JP2018172553A - Thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition capable of obtaining a compact that is light in weight and has excellent mechanical physicality such as hardness, tensile strength and tensile elongation and oil resistance.SOLUTION: A thermoplastic elastomer composition of the present invention includes a crystalline olefin polymer (A) and an alpha-olefin/nonconjugated polyene copolymer (B) having 4 to 20 ethylene/carbons, in which a parameter A obtained by curve-fitting with the following formula (1) to a scattering intensity curve obtained by X-ray scattering measurement of a dynamic crosslinking thermoplastic elastomer formed by crosslinking the thermoplastic elastomer composition is in the range of 10 to 125 nm.SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic elastomer composition. More specifically, an olefinic thermoplastic elastomer composition capable of providing a dynamically crosslinked thermoplastic elastomer excellent in oil resistance, a dynamically crosslinked thermoplastic elastomer obtained by dynamically crosslinking the composition, and a method for producing the same And its uses.

  Olefin-based thermoplastic elastomers (TPO) are lightweight and easy to recycle, so they are energy- and resource-saving thermoplastic elastomers, especially automotive parts, industrial machine parts, electronic / electric equipment parts as an alternative to vulcanized rubber, Widely used in building materials.

However, conventional olefinic thermoplastic elastomers have the disadvantages of being inferior in tensile strength, breaking elongation and compression set as compared with vulcanized rubber, and there has been a strong demand for improvement.
As an olefin-based thermoplastic elastomer with improved properties, Patent Document 1 discloses that a crystalline polyolefin resin and an ethylene / propylene / non-conjugated polyene copolymer rubber are dynamically crosslinked under specific conditions. Dynamically cross-linked thermoplastic elastomers (TPV) have been proposed.

  Depending on the application (for example, for automotive parts), a thermoplastic elastomer obtained by performing only dynamic heat treatment (dynamic kneading) without intentionally crosslinking may be used (see Patent Document 2).

  However, in automotive parts applications, weight reduction is always required to improve fuel efficiency, but the thermoplastic elastomers used contain a large amount of fillers, so the specific gravity tends to increase, which hinders weight reduction of parts. It was. In addition, automobile parts are often used in places where they come into contact with lubricating oil, grease, etc. In general, olefinic thermoplastic elastomer compositions made of crystalline polyolefin and olefinic rubber are all made from paraffin. Since the rubber component has a high affinity with the oil, and particularly the rubber component has low crystallinity at room temperature, it is easy to absorb the oil, so that the oil resistance as a composition is not sufficient. Therefore, these automobile parts obtained by including an olefinic thermoplastic elastomer also have low oil resistance, and further improvements have been demanded.

Japanese Patent Laid-Open No. 09-012797 JP 2002-146105 A

  An object of the present invention is to provide a thermoplastic elastomer composition that is lightweight and can obtain a molded article excellent in mechanical properties such as hardness, tensile strength and tensile elongation, and oil resistance.

  The present inventors have intensively studied to solve the above problems. As a result, ethylene such as ethylene, 1-butene, and nonconjugated diene (EBDM) is used instead of ethylene, propylene, and nonconjugated diene (EPDM) that are usually used as raw materials for dynamically crosslinked thermoplastic elastomers (TPV). -It discovered that the oil resistance of the molded object which consists of TPV improves by using C4-C20 alpha olefin and nonconjugated polyene. This is because the rubber component such as EBDM is finely dispersed in a crystalline polyolefin such as polypropylene and has a specific dispersion structure size, compared to the case where EPDM is used, thereby restricting the movement of the plasticizer in the TPV. Was found to be the cause.

  Conventionally, evaluation of dispersibility in thermoplastic elastomers has been performed mainly by the dispersed particle size of the rubber component in the cross-sectional photograph, but it has been found that quantitative evaluation is possible by X-ray scattering measurement.

The present inventors have completed the present invention based on these findings.
That is, the thermoplastic elastomer composition of the present invention is
A crystalline olefin polymer (A);
It contains an ethylene / C4-C20 α-olefin / non-conjugated polyene copolymer (B) and satisfies the following requirement (1).
(1) A scattering intensity curve obtained by X-ray scattering measurement of a dynamically cross-linked thermoplastic elastomer obtained by dynamically cross-linking the thermoplastic elastomer composition in the presence of a cross-linking agent (where the vertical axis indicates the scattering intensity I (q), the horizontal axis is the scattering vector size q), the parameter A obtained by curve fitting using the following formula (1) is in the range of 10 to 125 nm.

[In formula (1), I (0) is the scattering intensity when extrapolated to q = 0, and q is the following formula between the wavelength λ (nm) of incident light and the scattering angle 2θ (rad): 2). ]
λq = 4πsinθ (2)

  According to the present invention, it is possible to obtain a thermoplastic elastomer composition that is lightweight and can obtain a molded article having excellent mechanical properties such as hardness, tensile strength and tensile elongation, and oil resistance.

It is a schematic diagram which shows the example of arrangement | positioning of a X-ray-scattering measurement. It is a photograph at the time of morphological observation about TPV obtained in Example 1 and Comparative Example 1 using TEM. 2 is a scattering intensity curve obtained by X-ray scattering measurement of TPV obtained in Example 1 and Comparative Example 1.

Hereinafter, the present invention will be described in detail.
[Thermoplastic elastomer composition]
The thermoplastic elastomer composition of the present invention (hereinafter also referred to as “composition (I)”) comprises a crystalline olefin polymer (A) (hereinafter also simply referred to as “polymer (A)”), ethylene. A C 4-20 α-olefin / non-conjugated polyene copolymer (B) (hereinafter also referred to simply as “copolymer (B)”), and satisfying the following requirement (1): And

  Requirement (1): Scattering intensity curve obtained by X-ray scattering measurement of a dynamically crosslinked thermoplastic elastomer obtained by dynamically crosslinking the composition (I) in the presence of a crosslinking agent (where the vertical axis is scattered) Parameter A obtained by curve fitting using the following formula (1) is 10 to 125 nm, preferably 50 to 120 nm, with respect to the intensity I (q) and the horizontal axis as the scattering vector q. Preferably it is the range of 80-115 nm.

In equation (1), I (0) is the scattering intensity when extrapolated to q = 0, and q is the following equation (2) between the wavelength λ (nm) of incident light and the scattering angle 2θ (rad): ).
λq = 4πsinθ (2)
The parameter A obtained by the fitting is a characteristic length of the dispersion structure size in the dynamically crosslinked thermoplastic elastomer. That is, the dispersibility in the thermoplastic elastomer can be quantitatively evaluated by X-ray scattering measurement.

From the viewpoint that the dispersion structure is a polymer multi-component phase separation structure, the X-ray scattering measurement is preferably a small-angle X-ray scattering measurement or an ultra-small-angle X-ray scattering measurement.
The X-ray scattering measurement can be performed using a general X-ray scattering measurement apparatus. For example, the polymer dedicated beam line BL03XU installed in the large synchrotron radiation facility SPring-8 (Hyogo Prefecture) is used. Can be measured. As shown in FIG. 1, X-rays may be incident on the sample, and the detector may be disposed in the back direction of the sample with respect to the incident X-rays. May be adopted (see “Takenaka, M. NIPPON GOMU KYOKAISHI 2011, 84, (1), 7-13”).

  The composition (I) of the present invention may contain a phenol resin-based crosslinking agent (C) as a crosslinking agent when performing the dynamic crosslinking. Moreover, the composition (I) of this invention may contain components other than the said component (A)-(C).

<Crystalline Olefin Polymer (A)>
The polymer (A) is not particularly limited as long as it is a crystalline polymer obtained from an olefin, but it has a high crystallinity obtained by polymerizing one or more monoolefins by either the high pressure method or the low pressure method. A polymer comprising a molecular weight solid product is preferred. Examples of such a polymer include an isotactic monoolefin polymer and a syndiotactic monoolefin polymer.

The polymer (A) may be synthesized by a conventionally known method, or a commercially available product may be used. Moreover, a polymer (A) may be used individually by 1 type, and may be used in combination of 2 or more type.
Examples of the monoolefin used as a raw material for the polymer (A) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 2-methyl-1-propene, and 3-methyl- 1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and the like can be mentioned. These olefins may be used alone or in combination of two or more.

