenated alkyl group-substituted aryl group such as a (trifluoromethyl) phenyl group and a bis (trifluoromethyl) phenyl group.
The position of the substituent in these groups is preferably the meta position and / or the para position. Among these, a substituted phenyl group in which the substituent is located at the meta-position and / or the para-position is more preferable.

(Other characteristics of bridged metallocene compound (A))
In the formula (I), Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or non-conjugated diene having 4 to 10 carbon atoms, an anionic ligand or a lone electron pair. Represents a neutral ligand, j represents 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 include fluorine, chlorine, bromine, and iodine. Examples of the hydrocarbon group include a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms and a carbon atom having 3 carbon atoms. To 10 alicyclic hydrocarbon groups. Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a 2-methylpropyl group, a 1,1-dimethylpropyl group, a 2,2-dimethylpropyl group, and a 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 -A trimethylbutyl group and a neopentyl group. 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 for Q include groups 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 dienes 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-η4-3-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-ditolyl-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.

  In the formula (I), M represents a titanium atom, a zirconium atom or a hafnium atom, and the zirconium atom or the hafnium atom copolymerizes the 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 performed under conditions of high temperature and high pressure in order to secure high productivity, it is preferable that M is a hafnium atom from the above-described characteristics. This is because, under high pressure conditions, the abundance ratio of ethylene and α-olefin becomes higher than that of the macromonomer, and the molecular weight generally decreases under high temperature conditions. This is because it is preferable to use a catalyst having a performance capable of producing an olefin-based resin (β) having a molecular weight.

  Such characteristics due to the fact that M is a hafnium atom include (1) a hafnium atom having a lower Lewis acidity and a lower reactivity than a zirconium atom or a titanium atom, and (2) a zirconium atom or a titanium atom. The larger binding energy between the hafnium atom and the carbon atom than the titanium atom indicates that the chain including the β-hydrogen elimination reaction of the polymerization active species bonded to the produced polymer chain, which is one of the molecular weight determinants. This is considered to be due to the suppression of the transfer reaction.

(Examples of preferred bridged metallocene compounds (A))
Preferred specific examples of the bridged metallocene compound (A) are shown below. In the exemplified compounds, octamethyloctahydrodibenzofluorenyl refers to a group derived from the compound having the structure represented by the formula [II], and octamethyltetrahydrodicyclopentafluorenyl refers to a group represented by the formula [III]. Dibenzofluorenyl refers to a group derived from a compound having the structure represented by the formula [IV], and 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 includes 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].

As the bridged metallocene compound (A), for example,
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-butyl Rufuruoreniru) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,3,6,7-tetra-tert- butyl fluorenyl) zirconium dichloride.

As the bridged metallocene compound (A), for example,
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-dihydrodicyclopentafluoride (Olenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclo) Pentadienyl) (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 (cyclopen Dienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,3,6,7-tetra Methylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride.

As the bridged metallocene compound (A), for example,
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- Di-tert-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- (Tylfluorenyl) 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.

As the bridged metallocene compound (A), for example,
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- Di-tert-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- Thiofluorenyl) 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.

As the bridged metallocene compound (A), for example,
Di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (3,6-di 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 (cyclopentadiene) Enil) 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, (P-bromophenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert- Tylfluorenyl) 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-tetra-tert-butylfluorenyl) zirconium dichloride.

As the bridged metallocene compound (A), for example,
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) Zirconium 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) zirconi Mudichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoro Methyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentane Dienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride.

As the bridged metallocene compound (A), for example,
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) Zirconium 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) zirconi Mudichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoro Methyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentane Dienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride.

As the bridged metallocene compound (A), for example,
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) Zirconium 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, (P-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene ( Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, 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.

As the bridged metallocene compound (A), for example,
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) Zirconium 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 (cyclopentadie ) (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-butylfluoride (Enyl) zirconium dichloride.

As the bridged metallocene compound (A), for example,
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, (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) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) Enyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride.

As the bridged metallocene compound (A), for example,
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'-hexame 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-tetra-tert-butylfluorenyl) zirconium dichloride.

As the bridged metallocene compound (A), for example,
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'-hexame 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-tetra-tert-butylfluorenyl) zirconium dichloride.

As the bridged metallocene compound (A), for example,
Di (m-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (2,7-dimethylfluorene) Nyl) zirconium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride.

As the bridged metallocene compound (A), for example,
Di (p-isopropylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorene 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.

As the bridged metallocene compound (A), for example,
Diphenylsilylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (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, diphenylsilylene (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, diphenylsilylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2,7- ( Dimethylphenyl) -3,6-ditert-butyl Rufuruoreniru) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2,3,6,7-tetra-tert- butyl fluorenyl) zirconium dichloride.

  Examples of the bridged metallocene compound (A) include compounds in which “zirconium” of the above-mentioned exemplified compounds is changed to “hafnium” or “titanium”, “dichloride” is “difluoride”, “dibromide”, “diiodide”, “dimethyl”, “dimethyl”. A compound in which “methylethyl” or “dibenzyl” has been changed, and “cyclopentadienyl” has been replaced with “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 WO 01/27124 and WO 04/029062.

  One of these cross-linked metallocene compounds (A) can be used alone, or two or more 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 an olefin polymerization catalyst in the presence of the compound (C) described below.

（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 the formula [B], M represents a transition metal atom belonging to Group 4 or 5 of the periodic table.
m shows the integer of 1-4.
R ¹ represents an acyclic hydrocarbon group having 1 to 4 carbon atoms represented by the formula C _{n ′} H _{2n ′ + 1} (n ′ is an integer of 1 to 4).
R ^{2 to} R ⁵ may be the same or different, and each represents 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. , A sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be connected to each other to form a ring.
R ^{6 to} R ⁸ are each independently a hydrocarbon group or a halogenated hydrocarbon group, at least one of which is an aromatic hydrocarbon group or a halogenated aromatic hydrocarbon group, and when m is 2 or more, , Two of the groups represented by R ^{2 to} R ⁸ may be connected between the structural units of the formula [B].
n is a number that satisfies the valence of M, 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, Represents a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is an integer of 2 or more, even if a plurality of Xs are the same, And a plurality of groups represented by X may be bonded to each other to form a ring. )

  The olefin polymerization catalyst containing the transition metal compound (B) is used for synthesizing a macromonomer that is an ethylene polymer, and contributes to the formation of a 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 vinyl group at one end with a high selectivity is synthesized. can do. Furthermore, by using an olefin polymerization catalyst containing the transition metal compound (B), an ethylene polymer having a relatively low molecular weight (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 characteristics, the polymer [R1] having the side chain efficiently introduced therein can be easily obtained. The thermoplastic elastomer obtained by dynamic crosslinking using the 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 feature that it can highly selectively polymerize ethylene even in the coexistence of ethylene, α-olefin, polyene and macromonomer. A polymer [R1] having a side chain with good mechanical and thermal properties can be easily obtained. Therefore, the thermoplastic elastomer obtained by dynamically cross-linking using the olefin-based resin (β) obtained by using the olefin polymerization catalyst containing the transition metal compound (B) has high hardness and high rigidity. Excellent mechanical properties and rubber elasticity. Further, the above-mentioned feature is a preferable feature in adopting the polymerization method [b] among the production methods of the olefin-based resin (β) described later.