  Among the polymers (A), from the viewpoint of heat resistance and oil resistance, a propylene homopolymer or a propylene-based (co) polymer obtained from a monoolefin mainly composed of propylene is preferable. In the case of the propylene copolymer, the content of the structural unit derived from propylene is preferably 40 mol% or more, more preferably 50 mol% or more, and as a monoolefin that becomes a structural unit derived from a monomer other than propylene. Is preferably the above monoolefin other than propylene, more preferably ethylene or butene.

The polymerization mode may be random type or block type, and any polymerization mode may be adopted as long as a crystalline resinous material can be obtained.
The polymer (A) has an MFR (ASTM D1238-65T, 230 ° C., 2.16 kg load) of usually 0.01 to 100 (g / 10 minutes), preferably 0.05 to 50 (g / 10 minutes). It is.

The polymer (A) has a melting point (Tm) obtained by differential scanning calorimetry (DSC) of usually 100 ° C. or higher, preferably 105 ° C. or higher. The differential scanning calorimetry is performed, for example, as follows. About 5 mg of a sample is packed in a special aluminum pan, heated to 30 ° C. to 200 ° C. at 320 ° C./min using DSCPyris 1 or DSC 7 manufactured by Perkin Elmer, Inc., held at 200 ° C. for 5 minutes, and then 200 ° C. The melting point is determined from the endothermic curve when the temperature is lowered from 10 to 30 ° C. at 10 ° C./min, held at 30 ° C. for 5 minutes, and then heated at 10 ° C./min. When a plurality of peaks are detected during DSC measurement, the peak temperature detected on the highest temperature side is defined as the melting point (Tm).
The polymer (A) plays a role of improving the fluidity and heat resistance of the thermoplastic elastomer composition.

<Copolymer (B)>
The copolymer (B) is derived from a structural unit (B1) derived from ethylene, a structural unit (B2) derived from at least one α-olefin having 4 to 20 carbon atoms, and at least one non-conjugated polyene. And satisfy the following requirements (2) and (3).

(2) B value represented by following formula (i) is 1.20 or more.
B value = ([EX] +2 [Y]) / [2 × [E] × ([X] + [Y])] (i)
In the formula (i), [E], [X] and [Y] are respectively a mole fraction of the structural unit (B1) derived from ethylene and a structural unit (B2) derived from an α-olefin having 4 to 20 carbon atoms. , The molar fraction of the structural unit (B3) derived from non-conjugated polyene, [EX] is the structural unit derived from ethylene (B1)-structural unit derived from α-olefin having 4 to 20 carbon atoms (B2 ) Dyad chain fraction.

  (3) The molar ratio [(B1) / (B2)] of the structural unit (B1) derived from ethylene and the structural unit (B2) derived from an α-olefin having 4 to 20 carbon atoms is 40/60 to 90 / 10.

  Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene (4 carbon atoms), 1-nonene (9 carbon atoms), 1-decene (10 carbon atoms), 1-nonadecene (19 carbon atoms), 1- Linear α-olefin having no side chain such as eicosene (carbon number 20); 4-methyl-1-pentene having a side chain, 9-methyl-1-decene, 11-methyl-1-dodecene, 12- Examples include α-olefins having side chains such as ethyl-1-tetradecene. These α-olefins may be used alone or in combination of two or more. Among these, α-olefins having 4 to 10 carbon atoms are preferable, 1-butene, 1-hexene and 1-octene are more preferable, and 1-butene is an oil resistance of the obtained molded article, particularly at a relatively high temperature. The oil resistance, flexibility and impact resistance of the resin can be improved.

  Non-conjugated polyenes include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, etc. Cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6 -Cyclic non-conjugated dienes such as chloromethyl-5-isopropenyl-2-norbornene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2, 5-norbornadiene, 1,3,7-octatriene, 1,4,9-decatrie , 4,8-dimethyl-1,4,8-decatriene, etc. trienes and 4-ethylidene-8-methyl-1,7-nonadiene and the like. These non-conjugated polyenes may be used alone or in combination of two or more. Among these, a mixture of cyclic non-conjugated dienes such as 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene 5-Ethylidene-2-norbornene and 5-vinyl-2-norbornene are more preferable.

  Examples of the copolymer (B) include ethylene / 1-butene / 1,4-hexadiene copolymer, ethylene / 1-pentene / 1,4-hexadiene copolymer, ethylene / 1-hexene / 1,4-hexadiene. Copolymer, ethylene / 1-heptene / 1,4-hexadiene copolymer, ethylene / 1-octene / 1,4-hexadiene copolymer, ethylene / 1-nonene / 1,4-hexadiene copolymer, Ethylene / 1-decene / 1,4-hexadiene copolymer, ethylene / 1-butene / 1-octene / 1,4-hexadiene copolymer, ethylene / 1-butene / 5-ethylidene-2-norbornene copolymer , Ethylene / 1-pentene / 5-ethylidene-2-norbornene copolymer, ethylene / 1-hexene / 5-ethylidene-2-norbornene copolymer, ethylene 1-heptene-5-ethylidene-2-norbornene copolymer, ethylene / 1-octene / 5-ethylidene-2-norbornene copolymer, ethylene / 1-nonene / 5-ethylidene-2-norbornene copolymer, Ethylene / 1-decene / 5-ethylidene-2-norbornene copolymer, ethylene / 1-butene / 1-octene / 5-ethylidene-2-norbornene copolymer, ethylene / 1-butene / 5-ethylidene-2- Norbornene-5-vinyl-2-norbornene copolymer, ethylene / 1-pentene / 5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, ethylene / 1-hexene / 5-ethylidene-2- Norbornene-5-vinyl-2-norbornene copolymer, ethylene / 1-heptene-5-ethylidene-2-norbo Nene / 5-vinyl-2-norbornene copolymer, ethylene / 1-octene / 5-ethylidene-2-norbornene / 5-vinyl-2-norbornene copolymer, ethylene / 1-nonene / 5-ethylidene-2- Norbornene / 5-vinyl-2-norbornene copolymer, ethylene / 1-decene / 5-ethylidene-2-norbornene / 5-vinyl-2-norbornene copolymer, ethylene / 1-butene / 1-octene / 5 And ethylidene-2-norbornene / 5-vinyl-2-norbornene copolymer.

A copolymer (B) may be used individually by 1 type, and may be used in combination of 2 or more types.
Said B value of a copolymer (B) is 1.20 or more, Preferably it is 1.21-1.80, More preferably, it exists in the range of 1.22-1.40.

When the B value is less than 1.20, compression set becomes large, and there is a possibility that a thermoplastic elastomer composition excellent in balance between rubber elasticity and tensile strength cannot be obtained.
The B value is an index indicating the randomness of the copolymer monomer chain distribution in the copolymer (B), and [E], [X], [Y], [EX] in the above formula (i). measures the ¹³ C-NMR spectrum, JCRandall [Macromolecules, 15, 353 (1982)], J. Ray [Macromolecules, 10, 773 (1977)] can be determined based on these reports.

  The copolymer (B) has a molar ratio [(B1) / (B2)] of the structural unit (B1) derived from ethylene and the structural unit (B2) derived from α-olefin of 40/60 to 90. / 10 range. The lower limit of the molar ratio is preferably 45/55, more preferably 50/50, and particularly preferably 55/45. The upper limit of the molar ratio is preferably 80/20, more preferably 75/25, and further preferably 70/30.

When the molar ratio between the structural unit (B1) derived from ethylene and the structural unit (B2) derived from α-olefin is in the above range, the oil resistance, particularly the oil resistance at a relatively high temperature, is excellent, and the rubber elasticity A thermoplastic elastomer composition having an excellent balance with the tensile strength at room temperature can be obtained.
It is desirable that the copolymer (B) further satisfies at least one of the following requirements (4) and (5).

(4) Mooney viscosity ML _{(1 + 4)} (125 ° C.) at 125 ° C. obtained by measurement according to JIS K6300 (1994) is not particularly limited, but preferably 5 ˜120, more preferably 20˜115, and even more preferably 50˜110.
When the Mooney viscosity is within the above range, good post-treatment properties (ribbon handling properties) are exhibited and the rubber properties tend to be excellent.

  (5) The content of the structural unit (B3) derived from the non-conjugated polyene is preferably 0.1 to 6 with respect to 100 mol% of the total of the structural units (B1), (B2) and (B3). The range is 0.0 mol%. The lower limit of the content of the structural unit (B3) is preferably 0.5 mol%. As an upper limit of content of a structural unit (B3), Preferably it is 4.0 mol%, More preferably, it is 3.5 mol%, More preferably, it is 3.0 mol%. When the content of the structural unit (B3) derived from the non-conjugated polyene is in the above range, an ethylene copolymer having sufficient crosslinkability and flexibility tends to be obtained.