  The olefin polymerization catalyst containing the transition metal compound (B) has a property of substantially not generating an olefin structure (a so-called internal olefin) inside the polymer chain. It is preferable from the viewpoints of light resistance and coloring resistance of a thermoplastic elastomer obtained by dynamically cross-linking using the system resin (β).

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

  In the formula [B], N ... M generally indicates coordination, but in the present invention, it may or may not be coordinated.

  In the formula [B], M represents a transition metal atom belonging to Group 4 or 5 of the periodic table, specifically, titanium, zirconium, hafnium, vanadium, niobium, tantalum or the like, preferably a metal belonging to Group 4 of the periodic table. Atoms, specifically, titanium, zirconium, and hafnium, and more preferably zirconium.

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

R ¹ represents an acyclic hydrocarbon group having 1 to 4 carbon atoms represented by the formula C _{n ′} H _{2n ′ + 1} (n ′ is an integer of 1 to 4), and specifically, methyl Group, ethyl group, n-propyl group, n-butyl group, iso-propyl group, iso-butyl group and tert-butyl group. Preferably, it is a straight-chain hydrocarbon group, specifically, a methyl group, an ethyl group, an n-propyl group, or an n-butyl group. Among these, a methyl group, an ethyl group and an n-propyl group are preferred. More preferably, they are a methyl group and an ethyl group. When R ¹ is ^one of these hydrocarbon groups, an ethylene polymer having a relatively low molecular weight (for example, in the range of 500 to 10,000 in weight average molecular weight) can be synthesized. It is preferable to obtain a thermoplastic elastomer of the formula (1).

R ^{2 to} R ⁵ may be the same or different, and each represents 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. , A sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring.

When m is 2 or more, two of the groups represented by R ^{2 to} R ⁸ may be connected 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, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, and n-hexyl groups. A straight-chain or branched alkyl group having 1 to 30, preferably 1 to 20 carbon atoms; a straight-chain or branched alkyl group having 2 to 30 carbon atoms, preferably 2 to 20, such as a vinyl group, an allyl group or an isopropenyl group; A linear or branched alkynyl group having 2 to 30, preferably 2 to 20 carbon atoms, such as a chain or branched alkenyl group; an ethynyl group, a propargyl group; a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl A cyclic saturated hydrocarbon group having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as a cyclopentadienyl group, an adamantyl group, and an adamantyl group; A cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as an oleenyl group; a carbon unsaturated group having 6 to 30 carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, and an anthracenyl group; 20 aryl groups; and an alkyl-substituted aryl group such as a tolyl group, an isopropylphenyl group, a t-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-substituted alkyl group such as a benzyl group and a cumyl group.

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

  As the hydrocarbon group and the halogenated hydrocarbon group, particularly, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, a linear or branched alkyl group having 1 to 30, preferably 1 to 20 carbon atoms such as n-hexyl group; carbon such as phenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group and anthracenyl group Aryl groups having 6 to 30, preferably 6 to 20 atoms; halogen atoms, alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, 6 to 30 carbon atoms, preferably 6 Preferred are substituted aryl groups in which 1 to 5 substituents such as 20 to 20 aryl groups are substituted.

  Examples of the oxygen-containing group include an alkoxy 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, and a group containing a carboxylic acid anhydride group. And groups in which the hydrocarbon group is substituted with these groups. 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 carbon atoms, and an aryloxy group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms. Preferred are substituted aryl groups.

  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. And specific examples thereof include groups in which the hydrocarbon group is substituted with these groups.

  Examples of the boron-containing group include groups including a borandiyl group, a borantriyl group, a diboranyl group, and the like. Specific examples 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 thiocyanate ester group, an isothiocyanate ester group, a sulfone ester group, a sulfonamide group, and a thiocarboxyl group. Examples include groups containing a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, a sulfenyl group, and the like, and specific examples include a group in which the hydrocarbon group is substituted with these groups.

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

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

  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, a triethylsilyl group , A diphenylmethylsilyl group, a triphenylsilyl group, a dimethylphenylsilyl group, a dimethyl-t-butylsilyl group, a 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 groups in which 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, and a t-butoxy group.

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

  Specific examples of the aryloxy group include a phenoxy group, a 2,6-dimethylphenoxy group, and a 2,4,6-trimethylphenoxy group.

  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, and a p-chlorophenoxycarbonyl group.

  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 acetamido group, an N-methylacetamido group, and an N-methylbenzamide group.

  Specific examples of the imide group include an acetimido 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, and a phenylimino group.

  Specific examples of the sulfone ester group include a methyl sulfonate group, an ethyl sulfonate group, and a phenyl sulfonate 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 connected to each other to form an alicyclic ring, an aromatic ring, or a ring containing a hetero atom such as a nitrogen atom. And 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 represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, and a silicon-containing residue. Group, germanium-containing group or tin-containing group. When n is 2 or more, they may be the same or different.

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

Examples of the hydrocarbon group include the same groups as the groups exemplified for R ^{2 to} R ⁵ . Specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a nonyl group, a dodecyl group, and an icosyl group; A cycloalkyl group having 3 to 30 atoms; an alkenyl group such as a vinyl group, a propenyl group, and a cyclohexenyl group; an arylalkyl group such as a benzyl group, a phenylethyl group and a phenylpropyl group; a phenyl group, a tolyl group, and a dimethylphenyl group And aryl groups such as trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group, anthryl group and phenanthryl group, but are not limited thereto. Of these, groups having 1 to 20 carbon atoms are preferred.

Examples of the heterocyclic compound residue include the same groups as those exemplified above for R ^{2 to} R ⁵ .

Examples of the oxygen-containing group include the same groups as those exemplified above for R ^{2 to} R ⁵ , specifically, a hydroxy group; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; a phenoxy group But aryloxy groups such as methylphenoxy group, dimethylphenoxy group, and naphthoxy group; arylalkoxy groups such as phenylmethoxy group and phenylethoxy group; 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 the above R ^{2 to} R ⁵ , and specifically, a methylsulfonate group, a trifluoromethanesulfonate group, a phenylsulfonate group, a benzylsulfonate group Sulfonate groups such as phonate group, p-toluenesulfonate group, trimethylbenzenesulfonate group, triisobutylbenzenesulfonate group, p-chlorobenzenesulfonate group and pentafluorobenzenesulfonate group; A sulfinate group such as a ruffinate group, a phenylsulfinate group, a benzylsulfinate group, a p-toluenesulfinate group, a trimethylbenzenesulfinate group, a pentafluorobenzenesulfinate group; an alkylthio group; an arylthio group. But not limited to Not.

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

Specific examples of the boron-containing group include BR ₄ (R represents 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 trialkylphosphine group such as a trimethylphosphine group, a tributylphosphine group and a tricyclohexylphosphine group; a triarylphosphine group such as a triphenylphosphine group and a tolylphosphine group; a methylphosphite group But a phosphite group (phosphide group) such as an ethyl phosphite group and a phenyl phosphite group; a phosphonic acid group; a phosphinic acid group, but are not limited thereto.

Specific examples of the silicon-containing group include the same groups as those exemplified above for R ^{2 to} R ⁵ , and specific examples include a phenylsilyl group, a diphenylsilyl group, a trimethylsilyl group, a triethylsilyl group, and a triethylsilyl group. Hydrocarbon-substituted silyl groups such as propylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, methyldiphenylsilyl group, tolylsilyl group and trinaphthylsilyl group; hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether group; trimethylsilylmethyl A silicon-substituted alkyl group such as a group; and a silicon-substituted aryl group such as a trimethylsilylphenyl group.

Specific examples of the germanium-containing group and the tin-containing group include the same groups as the groups exemplified in the above R ^{2 to} R ^5. Specifically, silicon of the silicon-containing group is changed to germanium or tin. And substituted groups.

Specifically the halogen-containing group, PF _6, fluorine-containing groups such as BF _4, ClO _4, chlorine-containing groups, such as SBC _l6, iodine-containing groups, such as IO _4, wherein the hydrocarbon group having 1 to 20 carbon atoms And a group in which at least one hydrogen has been replaced by halogen, but is not limited thereto.

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

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

Specific examples of the hydrocarbon group include 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, and an n-hexyl group. A linear or branched alkyl group having 1 to 30, preferably 1 to 20 carbon atoms; having 2 to 30, preferably 2 to 20 carbon atoms such as a vinyl group, an allyl group and an isopropenyl group; A linear or branched alkenyl group; an ethynyl group, a propargyl group, or a straight or branched alkynyl group having 2 to 30, preferably 2 to 20 carbon atoms; a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, A cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20 carbon atoms, such as a cyclohexyl group and an adamantyl group; a cyclopentadienyl group and an indenyl group A cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as a fluorenyl group; having 6 to 30, preferably 6 to 30 carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, and an anthracenyl group; 20 aryl groups; and alkyl-substituted aryl groups such as a tolyl group, an isopropylphenyl group, a t-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-substituted alkyl group such as a benzyl group and a cumyl group.

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

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

Since at least one of the hydrocarbon groups 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. The thermoplastic elastomer obtained by using the produced olefin resin (β) is suitable for the production of the olefin resin (β) according to the present invention, and exhibits good performance.

When m is 2 or more, two of the groups represented by R ^{2 to} R ⁸ may be connected 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, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.

  The transition metal compound (B) as described above can be used alone or in combination of two or more.

[Compound (C)]
The compound (C) is a compound other than the compound (A) and the compound (B), and functions as a catalyst for olefin polymerization by reacting with the compound (A) and the compound (B). Is
(C-1) an organometallic compound,
(C-2) an organic aluminum oxy compound, and
(C-3) At least one compound selected from compounds that form an ion pair by reacting with compound (A) or compound (B).
Hereinafter, the compounds (C-1) to (C-3) will be sequentially described.

((C-1) Organometallic compound)
As the organometallic compound (C-1), specifically, an organoaluminum compound represented by the following formula (C-1a), a metal belonging to Group 1 of the periodic table represented by the formula (C-1b), and aluminum And a dialkyl compound of a Group 2 or Group 12 metal of the periodic table represented by 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), R ^a and R ^b may be the same or different from each other, represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and Y represents a halogen atom. P is 0 <p ≦ 3, q is 0 ≦ q <3, r is 0 ≦ r <3, s is a number of 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, preferably 1 to 4 carbon atoms.)

R ^{d Re} M ⁴ (C-1c)
(In formula (C-1c), R ^d and R ^e may be the same or different from each other, and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms or a halogenated hydrocarbon group. , 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)
(Wherein, R ^a and R ^b may be the same or different from each other, and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and p is preferably 1.5 ≦ p ≦ This is the number 3.)

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

_{^{R a p Al (OR b)}} q Y s (C-1a-4)
(Wherein, R ^a and R ^b may be the same or different from each other and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, Y represents a halogen atom, and p represents 0 <P ≦ 3, q is a number satisfying 0 ≦ q <3, s is a number satisfying 0 ≦ s <3, and p + q + s = 3.)

More specifically, as the organoaluminum compound represented by the formula (C-1a), trimethylaluminum, triethylaluminum, trin-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecyl Tri-n-alkyl aluminums such as aluminum;
Triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, tri-4 Tri-branched alkyl aluminums such as -methylpentyl aluminum, tri 2-methylhexyl aluminum, tri 3-methylhexyl aluminum, tri 2-ethylhexyl aluminum;
Tricycloalkyl aluminums such as tricyclohexyl aluminum, tricyclooctyl aluminum;
Triaryl aluminums such as triphenyl aluminum and tolyl aluminum;
Dialkyl aluminum hydrides such as diisobutyl aluminum hydride;
Trialkenyl aluminums such as triisoprenyl aluminum;
Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide;
Alkyl aluminum sesqui alkoxides such as ethyl aluminum sesqui ethoxide, butyl aluminum sesqui butoxide;
R ^a _2.5 Al (OR ^b) hydrocarbon aluminum (wherein partially been alkoxylated with an average composition represented by _0.5, R ^a and R ^b may be the same or different from each other, the number of carbon atoms Represents 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- Dialkyl aluminum 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 and diisobutylaluminum chloride;
Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide;
Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide;
Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
Partially hydrogenated alkylaluminums, such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride;
Partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide and ethylaluminum ethoxybromide can be mentioned.