  In the composition (I) of the present invention, the weight ratio (A) / (B) of the crystalline olefin polymer (A) and the ethylene / α-olefin / nonconjugated polyene copolymer (B) is preferably 90/10 to 10/90, more preferably 60/40 to 20/80. When the weight ratio (A) / (B) is in the above range, a molded article having excellent mechanical properties and moldability can be obtained.

The copolymer (B) is, for example,
(A) a transition metal compound represented by the following general formula [VII] (hereinafter also referred to as “bridged metallocene compound (a)”);
(B) (b-1) an organometallic compound,
(b-2) an organoaluminum oxy compound, and
(b-3) A compound that reacts with the transition metal compound (a) to form an ion pair (hereinafter also referred to as “ionized ionic compound (b-3)”).
At least one compound selected from the group consisting of:
Furthermore, in the presence of an olefin polymerization catalyst containing (c) a particulate support (hereinafter also simply referred to as “support (c)”), ethylene, an α-olefin having 4 to 20 carbon atoms, and a non-conjugated polyene as necessary. Can be produced by copolymerization. When ethylene, an α-olefin having 4 to 20 carbon atoms and a non-conjugated polyene are copolymerized in the presence of an olefin polymerization catalyst containing the bridged metallocene compound (a), the resulting copolymer can have a higher molecular weight. The advantage that it is is obtained.

  ≪Bridged metallocene compound (a) ≫

M, R ⁵ , R ⁶ , Q and j in the formula [VII] will be described below.

Y is an atom selected from the group consisting of a carbon atom, a silicon atom, a germanium atom, and a tin atom, and is preferably a carbon atom.
The above M is a titanium atom, a zirconium atom or a hafnium atom, preferably a hafnium atom.

R ⁵ and R ⁶ are substituted aryl groups obtained by substituting one or more hydrogen atoms of an aryl group with an electron donating substituent having a Hammett's rule substituent constant σ of −0.2 or less, In the case of having a plurality of electron-donating substituents, the electron-donating substituents may be the same or different. Other than the electron-donating substituent, a hydrocarbon group having 1 to 20 carbon atoms, silicon-containing May have a substituent selected from the group consisting of a group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group, and when there are a plurality of such substituents, each substituent may be the same or different. A substituted aryl group (hereinafter also referred to as “electron-donating group-containing substituted aryl group”).

  As the aryl group, phenyl group, 1-naphthyl group, 2-naphthyl group, anthracenyl group, phenanthrenyl group, tetracenyl group, chrysenyl group, pyrenyl group, indenyl group, azulenyl group, pyrrolyl group, pyridyl group, furanyl group, thiophenyl group Substituents derived from aromatic compounds such as The aryl group is preferably a phenyl group or a 2-naphthyl group. Examples of the aromatic compounds include aromatic hydrocarbons such as benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, pyrene, indene, azulene, pyrrole, pyridine, furan, thiophene, and heterocyclic aromatic compounds. Is mentioned.

  An electron donating group having a Hammett's rule substituent constant σ of −0.2 or less is defined and exemplified as follows. Hammett's rule is an empirical rule proposed by L. P. Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives, which is widely accepted today. Substituent constants obtained by Hammett's rule include σp when substituted at the para-position of the benzene ring and σm when substituted at the meta-position, and these values can be found in many general literatures. For example, the literature by Hansch and Taft [Chem. Rev., 91, 165 (1991)] gives a detailed description of a very wide range of substituents. However, σp and σm described in these documents may differ slightly depending on the document even if they are the same substituent. In the present invention, in order to avoid the confusion caused by such a situation, Table 1 (168-175) of the literature by Hansch and Taft [Chem. Rev., 91, 165 (1991)] is used for all the substituents described. The values described in (page) are defined as Hammett's rule substituent constants σp and σm. In the present invention, an electron donating group having a Hammett's rule substituent constant σ of −0.2 or less means that σp is −0 when the electron donating group is substituted at the para position (position 4) of the phenyl group. .2 or less electron donating group, and when substituted at the meta position (3-position) of the phenyl group, σm is an electron donating group of −0.2 or less. In addition, when the electron donating group is substituted at the ortho position (position 2) of the phenyl group, or when substituted at any position of the aryl group other than the phenyl group, σp is −0.2 or less. Electron donating group.

  As an electron donating substituent having Hammett's rule substituent constant σp or σm of −0.2 or less, p-amino group (4-amino group), p-dimethylamino group (4-dimethylamino group), p- Nitrogen-containing groups such as diethylamino group (4-diethylamino group) and m-diethylamino group (3-diethylamino group), oxygen-containing groups such as p-methoxy group (4-methoxy group) and p-ethoxy group (4-ethoxy group) Groups, tertiary hydrocarbon groups such as p-t-butyl group (4-t-butyl group), silicon-containing groups such as p-trimethylsiloxy group (4-trimethylsiloxy group), and the like. The electron donating substituent having Hammett's rule constant σp or σm of −0.2 or less as defined in the present invention is described in Hansch and Taft [Chem. Rev., 91, 165 (1991)]. The substituents are not limited to those described in Table 1 (pages 168-175). Even if the substituent is not described in the document, the substituent constant σp or σm when measured based on Hammett's rule is within the range thereof is the Hammett's rule substituent defined in the present invention. The constant σp or σm is included in the electron donating group having −0.2 or less. Examples of such a substituent include a pN-morpholinyl group (4-N-morpholinyl group) and an mN-morpholinyl group (3-N-morpholinyl group).

  In the electron-donating group-containing substituted aryl group, when a plurality of the electron-donating substituents are substituted, each electron-donating substituent may be the same or different. A substituent selected from the group consisting of 1 to 20 hydrocarbon groups, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups may be substituted, and a plurality of the substituents may be substituted. Each substituent may be the same or different, but the sum of the electron donating substituent contained in one substituted aryl group and the Hammett's rule substituent constant σ of each substituent is −0. .15 or less is preferable. Examples of such substituted aryl groups include m, p-dimethoxyphenyl group (3,4-dimethoxyphenyl group), p- (dimethylamino) -m-methoxyphenyl group (4- (dimethylamino) -3-methoxyphenyl. Group), p- (dimethylamino) -m-methylphenyl group (4- (dimethylamino) -3-methylphenyl group), p-methoxy-m-methylphenyl group (4-methoxy-3-methylphenyl group) , P-methoxy-m, m-dimethylphenyl group (4-methoxy-3,5-dimethylphenyl group) and the like.

  Examples of the hydrocarbon group having 1 to 20 carbon atoms that the electron-donating group-containing substituted aryl group may have include an alkyl group having 1 to 20 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, and 2 carbon atoms. -20 chain unsaturated hydrocarbon group, C3-C20 cyclic unsaturated hydrocarbon group, etc. are mentioned.

  Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and n-nonyl. Group, linear saturated hydrocarbon group such as n-decanyl group; isopropyl group, isobutyl group, s-butyl group, t-butyl group, t-amyl group, neopentyl group, 3-methylpentyl group, 1,1- Diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-dipropylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl Examples thereof include branched saturated hydrocarbon groups such as -2-methylpropyl group and cyclopropylmethyl group. Preferably the carbon number of the said alkyl group is 1-6.

  Examples of the cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornenyl group, 1-adamantyl group, and 2-adamantyl group. Substituted cyclic saturated hydrocarbon group; hydrogen atom of unsubstituted cyclic saturated hydrocarbon group such as 3-methylcyclopentyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 4-cyclohexylcyclohexyl group, 4-phenylcyclohexyl group, etc. Are groups in which is substituted with a hydrocarbon group having 1 to 17 carbon atoms. The number of carbon atoms of the cyclic saturated hydrocarbon group is preferably 5-11.

  Examples of the chain unsaturated hydrocarbon group having 2 to 20 carbon atoms include alkenyl groups such as ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group (allyl group), and 1-methylethenyl group (isopropenyl group). , An ethynyl group which is an alkynyl group, a 1-propynyl group, a 2-propynyl group (propargyl group) and the like. The chain unsaturated hydrocarbon group preferably has 2 to 4 carbon atoms.

  Examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms include unsubstituted cyclic unsaturated hydrocarbon groups such as cyclopentadienyl group, norbornyl group, phenyl group, naphthyl group, indenyl group, azulenyl group, phenanthryl group and anthracenyl group. Hydrogen group; 3-methylphenyl group (m-tolyl group), 4-methylphenyl group (p-tolyl group), 4-ethylphenyl group, 4-t-butylphenyl group, 4-cyclohexylphenyl group, biphenylyl group, A hydrogen atom of an unsubstituted cyclic unsaturated hydrocarbon group such as 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group (mesityl group) has 1 to 15 carbon atoms A group replaced by a hydrocarbon group; a hydrogen atom of a straight chain hydrocarbon group such as a benzyl group or a cumyl group or a branched saturated hydrocarbon group; Such groups which are replaced by 9 cyclic saturated hydrocarbon group or a cyclic unsaturated hydrocarbon group. The number of carbon atoms of the cyclic unsaturated hydrocarbon group is preferably 6-10.

  Examples of the silicon-containing group that the electron-donating group-containing substituted aryl group may have include an alkylsilyl group such as a trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, triisopropylsilyl group; dimethylphenylsilyl group, methyl Arylsilyl groups such as diphenylsilyl groups and t-butyldiphenylsilyl groups; groups in which carbon atoms are replaced by silicon atoms in hydrocarbon groups having 1 to 20 carbon atoms such as pentamethyldisiranyl groups and trimethylsilylmethyl groups, etc. Is mentioned. The alkylsilyl group preferably has 1 to 10 carbon atoms, and the arylsilyl group preferably has 6 to 18 carbon atoms.

Examples of the nitrogen-containing group that the electron-donating group-containing substituted aryl group may have include an amino group, a nitro group, an N-morpholinyl group, the above-described hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing group. groups CH- structural unit is replaced by a nitrogen atom, -CH ₂ - group in which the structural unit is replaced with a nitrogen atom bonded hydrocarbon group having 1 to 20 carbon atoms or -CH ₃ several structural units of carbon, 1 Examples thereof include a dimethylamino group, a diethylamino group, a dimethylaminomethyl group, a cyano group, a pyrrolidinyl group, a piperidinyl group, and a pyridinyl group, which are groups substituted with a nitrogen atom or a nitrile group to which 20 hydrocarbon groups are bonded. As the nitrogen-containing group, a dimethylamino group and an N-morpholinyl group are preferable.

Examples of the oxygen-containing group that the electron-donating group-containing substituted aryl group may have include a hydroxyl group, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a nitrogen-containing group, and a —CH ₂ — structural unit. A methoxy group, an ethoxy group, or a t-butoxy group in which is substituted with an oxygen atom or a carbonyl group, or a group in which the —CH ₃ structural unit is substituted with an oxygen atom bonded with a hydrocarbon group having 1 to 20 carbon atoms , Phenoxy group, trimethylsiloxy group, methoxyethoxy group, hydroxymethyl group, methoxymethyl group, ethoxymethyl group, t-butoxymethyl group, 1-hydroxyethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 2- Hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, n-2-oxabutylene group, n-2-oxapentylene N-3-oxapentylene group, aldehyde group, acetyl group, propionyl group, benzoyl group, trimethylsilylcarbonyl group, carbamoyl group, methylaminocarbonyl group, carboxy group, methoxycarbonyl group, carboxymethyl group, ethocarboxymethyl group, A carbamoylmethyl group, a furanyl group, a pyranyl group, etc. are mentioned. As the oxygen-containing group, a methoxy group is preferable.

Examples of the halogen atom that the electron-donating group-containing substituted aryl group may have include a group 17 element such as fluorine, chlorine, bromine, and iodine.
Examples of the halogen-containing group that the electron-donating group-containing substituted aryl group may have include a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, or an oxygen-containing group, in which a hydrogen atom is a halogen atom. Examples thereof include a trifluoromethyl group, a tribromomethyl group, a pentafluoroethyl group, and a pentafluorophenyl group, which are groups substituted by atoms.

  Q is an atom, substituent, or ligand selected from the group consisting of a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, and a neutral ligand that can coordinate with a lone electron pair, When there are a plurality of Qs, they may be the same or different.

  Specific examples of the halogen atom to be Q and the hydrocarbon group having 1 to 20 carbon atoms are the same as the halogen atom and the hydrocarbon group having 1 to 20 carbon atoms that the electron-donating group-containing substituted aryl group may have. It is. When Q is a halogen atom, a chlorine atom is preferable. When Q is a hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group preferably has 1 to 7 carbon atoms.

  Examples of the anionic ligand include alkoxy groups such as methoxy group, t-butoxy group and phenoxy group; carboxylate groups such as acetate and benzoate; sulfonate groups such as mesylate and tosylate.

Examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine; tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane, etc. An ether compound etc. are mentioned.
j is an integer of 1 to 4, preferably 2.

  Since the 2,3,6,7-tetramethylfluorenyl group contained in the bridged metallocene compound (a) has four substituents at the 2, 3, 6 and 7 positions, the electronic effect is large. As a result, it is presumed that a high polymerization activity and high molecular weight ethylene copolymer is produced. On the other hand, since non-conjugated polyenes are generally bulkier than α-olefins, the polymerization catalyst for polymerizing the non-conjugated polyenes should not be bulky in the vicinity of the central metal of the metallocene compound, which is the polymerization active site. Presumed to lead to performance improvement. Since the four methyl groups contained in the 2,3,6,7-tetramethylfluorenyl group are not bulky compared to other hydrocarbon groups, this contributes to high non-conjugated polyene copolymerization performance. It is thought that. From the above, the crosslinked metallocene compound (a) containing a 2,3,6,7-tetramethylfluorenyl group, in particular, has a high molecular weight of the ethylene-based copolymer produced, and a high non-conjugated polyene copolymerization performance, It is presumed that high polymerization activity is simultaneously achieved at a high level and in a well-balanced manner.

  The bridged metallocene compound (a) can be synthesized by a simple method such as the following formula [VIII].

In formula [VIII], specific examples and preferred examples of definitions of M, R ⁵ and R ⁶ are the same as those in formula [VII].

In the above formula [VIII], R ⁵ and R ⁶ are as described above. Various ketones satisfying such a condition represented by the general formula R ⁵ —C (═O) —R ⁶ are generally used. Since it is commercially available from reagent manufacturers, it is easy to obtain the raw material for the bridged metallocene compound (a). Even if such a ketone is not commercially available, it can be easily synthesized, for example, by the method of Olah et al. [Heterocycles, 40, 79 (1995)]. As described above, the bridged metallocene compound (a) has a relatively simple and easy production process, further reduces the production cost, and further reduces the production cost of the ethylene copolymer by using the bridged metallocene compound. The advantage of being obtained. Further, when ethylene, an α-olefin having 4 or more carbon atoms and a non-conjugated polyene are copolymerized in the presence of an olefin polymerization catalyst containing the bridged metallocene compound (a), the resulting copolymer has a higher molecular weight. There is also an advantage that it is possible.

In the bridged metallocene compound (a), R ⁵ and R ⁶ are preferably a group selected from the group consisting of an aryl group and a substituted aryl group. When ethylene, an α-olefin having 4 or more carbon atoms and a non-conjugated polyene are copolymerized in the presence of an olefin polymerization catalyst containing the bridged metallocene compound, the polymerization activity is further improved and the resulting copolymer has a higher molecular weight. Can be obtained. At the same time, there is an advantage that the copolymerization performance of the nonconjugated polyene is improved (for example, the content of the nonconjugated polyene unit in the copolymer is increased, and the nonconjugated polyene unit is easily dispersed uniformly in the copolymer). can get.

In the bridged metallocene compound (a), R ⁵ and R ⁶ are more preferably the same group. By selecting R ⁵ and R ⁶ in this way, the synthesis process of the bridged metallocene compound is simplified, and the production cost is further reduced. By using this bridged metallocene compound, the production cost of the copolymer is reduced. The advantage of being obtained. Furthermore, when ethylene, an α-olefin having 4 or more carbon atoms and a non-conjugated polyene are copolymerized in the presence of an olefin polymerization catalyst containing the bridged metallocene compound, the resulting copolymer can have a higher molecular weight. There is an advantage of being.

As a result of intensive studies on various bridged metallocene compounds, the present applicant has found that when the above-mentioned bridged metallocene compound (a) has R ⁵ and R ⁶ as the above group, the olefin polymerization catalyst contains the bridged metallocene compound (a). It has been found for the first time that the molecular weight of the copolymer produced can be further increased when ethylene, an α-olefin having 4 to 20 carbon atoms, and a non-conjugated polyene are copolymerized in the presence of.