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

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.

  Further, as the (C-1) organometallic compound, in addition to the above compounds, methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide , Propylmagnesium chloride, butylmagnesium bromide, butylmagnesium chloride and the like can also be used.

  Further, a compound capable of forming the organoaluminum compound in the polymerization system, for example, a combination of an aluminum halide and an alkyl lithium, or a combination of an aluminum halide and an alkylmagnesium may be used as the (C-1) organometallic compound. It can also be used as a compound.

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

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

A 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 water of adsorption or salts containing water of crystallization, for example, magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerous chloride hydrate and the like A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension of the above, and the adsorbed water or water of crystallization reacts with the organoaluminum compound.
(2) A method in which water, ice or water vapor is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method 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 organic metal component.
After distilling off the solvent or unreacted organoaluminum compound from the obtained aluminoxane solution, the obtained aluminoxane may be redissolved in a solvent or suspended in a poor solvent for aluminoxane.

Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as the compounds exemplified as the organoaluminum compound belonging to the formula (C-1a).
Of these, trialkyl aluminum and tricycloalkyl aluminum are preferred, and trimethyl aluminum is particularly preferred.

  The organoaluminum compound may be used alone or in combination of two or more.

  Solvents used in the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, octadecane, and cyclopentane , Cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclopentane, gasoline, kerosene, petroleum fractions such as light oil, or the aromatic hydrocarbons, aliphatic hydrocarbons, halides of alicyclic hydrocarbons, In particular, halogenated hydrocarbon solvents such as chlorinated products and brominated products are exemplified. Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

  The benzene-insoluble organoaluminum oxy compound is a compound in which the Al component soluble in benzene at 60 ° C. is usually 10% by mass or less, preferably 5% by mass or less, particularly preferably 2% by mass or less in terms of Al atom. Preferably, there is.

  Examples of the organoaluminum oxy compound (C-2) include a boron-containing organoaluminum oxy compound represented by the following formula (III).

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

  The organoaluminum oxy compound containing boron represented by the formula (III) can be obtained, for example, by reacting an alkylboronic acid represented by the following formula (IV) and an organoaluminum compound with an inert solvent under an inert gas atmosphere. The reaction can be carried out at -80 ° C to room temperature for 1 minute to 24 hours.

R ¹⁹ -B (OH) ₂ (IV)
(In the formula (IV), R ¹⁹ represents the same group as R ¹⁷ in the 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, and 3,5-bis (trifluoromethyl) phenylboronic acid. Of these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These can be used alone or in combination of two or more.

Specific examples of the organoaluminum compound to be reacted with the alkylboronic acid include the same organoaluminum compounds as the compounds exemplified as the organoaluminum compound belonging to the formula (C-1a).
As the organic aluminum 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.

  The (A-2) organic aluminum oxy compound may be used alone or in combination of two or more.

((C-3) a compound which forms an ion pair by reacting with a bridged metallocene compound (A) or a transition metal compound (B))
The compound (C-3) which forms an ion pair by reacting with the crosslinked metallocene compound (A) or transition metal compound (B) (hereinafter referred to as "ionized ionic compound") is described in JP-A-1-501950. Japanese Patent Application Laid-Open Nos. Hei 1-52036, Hei 3-179005, Hei 3-179006, Hei 3-207703, Hei 3-207704, U.S. Pat. No. 5,321,106, etc. And the like, ionic compounds, borane compounds and carborane compounds. Furthermore, 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 and a trifluoromethyl group). Examples include compounds such as trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, and tris (pentafluorophenyl). Boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like.

  Examples of the ionic compound include a compound 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 the formula (V), R ²⁰ is H ⁺ , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation or a ferrocenium cation having a transition metal, and R ^{21 to} R ²⁴ are Which may be the same or different, and are an organic group, preferably an aryl group or a substituted aryl group.).

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

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

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

R ²⁰ is preferably a carbonium cation or an ammonium cation, particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation, or an N, N-diethylanilinium cation.

  Further, examples of the ionic compound include a trialkyl-substituted ammonium salt, an N, N-dialkylanilinium salt, a dialkylammonium salt, and a triarylphosphonium salt.

  Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) ) Boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (M, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditrifluoromethylphenyl) Yl) boron, tri (n- butyl) ammonium tetra (o-tolyl) and boron and the like.

  Specific examples of the N, N-dialkylanilinium salt include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N, 2,4, 6-pentamethylanilinium tetra (phenyl) boron and the like.

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

  Further, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentane Examples thereof include a phenylcyclopentadienyl complex, an N, N-diethylanilinium pentaphenylcyclopentadienyl complex, and a boron compound represented by the following formula (VI) or (VII).

（式（ＶＩ）中、Ｅｔはエチル基を示す。）

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

（式（ＶＩＩ）中、Ｅｔはエチル基を示す。）

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

Specific examples of the borane compound include, 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 Salts of anions such as, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate;
Of metal borane anions such as tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III) and bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III) Salts.

Specific examples of the carborane compound include, for example, 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodeca Hydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarboundecaborane, 2,7-dicarboundoca Borane, undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, tri (n-butyl) ammonium 1-carbadecaborate, Tri (n-butyl) ammonium 1-carboundecaborate, tri (n-butyl) ammonium 1-carb Dodecaborate, 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-carboundecaborate, tri (n-butyl) ammonium 7-carboundecaborate, tri (n-butyl) ammonium 7,8-dicarboundecaborate, tri (n-butyl) ammonium 2 , 9-Dicarboundecaborate, tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarboundecaborate, tri (n-butyl) ammoniumundecahydride-8-ethyl-7,9- Dicarboundecaborate, tri (n-butyl Ammonium undecahydride-8-butyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium Salts of anions such as decahydrate-9-trimethylsilyl-7,8-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carboundecaborate;
Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) Ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-Dicarboundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cuprate (III), tri (n-butyl) Ammonium bis (undecahydride-7,8-dicarboundecaborate) aurate (III) Tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8) -Dimethyl-7,8-dicarboundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarboundecaborate) cobaltate (III), tris [Tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundeca Borate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undeca Metal carborane anions such as idride-7-carboundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) nickelate (IV) Salts.