In the coordination polymerization of olefins using an organometallic complex catalyst such as the bridged metallocene compound (a), the olefin polymer is repeatedly polymerized on the central metal of the catalyst, whereby the molecular chain of the resulting olefin polymer grows (growth reaction). ), The molecular weight of the olefin polymer is known to increase. On the other hand, in a reaction called chain transfer, the molecular chain of the olefin polymer is dissociated from the central metal of the catalyst, so that the growth reaction of the molecular chain is stopped, and therefore the increase in the molecular weight of the olefin polymer is also stopped. Are known. From the above, the molecular weight of the olefin polymer is characterized by the ratio between the frequency of the growth reaction and the frequency of the chain transfer reaction inherent to the organometallic complex catalyst that produces it. That is, the larger the ratio between the frequency of the growth reaction and the frequency of the chain transfer reaction, the higher the molecular weight of the olefin polymer produced, and vice versa. Here, the frequency of each reaction can be estimated from the activation energy of each reaction. A reaction with a low activation energy is high in frequency, and conversely, a reaction with a high activation energy is low in frequency. It is thought that it can be done. In general, it is known that the frequency of the growth reaction in olefin polymerization is sufficiently high compared to the frequency of the chain transfer reaction, that is, the activation energy of the growth reaction is sufficiently low compared to the activation energy of the chain transfer reaction. Yes. Accordingly, the value obtained by subtracting the activation energy of the growth reaction from the activation energy of the chain transfer reaction (hereinafter referred to as ΔEc) is positive, and the larger the value, the greater the frequency of the growth reaction compared to the frequency of the chain transfer reaction. It is presumed that the molecular weight of the produced olefin polymer is high. The validity of the estimation of the molecular weight of the olefin polymer thus performed is supported by, for example, the calculation results of Laine et al. [Organometallics, 30, 1350 (2011)]. In the bridged metallocene compound (a), R ⁵ and R ⁶ are substituted with one or more electron-donating substituents, in particular, one or more electron-donating substituents having a Hammett's rule substituent constant σ of −0.2 or less. When it is used as a group, ΔEc increases, and when copolymerizing ethylene, an α-olefin having 4 to 20 carbon atoms and a non-conjugated polyene in the presence of an olefin polymerization catalyst containing the bridged metallocene compound (a). The molecular weight of the produced copolymer is estimated to be high.

In the bridged metallocene compound (a), the electron-donating substituent contained in R ⁵ and R ⁶ is more preferably a group selected from the group consisting of a nitrogen-containing group and an oxygen-containing group.

In the bridged metallocene compound (a), R ⁵ and R ⁶ are more preferably a substituted phenyl group containing a group selected from the group consisting of a nitrogen-containing group and an oxygen-containing group as the electron-donating substituent. For example, when synthesizing according to the method of the above formula [VIII], since various benzophenones as raw materials are commercially available from general reagent manufacturers, it is easy to obtain the raw materials, the manufacturing process is simplified, and the manufacturing cost is further reduced. By using this bridged metallocene compound, the production cost of the copolymer (B) can be reduced.

  Here, examples of the substituted phenyl group containing a group selected from the group consisting of a nitrogen-containing group and an oxygen-containing group as the electron-donating substituent include an o-aminophenyl group (2-aminophenyl group) and p-aminophenyl. Group (4-aminophenyl group), o- (dimethylamino) phenyl group (2- (dimethylamino) phenyl group), p- (dimethylamino) phenyl group (4- (dimethylamino) phenyl group), o- ( Diethylamino) phenyl group (2- (diethylamino) phenyl group), p- (diethylamino) phenyl group (4- (diethylamino) phenyl group), m- (diethylamino) phenyl group (3- (diethylamino) phenyl group), o- Methoxyphenyl group (2-methoxyphenyl group), p-methoxyphenyl group (4-methoxyphenyl group), o-eth Siphenyl group (2-ethoxyphenyl group), p-ethoxyphenyl group (4-ethoxyphenyl group), o-N-morpholinylphenyl group (2-N-morpholinylphenyl group), pN-morpholine Nylphenyl group (4-N-morpholinylphenyl group), m-N-morpholinylphenyl group (3-N-morpholinylphenyl group), o, p-dimethoxyphenyl group (2,4-dimethoxyphenyl) Group), m, p-dimethoxyphenyl group (3,4-dimethoxyphenyl group), p- (dimethylamino) -m-methoxyphenyl group (4- (dimethylamino) -3-methoxyphenyl group), p- ( Dimethylamino) -m-methylphenyl group (4- (dimethylamino) -3-methylphenyl group), p-methoxy-m-methylphenyl group (4-methoxy) 3-methylphenyl group), p-methoxy -m, m-dimethylphenyl group (4-methoxy-3,5-dimethylphenyl group).

In the bridged metallocene compound (a), R ⁵ and R ⁶ are each derived from a nitrogen-containing group and an oxygen-containing group as the electron-donating substituent at the meta position and / or para position with respect to the bond to the carbon atom as Y. More preferably, it is a substituted phenyl group containing a group selected from the group consisting of For example, when synthesizing according to a method such as the above formula [VIII], the synthesis is facilitated compared to the case where the group is substituted at the ortho position, the production process is simplified, the production cost is further reduced, and this bridged metallocene is eventually produced. The advantage that the production cost of the ethylene copolymer is reduced is obtained by using the compound.

In the bridged metallocene compound (a), R ⁵ and R ⁶ are substituted phenyl groups containing a nitrogen-containing group as the electron-donating substituent at the meta position and / or para position with respect to the bond to the carbon atom as Y. In this case, the nitrogen-containing group is more preferably a group represented by the following general formula [II].

In the formula [II], R ⁷ and R ⁸ are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group and a halogen-containing group or a substituent selected from the group, They may be the same or different and may be bonded to each other to form a ring, and the line drawn to the right of N represents a bond with a phenyl group.

Specific examples and preferred examples of the hydrocarbon group having 1 to 20 carbon atoms, the silicon-containing group, the oxygen-containing group and the halogen-containing group as R ⁷ and R ^{8 are the same} as those in the above formula [VII].
Such a bridged metallocene compound (a-4) is represented by the following general formula [IX].

In formula [IX], the definitions, specific examples, and preferred examples of M, Q, and j are the same as those in formula [VII]. R ⁷ , R ⁸ and R ¹⁰ are substituents selected from the group consisting of hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups. May be the same or different, and adjacent substituents of R ⁷ , R ⁸ and R ¹⁰ may be bonded to each other to form a ring, and NR ⁷ R ⁸ is a Hammett's substituent constant. σ is a nitrogen-containing group having −0.2 or less, and when a plurality of nitrogen-containing groups are present, each nitrogen-containing group may be the same as or different from each other, and n is an integer of 1 to 3. , M is an integer from 0 to 4.

In the bridged metallocene compound (a), R ⁵ and R ⁶ are substituted phenyl groups containing an oxygen-containing group as the electron-donating substituent at the meta position and / or the para position with respect to the bond to the carbon atom as Y. In this case, the oxygen-containing group is more preferably a group represented by the following general formula [III].

In the formula [III], R ⁹ is an atom or substituent selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group and a halogen-containing group, The drawn line represents the bond with the phenyl group.

Specific examples and preferred examples of the hydrocarbon group having 1 to 20 carbon atoms, the silicon-containing group, the nitrogen-containing group and the halogen-containing group as R ^{9 are the same} as those in the formula [VII].
Such a bridged metallocene compound (a-5) is represented by the following general formula [X].

In the formula [X], the definitions, specific examples and preferred examples of M, Q and j are the same as those in the formula [VII]. R ⁹ and R ¹⁰ are each a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, an atom or a substituent selected from the group consisting of a halogen atom and a halogen-containing group; Each may be the same or different, and adjacent substituents of R ¹⁰ may be bonded to each other to form a ring, and OR ⁹ is an oxygen-containing group having a Hammett's rule substituent constant σ of −0.2 or less. And when there are a plurality of such oxygen-containing groups, the oxygen-containing groups may be the same or different from each other, n is an integer of 1 to 3, and m is an integer of 0 to 4.

  The bridged metallocene compound (a) represented by the general formula [VII], the bridged metallocene compound (a-4) represented by the general formula [IX] or the bridged metallocene compound represented by the general formula [X] ( In a-5), M is more preferably a hafnium atom. When copolymerizing ethylene, an α-olefin having 4 or more carbon atoms and a non-conjugated polyene in the presence of an olefin polymerization catalyst containing the above bridged metallocene compound in which M is a hafnium atom, the resulting copolymer has a higher molecular weight. And the advantage of improving the copolymerization performance of the non-conjugated polyene can be obtained.

As such a bridged metallocene compound (a-6),
[Dimethylmethylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [Diethylmethylene (η ⁵ -cyclopentadienyl) (η ^5- 2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [di-n-butylmethylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorene) Nyl)] hafnium dichloride, [dicyclopentylmethylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [dicyclohexylmethylene (η ⁵ -cyclopenta Dienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride,
[Cyclopentylidene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [cyclohexylidene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride,
[Diphenylmethylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [di-1-naphthylmethylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [di-2-naphthylmethylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7- Tetramethylfluorenyl)] hafnium dichloride,
[Bis (3-methylphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis (4-methylphenyl) methylene ( η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis (3,4-dimethylphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis (4-n-hexylphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3, 6,7-tetramethylfluorenyl)] hafnium dichloride, [bis (4-cyclohexylphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl) ] Hafnium dichloride, [bis (4-t-butylphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethyl) Rufluorenyl)] hafnium dichloride,
[Bis (3-methoxyphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis (4-methoxyphenyl) methylene ( η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis (3,4-dimethoxyphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis (4-methoxy-3-methylphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2, 3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis (4-methoxy-3,4-dimethylphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6, 7-tetramethylfluorenyl)] hafnium dichloride, [bis (4-ethoxyphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis (4-phenoxyphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6, 7-tetramethylfluorenyl)] hafnium dichloride, [bis {4- (trimethylsiloxy) phenyl} methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl) )] Hafnium dichloride,
[Bis {3- (dimethylamino) phenyl} methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis {4- (dimethyl Amino) phenyl} methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis (4-N-morpholinylphenyl) (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride,
[Bis {4- (trimethylsilyl) phenyl} methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride,
[Bis (3-chlorophenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis (4-chlorophenyl) methylene (η ⁵ -Cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis (3-fluorophenyl) methylene (η ⁵ -cyclopentadienyl) (η ^5- 2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis (4-fluorophenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethyl Fluorenyl)] hafnium dichloride, [bis {3- (trifluoromethyl) phenyl} methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium Dichloride, [bis {4- (trifluoromethyl) phenyl} methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride,
[Methylphenylmethylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [Methyl (4-methylphenyl) methylene (η ⁵ -cyclopenta Dienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [methyl (4-methoxyphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3 , 6,7-tetramethylfluorenyl)] hafnium dichloride, [methyl {4- (dimethylamino) phenyl} methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethyl Fluorenyl)] hafnium dichloride, [methyl (4-N-morpholinylphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium Dichloride,
[Dimethylsilylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [Diethylsilylene (η ⁵ -cyclopentadienyl) (η ^5- 2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [dicyclohexylsilylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium Dichloride, [diphenylsilylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [di (4-methylphenyl) silylene (η ⁵ -cyclo Pentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride,
[Dimethylgermylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [Diphenylgermylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride,
[1- (η ⁵ -cyclopentadienyl) -2- (η ⁵ -2,3,6,7-tetramethylfluorenyl) ethylene] hafnium dichloride, [1- (η ⁵ -cyclopentadienyl) -3- (η ⁵ -2,3,6,7-tetramethylfluorenyl) propylene] hafnium dichloride, [1- (η ⁵ -cyclopentadienyl) -2- (η ⁵ -2,3,6 , 7-tetramethylfluorenyl) -1,1,2,2-tetramethylsilylene] hafnium dichloride, [1- (η ⁵ -cyclopentadienyl) -2- (η ⁵ -2,3,6, 7-tetramethylfluorenyl) phenylene] hafnium dichloride, compounds in which the hafnium atom of these compounds is replaced with a zirconium atom, or compounds in which a chloro ligand is replaced with a methyl group. Among these catalysts, [bis (4-methylphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride is preferable.

  The bridged metallocene compound used for the production of the copolymer (B) can be produced by a known method, and the production method is not particularly limited. As a manufacturing method, for example, J. et al. Organomet. Chem. 63, 509 (1996), WO2006 / 123759, WO01 / 27124, JP2004-168744, JP2004-175759, and JP2000-2000, which are publications related to the application by the present applicant. And the production method described in Japanese Patent No. 212194.

<< Compound (b) >>
The compound (b) is composed of (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) a compound that reacts with the bridged metallocene compound (a) to form an ion pair. At least one compound selected from the group consisting of:

(B-1) Organometallic compound As the organometallic compound (b-1) used for the production of the copolymer (B), specifically, the periodic table such as the following general formulas [X] to [XII] is used. Organometallic compounds of Groups 1, 2, and 13 and 13 are used.

a) the general formula _{^{R a m Al (OR b)}} n H p X q ··· [X]
(In the formula [X], R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number 0 ≦ q <3, and m + n + p + q = 3. Compound.

  As a compound represented by the general formula [X], trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, tricycloalkylaluminum, isobutylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, Examples include ethylaluminum sesquichloride, methylaluminum dichloride, dimethylaluminum chloride, and diisobutylaluminum hydride.

b) General formula M ² AlR ^a ₄ ... [XI]
(In the formula [XI], M ² represents Li, Na or K, and R ^a is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms). Complex alkylated product of Group 1 metal and aluminum.
Examples of the compound represented by the general formula [XI] include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

c) General formula R ^a R ^b M ³ ... [XII]
(In the formula [XII], R ^a and R ^b may be the same or different and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ³ represents Mg, Zn or A dialkyl compound having a metal of Group 2 or Group 12 of the periodic table represented by Cd.

  Among the above organometallic compounds (b-1), organoaluminum compounds such as triethylaluminum, triisobutylaluminum, and tri-n-octylaluminum are preferable. Moreover, these organometallic compounds (b-1) may be used individually by 1 type, and may be used in combination of 2 or more type.

(B-2) Organoaluminum oxy compound The organoaluminum oxy compound (b-2) used in the production of the copolymer (B) may be a conventionally known aluminoxane, and disclosed in JP-A-2-78687. It may be a benzene-insoluble organoaluminum oxy compound as exemplified. An organoaluminum oxy compound (b-2) may be used individually by 1 type, and may be used in combination of 2 or more type.

(B-3) Ionized ionic compound As the ionized ionic compound (b-3) used for the production of the copolymer (B), JP-A-1-501950, JP-A-1-503636, Lewis acids, ionic compounds, borane compounds and carboranes described in JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321106 and the like. A compound etc. can be mentioned. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

  Among the ionized ionic compounds (b-3), triphenylcarbenium tetrakis (pentafluorophenyl) borate and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate are preferable. An ionized ionic compound (b-3) may be used individually by 1 type, and may be used in combination of 2 or more type.

  When the bridged metallocene compound (a) is used as a catalyst, an organometallic compound (b-1) such as triisobutylaluminum, an organoaluminum oxy compound (b-2) such as methylaluminoxane, or triphenylcarbenium tetrakis (pentafluorophenyl). ) When an ionized ionic compound (b-3) such as borate is used in combination, a very high polymerization activity is exhibited in the production of the copolymer (B).

≪Carrier (c) ≫
The carrier (c) is an inorganic compound or an organic compound and is a granular or particulate solid.

Among the above inorganic compounds, porous oxides, inorganic halides, clays, clay minerals or ion-exchangeable layered compounds are preferable.
Examples of the porous oxide include inorganic oxides such as SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, and ThO ₂ , or composites containing these inorganic oxides. or mixtures porous material is the main component, which, as the porous oxide, specifically, natural or synthetic _{zeolites; SiO 2 -MgO, SiO 2 -Al} 2 O 3, SiO 2 -TiO 2, Examples thereof include porous oxides mainly composed of SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO ₂ —TiO ₂ —MgO. Of these, porous oxides mainly composed of SiO ₂ and / or Al ₂ O ₃ are preferred. Such porous oxides have different properties depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of usually 50 to 1000 m ² / g, preferably in the range of 100~700m ² / g, it is desirable that the pore volume is in the range of 0.3~3.0cm ³ / g. Such a carrier is used after calcining at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

Examples of the inorganic halide include MgCl ₂ , MgBr ₂ , MnCl ₂ , and MnBr ₂ . The inorganic halide may be used as it is or after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a material in which an inorganic halide is dissolved in a solvent such as alcohol and then precipitated into fine particles with a precipitating agent.