  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, phosphorus vanadic acid, germanovanadate, arsenic vanadate, phosphorus niobate, germanoniobate, siliconomolybdate, phosphomolybdate, titanium molybdate, germanomolybdate, arsenic molybdate, tin molybdate, phosphorus molybdate, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphorus tungstovanadic acid, germanotangostovanadate acid, phosphomolybdenum tungstovanadate, germano molybdo tungstovanadate, phosphomolybdotungstate , Phosphomolybdniobic acid, and salts of these acids, but are not limited thereto. Examples of the salt include salts of the acids, for example, metals of Group 1 or 2 of the Periodic Table, specifically, salts of lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and the like. And organic salts such as triphenylethyl salt.

  The isopoly compound is a compound composed of a metal ion of one kind of atom selected from vanadium, niobium, molybdenum, and tungsten, and can be regarded as a molecular ionic species of a metal oxide. Specific examples include, but are not limited to, vanadic acid, niobic acid, molybdic acid, tungstic acid, and salts of these acids. Further, as the salt, for example, a metal of the first or second group of the periodic table of the acid, specifically, a salt of lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, or the like; Organic salts such as triphenylethyl salt are exemplified.

  The preionized ionic compound (C-3) can be used alone or in combination of two or more.

  When an organoaluminum oxy compound (C-2) such as methylaluminoxane as a co-catalyst component is used in addition to the crosslinked metallocene compound (A), a very high polymerization activity is exhibited for the olefin compound.

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

  In the liquid-phase polymerization method, an inert hydrocarbon medium can be used. Specific examples of the medium include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene. Alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof. Alternatively, the olefin itself can be used as a solvent.

When the above-mentioned olefin polymerization catalyst is used in the production of the olefin resin (β), the crosslinked metallocene compound (A) is used in an amount of usually 10 ⁻⁸ to 1 mol, preferably 10 ⁻⁷ to 0.1 mol per liter of the reaction volume. The transition metal compound (B) is used in an amount of usually 10 ^-12 to 10 ^-2 mol, preferably 10 ^-10 to 10 ^-3 mol, per liter of reaction volume. Used in

  In addition, the crosslinked metallocene compound (A) and the transition metal compound (B) have a molar ratio (B / A) of the transition metal compound (B) and the crosslinked metallocene compound (A) of usually 0.00001 to 100, preferably It is used in an amount of 0.00005 to 10, more preferably 0.0001 to 5.

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

  The organoaluminum oxy compound (C-2) is composed of an aluminum atom in the organoaluminum oxy compound (C-2) and a transition metal atom (M) (bridged metallocene) in the bridged metallocene compound (A) and the transition metal compound (B). In the compound (A), the compound is used in an amount such that the molar ratio (C-2 / M) to a titanium atom, a zirconium atom or a hafnium atom is usually 10 to 500,000, preferably 20 to 100,000.

  The ionized ionic compound (C-3) is composed of the ionized ionic compound (C-3), the transition metal atom (M) in the bridged metallocene compound (A) and the transition metal compound (B) (the bridged metallocene compound (A)). Is used in such an amount that the molar ratio (C-3 / M) to a titanium atom, a zirconium atom or a hafnium atom is usually 1 to 10, preferably 1 to 5.

Further, 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 ). Either method can be used.

  The molecular weight of the obtained olefin-based resin (β) can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature, and furthermore, the compounds (A), (B) and (C) ) Can be adjusted by selecting any of the compounds or the selection of the combination.

  Examples of the olefin used for the polymerization include ethylene and the aforementioned α-olefin having 3 to 20 carbon atoms and polyene. These olefins can be used in combination with ethylene as an essential monomer and one or more other monomers.

  In the present invention, the olefin-based resin (β) can be produced by any one of the following polymerization methods [a] and [b].

・ Polymerization method [a]
A pre-process [a-1] of obtaining a macromonomer by polymerizing ethylene 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 at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms, a polyene, and a post-process [a-2] of copolymerizing the reaction product of the preceding process [a-1]. A method that includes

Pre-process [a-1]
The pre-process [a-1] is a process of mainly polymerizing ethylene using the transition metal compound (B) and the compound (C) to obtain a macromonomer which is substantially an ethylene polymer. There is no particular limitation, and examples include the above-described method. In this pre-process [a-1], a vinyl-terminated macromonomer can be obtained. In the case of liquid phase polymerization, the obtained reaction solution may be directly introduced into a post-process, or after taking out a macromonomer, the macromonomer may be introduced into a post-process as a lump or as a powder, or taken out. A slurry or a solution may be prepared using the obtained macromonomer, and the obtained slurry or solution may be introduced to a subsequent step.

Post-process [a-2]
The post-step [a-2] includes, in the presence of the bridged metallocene compound (A) and the compound (C), ethylene, at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms, and polyene. And the macromonomer obtained in the preceding step [a-1]. The polymerization method is not particularly limited, and includes, for example, the above-described methods.However, a liquid-phase polymerization method is preferable because an amorphous or low-crystalline ethylene / α-olefin / polyene copolymer site is generated. Solution polymerization is preferred for controlling the concentration of each monomer and obtaining an olefin resin (β) having a desired structure.

  The polymerization reaction may be performed in a batchwise manner in the preceding step [a-1], and also in a batchwise manner in the subsequent step [a-2], or in a batchwise manner in the preceding step [a-1]. And the subsequent step [a-2] may be performed in a continuous manner. 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 performed in a continuous manner. Further, the preceding step [a-1] can be performed in a continuous manner, and the subsequent step [a-2] can be performed in a batch manner.

・ Polymerization method [b]
In the presence of a bridged metallocene compound (A), a transition metal compound (B), and a compound (C), ethylene, at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms, and polyene This is a method of polymerizing in a single stage, and can be performed in one polymerization vessel. Use of the transition metal compound (B) and the compound (C) tends to allow highly selective polymerization of ethylene even when an olefin other than ethylene is present in the polymerization system. Further, by using the transition metal compound (B) and the compound (C), an ethylene polymer (macromone) having a relatively small molecular weight and having a vinyl terminal tends to be produced. By using the crosslinked metallocene compound (A) and the compound (C), a polymer [R1] having a large molecular weight can be produced. Thus, the olefin resin (β) can be synthesized under one polymerization reaction condition.

  In the method for producing the olefin-based resin (β), the subsequent step [a-2] and the polymerization method [b] are preferably performed 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 performing polymerization in a state where a polymer is dissolved in an inert hydrocarbon solvent described below. The polymerization temperature of the solution polymerization is preferably 80 to 300C, more preferably 90 to 250C. When the polymerization temperature is lower than 80 ° C. in the solution polymerization, the macromonomer may not be sufficiently dissolved, and the polymer [R1] may not be efficiently produced. Further, when the polymerization temperature is lower than 80 ° C., the polymerization activity is extremely lowered, so that it tends to be impractical in terms of productivity. In the polymerization temperature range of 80 ° C. or higher, as the temperature increases, the solution viscosity during the polymerization decreases, the heat of the polymerization heat can be easily removed, and the resulting polymer [R1] can have a high molecular weight. However, if the polymerization temperature exceeds 300 ° C., the resulting polymer may deteriorate, which is not preferable.

  The polymerization pressure is usually from normal pressure to 10 MPa gauge pressure, preferably from normal pressure to 8 MPa gauge pressure, and the polymerization reaction can be carried out by any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization can be performed 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 in the polymerization system or the polymerization temperature, and can also be adjusted by the amount of the compound (C) used. . When hydrogen is added, the amount is suitably 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 include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, and kerosene; and alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane. In addition, 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 the inert hydrocarbon solvent, and the use thereof is not limited.

  In the production of the olefin resin (β), rubber, an inorganic filler, a weathering stabilizer, a heat stabilizer, an antistatic agent, an anti-slip agent, an anti-blocking agent, as long as the object of the present invention is not impaired. Additives such as agents, antifoggants, lubricants, pigments, dyes, plasticizers, antioxidants, hydrochloric acid absorbents, antioxidants, and crystal nucleating agents may be used. When such an additive is used, the resulting component may include such an additive. In the present invention, the case where such an additive is included is also referred to as an olefin-based resin (β).

The olefin-based resin (β) can be used for the following pellets, thermoplastic elastomers, and the like. In this case, the olefin-based resin (β) contains various additives as described above and resins other than the polymer [R1]. These can be used as compositions.
The amount of the additive or other resin added is not particularly limited as long as the object of the present invention is not impaired. For example, the total amount of the olefin resin (β) and the additive or other resin is 100% by weight. In contrast, 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, and still more preferably 70 to 100% by weight. Examples can be given.

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

  Although the pellets of the present invention can be used as they are, they are preferably used as a raw material of a thermoplastic elastomer, if necessary, mixed with another resin and crosslinked.

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

  Although the pellet of the present invention is not particularly limited, examples of the shape include a sphere, a column, a prism, and a sponge, and the aspect ratio is preferably 5 or less, more preferably 3 or less, and still more preferably 1-2. And 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.

The size of the pellet is determined by measuring the maximum length Lmax1 to 10 and the minimum length Lmin1 to 10 of the arbitrarily selected 10 pellets (pellets 1 to 10) using calipers, and averaging the average value. Expressed as the size of
Size of pellet = (Lmax1 + Lmax2 + Lmax3 + Lmax4 + Lmax5 + Lmax6 + Lmax7 + Lmax8 + Lmax9 + Lmax10 + Lmin1 + Lmin2 + Lmin3 + Lmin4 + Lmin5 + Lmin6 + Lmin7 + Lmin + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin6 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin6 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin5 + Lmin5 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin6 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7 + Lmin7

≪Thermoplastic elastomer≫
The thermoplastic elastomer of the present invention is prepared using a composition containing the olefin resin (β), the crystalline polyolefin resin (α), and the crosslinking agent (γ) (hereinafter, also referred to as “polymer composition”). Preferably, it is a cross-linked product of the polymer composition, or prepared using the pellets, preferably a cross-linked product using the pellets, more preferably dynamically the polymer composition This is a dynamic heat treatment 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. Such polyolefins include, for example, 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 for the crystalline polyolefin resin (α) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, and 2-methyl-1-propene. And α-olefins having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, such as, 3-methyl-1-pentene, 4-methyl-1-pentene and 5-methyl-1-hexene. These α-olefins can be used alone or in combination of two or more.
Regarding the polymerization mode, any type of polymerization mode may be adopted as long as a resinous material can be obtained, whether a random type or a block type.

  As the crystalline polyolefin resin (α), a propylene 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) of usually 0.01 to 100 g / 10 min, preferably 0.05 to 50 g / 10. Desirably within the range of minutes.

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

[Crosslinking agent (γ)]
Examples of the crosslinking agent (γ) include organic peroxides, sulfur, sulfur compounds, and phenol-based vulcanizing agents such as phenolic resins. Among them, organic peroxides are preferably used.
The crosslinking 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) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n -Butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperbenzoate, tert-butylperoxyisopropyl Carbonate Diacetyl peroxide, lauroyl peroxide, etc. tert- butyl cumyl peroxide.

  Among them, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane and 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne are preferred 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-butyl) Butyl peroxy) valerate is preferred.

  The crosslinking agent (γ) is used in an amount of 0.01 to 15 parts by weight, preferably 0.03 to 12 parts by weight, based on 100 parts by weight of the olefin resin (β). When the crosslinking agent is used in the above ratio, a thermoplastic elastomer in which the olefin-based resin (β) is crosslinked is obtained, and a molded article having sufficient heat resistance, tensile properties, and rubber elasticity is obtained. Further, this thermoplastic elastomer is excellent in moldability.

[Crosslinking aid]
In the present invention, in the crosslinking treatment with the crosslinking agent (γ), sulfur, p-quinonedioxime, p, p′-dibenzoylquinonedioxime, N-methyl-N, 4-dinitrosoaniline, nitrobenzene, diphenylguanidine Trimethylolpropane-N, N'-m-phenylenedimaleimide, 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 included. By using such a compound, a uniform and mild crosslinking reaction can be expected. In particular, divinylbenzene is easy to handle, has good compatibility with the olefin resin (β), and has an organic peroxide solubilizing effect when an organic peroxide is used as the cross-linking agent (γ). Since it functions as a peroxide dispersing agent, it is most preferable because a thermoplastic elastomer having a uniform cross-linking effect by heat treatment and a good balance of fluidity and physical properties can be obtained.
The crosslinking assistant may be used alone, or two or more kinds may be used.