  The clay used as the carrier (c) is usually composed mainly of a clay mineral. The ion-exchangeable layered compound used in the present invention is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other with a weak binding force, and the contained ions can be exchanged. . Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used.

Further, as clay, clay mineral, or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal close packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. Can be mentioned.

  Examples of clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, unmo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite, halloysite, etc. Is mentioned.

Examples of the ion-exchange layered compound include α-Zr (HAsO ₄ ) ₂ .H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ .3H ₂ O, α-Ti (HPO ₄ ). ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti ( Examples thereof include crystalline acidic salts of polyvalent metals such as NH ₄ PO ₄ ) ₂ .H ₂ O.

  Such a clay, clay mineral, or ion-exchange layered compound preferably has a pore volume of 0.1 cc / g or more and a diameter of 0.3 to 5 cc / g measured by mercury porosimetry. Particularly preferred. Here, the pore volume is measured in a range of pore radius of 20 to 30000 mm by mercury porosimetry using a mercury porosimeter.

When a carrier having a pore volume with a radius of 20 mm or more and smaller than 0.1 cc / g is used as a carrier, high polymerization activity tends to be difficult to obtain.
It is also preferable to subject the clay and clay mineral used as the carrier (c) to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic matter treatment, an ion complex, a molecular complex, an organic derivative, and the like can be formed, and the surface area and interlayer distance can be changed.

The ion-exchangeable layered compound used as the carrier (c) is a layered compound in which the layers are expanded by exchanging the exchangeable ions between the layers with other large and bulky ions using the ion-exchange property. May be. Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ ; metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) ₃ ( R is a hydrocarbon group), metal hydroxides such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , and [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ And ions. These compounds can be used alone or in combination of two or more. Further, when these compounds were intercalated, they were obtained by hydrolyzing metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.). Polymers, colloidal inorganic compounds such as SiO _2, and the like can also coexist. Examples of the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers.

  The clay, clay mineral, and ion-exchange layered compound may be used as they are, or may be used after a treatment such as ball milling or sieving. Further, it may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. These substances to be the carrier (c) may be used alone or in combination of two or more.

Among these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, hectorite, teniolite and synthetic mica.
Examples of the organic compound include granular or fine particle solids having a particle size in the range of 10 to 300 μm. Specifically, a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, styrene. (Co) polymers produced by the main component, and their modified products.

<< Production of Copolymer (B) >>
When ethylene, an α-olefin, and a non-conjugated polyene are copolymerized, the usage and order of addition of each component constituting the polymerization catalyst are arbitrarily selected, and the following methods are exemplified.
(1) A method of adding the compound (a) alone to a polymerization vessel.
(2) A method of adding the compound (a) and the compound (b) to the polymerization vessel in an arbitrary order.
(3) A method in which the catalyst component carrying the compound (a) on the carrier (c) and the compound (b) are added to the polymerization vessel in any order.
(4) A method in which the catalyst component carrying the compound (b) on the carrier (c) and the compound (a) are added to the polymerization vessel in any order.
(5) A method in which a catalyst component in which the compound (a) and the compound (b) are supported on the carrier (c) is added to a polymerization vessel.

In each of the above methods (2) to (5), at least two of the compound (a), the compound (b) and the carrier (c) may be contacted in advance.
In the above methods (4) and (5) in which the compound (b) is supported, the unsupported compound (b) may be added in any order as necessary. In this case, the compound (b) may be the same as or different from the compound (b) supported on the carrier (c).

  The solid catalyst component in which the compound (a) is supported on the carrier (c) and the solid catalyst component in which the compound (a) and the compound (b) are supported on the carrier (c) are prepolymerized with olefin. Alternatively, a catalyst component may be further supported on the prepolymerized solid catalyst component.

The copolymer (B) can be produced by either a liquid phase polymerization method such as solution (dissolution) polymerization or suspension polymerization, or a gas phase polymerization method.
Examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; fats such as cyclopentane, cyclohexane, and methylcyclopentane. Cyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane. The said inert hydrocarbon medium may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, olefin itself can also be used as a solvent.

In the polymerization of ethylene or the like using the copolymer catalyst as described above, the crosslinked metallocene compound (a) is usually 10 ⁻¹² to 10 ⁻² mol, preferably 10 ⁻¹⁰ , per liter of reaction volume. It is used in such an amount that it becomes -10 ^-8 mol.

  In the organometallic compound (b-1), the molar ratio [(b-1) / M] of the compound (b-1) and all transition metal atoms (M) in the bridged metallocene compound (a) is usually 0. 0.01 to 50000, preferably 0.05 to 10,000. The organic aluminum oxy compound (b-2) has a molar ratio [(b-2) / M] of the aluminum atom in the compound (b-2) and the total transition metal (M) in the compound (a). The amount is usually 10 to 50000, preferably 20 to 10000. In the ionized ionic compound (b-3), the molar ratio [(b-3) / M] of the compound (b-3) and the transition metal atom (M) in the compound (a) is usually 1-20. The amount is preferably 1 to 15.

The polymerization temperature of the copolymer (B) is usually −50 to + 200 ° C., preferably 0 to + 200 ° C., more preferably +80 to + 200 ° C.
Depending on the target molecular weight to be reached and the polymerization activity of the catalyst used, the polymerization temperature is preferably higher (+ 80 ° C. or higher) from the viewpoint of productivity.

  The polymerization pressure of the copolymer (B) is usually in the range of normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure. The polymerization reaction mode of the copolymer (B) may be any of batch type, semi-continuous type, and continuous type. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.

  The molecular weight of the obtained copolymer (B) can be adjusted, for example, by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. When the molecular weight is adjusted to allow hydrogen to be present in the polymerization system, the amount of hydrogen added is suitably about 0.001 to 100 NL per kg of olefin. Moreover, when using a compound (b) (for example, triisobutylaluminum, methylaluminoxane, diethylzinc etc.) as a catalyst component, the molecular weight of a copolymer can be adjusted with the usage-amount of a compound (b).

<Phenolic resin crosslinking agent (C)>
Examples of the phenol resin crosslinking agent (C) (hereinafter also referred to as “crosslinking agent (C)”) include halogenated phenol resin crosslinking agents.

  The crosslinking agent (C) is a resole resin, which is produced by condensation of an alkyl-substituted phenol or unsubstituted phenol with an aldehyde in an alkaline medium, preferably with formaldehyde, or with a bifunctional phenol dialcohol. It is also preferable. The alkyl-substituted phenol is preferably an alkyl group-substituted product having 1 to 10 carbon atoms. Furthermore, dimethylolphenols or phenol resins substituted with an alkyl group having 1 to 10 carbon atoms in the p-position are preferred. The phenolic resin-based cured resin is typically a heat-crosslinkable resin and is also called a phenolic resin-based crosslinking agent or a phenol resin.

  Examples of the phenol resin-based cured resin (phenol resin-based cross-linking agent) include the following general formula (I).

In formula (I), Q is a divalent group selected from the group consisting of —CH ₂ — and —CH ₂ —O—CH ₂ —, m is 0 or a positive integer of 1 to 20, R ′ is an organic group.

Preferably, Q is a divalent group —CH ₂ —O—CH ₂ —, m is 0 or a positive integer from 1 to 10, and R ′ is an organic group having less than 20 carbon atoms. More preferably, m is 0 or a positive integer of 1 to 5, and R ′ is an organic group having 4 to 12 carbon atoms. Specific examples include alkylphenol formaldehyde resins, methylolated alkylphenol resins, halogenated alkylphenol resins, and the like, preferably halogenated alkylphenol resins, and more preferably brominated terminal hydroxyl groups. In the phenol resin-based cured resin, an example in which the terminal is brominated is shown in the following general formula (II).

In formula (II), n is an integer of 0 to 10, and R is a saturated hydrocarbon group having 1 to 15 carbon atoms.