[Production 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-based resin (β), the crystalline polyolefin resin (α), and a cross-linking agent ( γ), preferably obtained by dynamically heat-treating and crosslinking a mixture of an organic peroxide and other optional components.

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” refers to 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 from the melting point of the olefin-based resin (β) to 300 ° C, preferably from 150 to 280 ° C, more preferably from 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 It is in the range of -17,000 sec ⁻¹ .

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

[Uses of thermoplastic elastomers]
The thermoplastic elastomer of the present invention is appropriately molded and used depending on the application. 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 weather strips, ceiling materials, interior seats, bumper molding, side moldings, air spoilers, air duct hoses, cup holders, side brake grips, shift knob covers, seat adjustment knobs, flapper door seals, wire harness grommets, 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 engineering / building material parts (water stoppage material, joint material, window frame for construction, etc.), sporting goods (golf clubs, grips for tennis rackets) Etc.), industrial parts (hose tube, gaskets, etc.), household electric appliance parts (hose, packings, etc.), medical equipment parts, electric wires, and a wide range of areas such as miscellaneous goods.

≪Crosslinked rubber≫
The crosslinked rubber of the present invention is produced 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 crosslinking 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. For example, using the kneading apparatus, the olefin resin (β) and / or pellets and the crosslinking agent (γ) are compounded as necessary. A composition with other components to be prepared is prepared and molded into an intended shape by various molding methods using an extruder, a calender roll, a press, an injection molding machine, a transfer molding machine, etc., and simultaneously or simultaneously with molding. It can be obtained by introducing a substance into a vulcanization tank and crosslinking.

  The crosslinked rubber is a weather strip for automobiles; hoses for automobile hoses, water supply hoses, gas hoses, etc .; automobile anti-vibration rubbers, railway anti-vibration rubbers, industrial machinery anti-vibration rubbers, building seismic isolation rubbers, and the like. Belts such as power transmission belts and conveyor belts; sealing materials such as cups and seals for automobiles and seals for industrial machinery; weatherstrip sponges for automobiles, seal sponges for construction, and other sponges and cushions for hose protection. Foams such as sponges, heat insulating sponges, insulation pipes, etc .; coated electric wires, electric wire joints, electric insulating parts, semiconductive rubber parts; OA equipment rolls, industrial rolls; rain gear, rubber bands, shoes, rubber gloves, latex products, Household goods such as golf balls; for plastic modification, thermoplastic elastomer, engineering plastic modification Widely used in applications such as.

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

(1) Measurement of melting temperature (Tm) and heat of fusion ΔH Measurement of the melting temperature (Tm) and heat of fusion ΔH of the olefin-based resin was obtained by performing DSC measurement under the following conditions.
Using a differential scanning calorimeter (RDC220, manufactured by SII), about 10 mg of the sample was heated from 30 ° C. to 200 ° C. at a rate of 50 ° C./min in a nitrogen atmosphere, and kept at that temperature for 10 minutes. Furthermore, the temperature was lowered to 30 ° C. at a rate of 10 ° C./min, and the temperature was maintained for 5 minutes. Then, the temperature was raised to 200 ° C. at a rate of 10 ° C./min. The endothermic peak observed at the time of the second temperature rise was defined as a melting peak, and the peak top temperature was determined as a melting temperature (Tm). The heat of fusion ΔH was determined by calculating the area of the melting peak. When the melting peak was multimodal, the area of the entire melting peak was calculated and determined.

(2) Measurement of glass transition temperature (Tg) The measurement of the glass transition temperature (Tg) of the olefin-based resin was obtained by performing DSC measurement under the following conditions.
Using a differential scanning calorimeter (RDC220, manufactured by SII), about 10 mg of the sample was heated from 30 ° C. to 200 ° C. at a rate of 50 ° C./min in a nitrogen atmosphere, and kept at that temperature for 10 minutes. Further, the temperature was lowered to -100 ° C at a temperature lowering rate of 10 ° C / min, kept at that temperature for 5 minutes, and then raised to 200 ° C at a temperature increasing rate of 10 ° C / min. At the time of the second temperature rise, the DSC curve is bent due to a change in specific heat, and the temperature at the intersection of the tangent to the base line at a portion lower in temperature than the bend and the tangent at the point where the slope becomes the maximum at the bent portion is determined by the glass. The transition temperature (Tg) was used.

(3) ¹³ C-NMR measurement For the purpose of analyzing the composition of ethylene, α-olefin and diene in the olefin resin, confirming the graft structure, the number of grafts (per 1000 C) and the structure of the following macromonomer (P-1), ¹³ C-NMR measurement was performed under the following conditions.
Apparatus: Bruce Biospin AVANCE III500 CryoProbe Prodigy type nuclear magnetic resonance apparatus, 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), repetition time: 5.5 seconds, integration frequency: 512 times, measurement solvent: ortho-dichlorobenzene / 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 GPC analysis was performed under the following conditions for the molecular weight analysis of the olefin resin, the molecular weight analysis of the following macromonomer (P-1), and the calculation of the residual macromonomer amount.
Apparatus: Waters Alliance GPC 2000, columns: TSKgel GMH6-HT × 2 and TSKgel GMH6-HTL × 2 (both manufactured by Tosoh Corporation, inner diameter 7.5 mm × 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 Corporation)

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

(6) Components eluted below 20 ° C ([wt%])
The components eluted at 20 ° C. or lower in the olefin-based resin were measured for the components soluble in orthodichlorobenzene at a temperature of 20 ° C. or lower using a cross fractionation chromatograph (CFC). Specifically, the test was performed under the following conditions.
Device: cross fractionation chromatograph CFC2 (Polymer ChAR Co.), the detector (internal): (manufactured by Polymer ChAR Ltd.) infrared spectrophotometer IR ^4, detection wavelength: 3.42μm (2,920cm ^-1) fixed sample Concentration: 120 mg / 30 mL, injection volume: 0.5 mL, cooling rate: 1.0 ° C./min, elution category: 4.0 ° C. interval (−20 ° C. to 140 ° C.), GPC column: Shodex HT-806M × 3 (Manufactured by Showa Denko KK), GPC column temperature: 140 ° C, GPC column calibration: monodisperse polystyrene (manufactured by Tosoh Corporation), 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 a sample amount necessary for the evaluation, the production by the following method may be performed plural times.

[Example 1] Production of olefin-based resin (β-1) <Synthesis of macromonomer (P-1) (pre-process [a-1])>
The compound (1) represented by the following formula, which was used as a catalyst, was synthesized according to [Synthesis Example 3] of WO 2006/057229, and the macromonomer (P-1) was synthesized according to [Example 1] of the same publication. did. The product had Mw of 1600 in terms of polyethylene, Mw / Mn of 2.32, and an unsaturation at one end measured by ¹ H-NMR of 99.0 mol%.

（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.
After charging 5.0 g of macromonomer (P-1) and 500 ml of xylene into a glass reactor having an internal volume of 1 L which had been sufficiently purged with nitrogen, the temperature was raised to 95 ° C. to dissolve the macromonomer. 180 liter / hr of ethylene and 50 liter / hr of propylene were continuously supplied thereto to saturate the liquid phase and the gas phase. Subsequently, while ethylene and propylene were continuously supplied, 1.5 mL (11.1 mmol) of 5-ethylidene-2-norbornene (also referred to as ENB) and a decane solution of triisobutylaluminum (1.0 mol / L) were added. 0 mL (2.0 mmol) and 3.0 mL (0.030 mmol) of a toluene solution of compound (2) (0.010 mol / L) were added, and then triphenylcarbenium tetrakis (pentafluorophenyl) borate (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. Termination of the polymerization was carried out by adding a small amount of isobutanol. The obtained polymerization reaction solution was added to 1.5 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After the precipitate was washed with methanol, a methanol solution containing an antioxidant Irganox 1010 (manufactured by BASF) was added, followed by drying under reduced pressure at 80 ° C. for 10 hours to obtain 22.4 g of an olefin resin (β-1). Table 1 shows the analysis results of the obtained olefin-based resin (β-1).

[Comparative Example 1] Production of olefin-based resin (β'-1) In the subsequent step [a-2] of Example 1, polymerization was carried out in the same manner as in Example 1 except that the macromonomer (P-1) was not added. By carrying out, 18.8 g of an olefin-based resin (β′-1) was obtained. Table 1 shows the analysis results of the obtained olefin-based resin (β′-1).

[Comparative Example 2] Production of olefin-based resin (β "-1) In a 1 L glass-made reactor sufficiently purged with nitrogen, 17.4 g of olefin-based resin (β'-1) and macromonomer (P-1) were added. After 5.0 g of xylene and 500 ml of xylene were charged, the temperature was raised to 95 ° C. to dissolve the olefin resin (β′-1) and the macromonomer (P-1). The precipitate was washed with methanol, and a methanol solution containing an antioxidant Irganox 1010 (manufactured by BASF) was added thereto, followed by addition at 80 ° C. for 10 hours. Drying under reduced pressure gave 22.4 g of an olefin resin (β ″ -1). Table 1-1 shows the analysis results of the obtained olefin-based resin (β ″ -1).

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

[Comparative Examples 3 and 4]
A thermoplastic elastomer was obtained in the same manner as in Example 2 except that the components shown 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. under a load of 10 kg in accordance with ASTM D1238. Table 3 shows the results.

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

(3) Tensile test Using the sheet obtained in the same manner as in the above (2), a tensile test was conducted at a measurement temperature of 23 ° C. and a tensile speed of 500 mm / min according to JIS K6251, and the modulus, breaking strength, and fracture were measured. The elongation was measured. Table 3 shows the results.

(4) Compression set (CS)
Using the sheet obtained in the same manner as in the above (2), the compression set after treatment for 22 hours was measured at each temperature shown in Table 3 in accordance with JIS K6250 6.5 and JIS K6262 (2013). . Table 3 shows the results.

  From the results in Table 3, the thermoplastic elastomer of Example 2 had higher hardness, modulus and breaking strength than the thermoplastic elastomers of Comparative Examples 3 and 4, and had a compression of -30 ° C to 23 ° C. The permanent set (CS) has a small value. This is because a thermoplastic elastomer obtained using a resin (β-1) containing a graft-type olefin polymer can be obtained by using a blend resin (β "-1) of an ethylene-propylene-diene copolymer and an ethylene polymer. Compared to the thermoplastic elastomer obtained and the thermoplastic elastomer obtained using the existing ethylene-propylene-diene copolymer, it not only shows that the mechanical properties such as hardness, rigidity and strength have been greatly improved, At the same time, the compression set resistance, that is, the rubber elasticity was also significantly improved, indicating that the ethylene polymer which is a side chain of the graft-type olefin-based polymerization contained in the resin (β-1) was It is considered that, by imparting high rigidity and strength to the elastomer, and by forming physical crosslinking points in the elastomer component, good rubber elasticity is also imparted.

Claims (6)

A thermoplastic elastomer which is a crosslinked product of a composition containing an olefin resin (β), a crystalline polyolefin resin (α), and a crosslinking agent (γ) satisfying the following requirements (I) to (IV) .
(I) Including 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) The main chain polymer of the graft-type olefin polymer [R1] has an average of 0.5 to 20 side chains per 1000 carbon atoms in the molecular chain.
(III) In the measurement by differential scanning calorimetry (DSC), the melting temperature (Tm) is shown in the range of 60 to 130 ° C, 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 -30C. The thermoplastic elastomer according to claim 1, wherein the weight average molecular weight of the side chain of the graft-type olefin polymer [R1] is in the range of 500 to 10,000. A thermoplastic elastomer which is a crosslinked product using a pellet containing an olefin-based resin (β) satisfying the following requirements (I) to (IV) .
(I) Including 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) The main chain polymer of the graft-type olefin polymer [R1] has an average of 0.5 to 20 side chains per 1000 carbon atoms in the molecular chain.
(III) In the measurement by differential scanning calorimetry (DSC), the melting temperature (Tm) is shown in the range of 60 to 130 ° C, 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 -30C. The thermoplastic elastomer according to claim 3, wherein the weight average molecular weight of the side chain of the graft-type olefin polymer [R1] is in the range of 500 to 10,000. A crosslinked rubber, which is a crosslinked product of a composition containing an olefin resin (β) and a crosslinking agent (γ) satisfying the following requirements (I) to (IV) .
(I) Including 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) The main chain polymer of the graft-type olefin polymer [R1] has an average of 0.5 to 20 side chains per 1000 carbon atoms in the molecular chain.
(III) In the measurement by differential scanning calorimetry (DSC), the melting temperature (Tm) is shown in the range of 60 to 130 ° C, 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 -30C.   The crosslinked rubber according to claim 5, wherein the weight average molecular weight of the side chain of the graft-type olefin polymer [R1] is in the range of 500 to 10,000.