  Examples of products of the above-mentioned phenol resin-based cured resin include tackolol (registered trademark) 201 (alkylphenol formaldehyde resin, manufactured by Taoka Chemical Co., Ltd.), tackirol (registered trademark) 250-I (bromination with a bromination rate of 4%). Alkylphenol formaldehyde resin, manufactured by Taoka Chemical Industry Co., Ltd.), Tactrol (registered trademark) 250-III (brominated alkylphenol formaldehyde resin, manufactured by Taoka Chemical Industry Co., Ltd.), PR-4507 (Gunei Chemical Industry Co., Ltd.) Vulkaresat 510E (manufactured by Hoechst), Vulcaresat 532E (manufactured by Hoechst), Vulkaresen E (manufactured by Hoechst), Vulkaresen 105E (manufactured by Hoechst), Vulkarensen 130E (Hoechs) Vulcaresol 315E (Hoechst), Amberol ST 137X (Rohm & Haas), Sumilite Resin (registered trademark) PR-22193 (Sumitomo Dures Co., Ltd.), Symphor-C-100 (Anchor Chem.) ), Symform-C-1001 (manufactured by Anchor Chem.), Tamanol (registered trademark) 531 (manufactured by Arakawa Chemical Co., Ltd.), Scientady SP1059 (manufactured by Schematy Chem.), And Scientady SP1045 (SchematyChem.) , CRR-0803 (manufactured by U.C.C.), Schenectady SP1055F (manufactured by Schenectady Chem., Brominated alkylphenol formaldehyde) Hydride resin), Spectady SP1056 (manufactured by SCHENCYDY Chem.), CRM-0803 (manufactured by Showa Union Synthesis Co., Ltd.), and Vulkadur A (manufactured by Bayer). Among these, a halogenated phenol resin-based crosslinking agent is preferable, and brominated alkylphenol / formaldehyde resins such as Taccolol (registered trademark) 250-I, Taccolol (registered trademark) 250-III, and Schenectady SP1055F can be more preferably used.

  Specific examples of the crosslinking of thermoplastic vulcanizates with phenolic resins include US Pat. No. 4,311,628, US Pat. No. 2,972,600 and US Pat. No. 3,287,440. These techniques are also described and can be used in the present invention.

U.S. Pat. No. 4,311,628 discloses a phenolic curative system consisting of a phenolic curing resin and a cure activator. The basic component of the system is the condensation of substituted phenols (eg halogen-substituted phenols, C ₁ -C ₂ alkyl-substituted phenols) or unsubstituted phenols with aldehydes, preferably formaldehyde, in an alkaline medium, or bifunctional phenols dialcohols (preferably, the para position is C ₅ -C ₁₀ alkyl dimethylol phenols substituted in the group) is a phenol resin-based crosslinking agent produced by condensation of. Particularly suitable are halogenated alkyl-substituted phenolic resin crosslinking agents prepared by halogenation of alkyl-substituted phenolic resin crosslinking agents. A phenolic resin-based crosslinking agent comprising a methylolphenol curable resin, a halogen donor and a metal compound can be particularly recommended, and details thereof are described in US Pat. Nos. 3,287,440 and 3,709,840. Has been. Non-halogenated phenolic resin-based crosslinkers are used simultaneously with the halogen donor, preferably with a hydrogen halide scavenger. Usually, halogenated phenolic resin-based crosslinking agents, preferably brominated phenolic resin-based crosslinking agents containing 2 to 10% by weight of bromine, do not require halogen donors, for example iron oxide, titanium oxide, oxidation Used simultaneously with a hydrogen halide scavenger such as a metal oxide such as magnesium, magnesium silicate, silicon dioxide and zinc oxide, preferably zinc oxide. These hydrogen halide scavengers such as zinc oxide are usually used in an amount of 1 to 20 parts by weight with respect to 100 parts by weight of the phenol resin crosslinking agent. The presence of such a scavenger promotes the crosslinking action of the phenol resin-based crosslinking agent, but it is desirable to share a halogen donor and zinc oxide in the case of rubber that is not easily vulcanized with the phenol resin-based crosslinking agent. The preparation of halogenated phenolic curable resins and their use in vulcanizing systems using zinc oxide are described in US Pat. Nos. 2,972,600 and 3,093,613. , The disclosure of which is incorporated herein by reference in conjunction with the disclosure of the aforementioned US Pat. Nos. 3,287,440 and 3,709,840. Examples of suitable halogen donors include stannous chloride, ferric chloride, or halogen donating heavys such as chlorinated paraffin, chlorinated polyethylene, chlorosulfonated polyethylene and polychlorobutadiene (neoprene rubber). Coalescence is mentioned. As used herein, the term “vulcanization accelerator” refers to any substance that substantially increases the crosslinking efficiency of a phenolic resin-based crosslinking agent, and includes metal oxides and halogen donors, which are Used alone or in combination. For more details on phenolic vulcanizing systems, see “Vulcanization and Vulcanizing Agents” (W. Hoffman, Palmerton Publishing Company). Suitable phenolic resin-based crosslinkers and brominated phenolic resin-based crosslinkers are commercially available, for example such crosslinkers are available from Schenectady Chemicals, Inc. under the trade names “SP-1045”, “CRJ-352”, It can be purchased as “SP-1055F” and “SP-1056”. Similar functionally equivalent phenolic resin crosslinkers can also be obtained from other suppliers.

  The crosslinking agent (C) is a suitable vulcanizing agent from the viewpoint of preventing fogging because it hardly generates decomposition products. Crosslinker (C) is used in an amount sufficient to achieve essentially complete vulcanization of the rubber.

  In the present invention, during dynamic crosslinking with the crosslinking agent (C), sulfur, p-quinonedioxime, p, p′-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, Peroxy crosslinking aids such as diphenylguanidine, trimethylolpropane-N, N'-m-phenylenedimaleimide, divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane Auxiliaries such as polyfunctional methacrylate monomers such as trimethacrylate and allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate can be blended.

  By using the auxiliary agent, a uniform and gentle crosslinking reaction can be expected. As the auxiliary agent, divinylbenzene is preferable. Divinylbenzene is easy to handle, has good compatibility with the polymer (A) and the copolymer (B), and has an action of solubilizing the crosslinking agent (C). Since it acts as a dispersant, a thermoplastic elastomer composition having a uniform crosslinking effect by heat treatment and having a balance between fluidity and physical properties can be obtained.

The auxiliary agent is used in an amount of usually 2 parts by weight or less, preferably 0.3 to 1 part by weight, based on 100 parts by weight of the copolymer (B).
Moreover, in order to accelerate | stimulate decomposition | disassembly of a crosslinking agent (C), you may use a dispersion | distribution promoter. As the decomposition accelerator, tertiary amines such as triethylamine, tributylamine, 2,4,6-tri (dimethylamino) phenol;
Naphthenic acid and various metals (for example, Pb, Co, Mn, Ca, Cu, Ni, Fe, Zn, rare earth) such as aluminum, cobalt, vanadium, copper, calcium, zirconium, manganese, magnesium, lead, mercury Examples thereof include naphthenate.

  In the composition (I) of the present invention, the crosslinking agent (C) is usually 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight with respect to 100 parts by weight of the copolymer (B). Used in quantity. By setting the blending amount of the crosslinking agent (C) within the above range, a composition having excellent moldability can be obtained, and the obtained molded body has high strength, excellent oil resistance, and sufficient Has heat resistance and mechanical properties.

<Other ingredients>
In addition to the polymer (A), the copolymer (B) and the cross-linking agent (C), the composition (I) of the present invention may contain additives as long as the effects of the present invention are not impaired. Good. Although it does not specifically limit as an additive, A softener (D), an inorganic filler (E), etc. are mentioned. Examples of additives include rubbers other than the copolymer (B) (for example, polyisobutylene, butyl rubber, propylene / ethylene copolymer rubber, propylene / butene copolymer rubber, and propylene / butene / ethylene copolymer rubber). Styrene such as ethylene propylene elastomer, ethylene elastomer such as ethylene / propylene copolymer rubber, styrene / butadiene / styrene block polymer, styrene / isoprene / styrene block polymer, styrene / isobutylene / styrene block polymer and hydrogenated products thereof Elastomers); resins other than thermosetting resins and crystalline olefin polymers (A); UV absorbers; antioxidants; heat stabilizers; anti-aging agents; light stabilizers, weather stabilizers; Inhibitor; Metal soap Aliphatic amides; lubricants such as such as waxes, known additives used in the field of polyolefins.
These additives may be used individually by 1 type, respectively, and may be used in combination of 2 or more type.

  Further, the amount of additives other than those specifically mentioned in the present specification is not particularly limited as long as the effects of the present invention are exhibited, but the total of the polymer (A) and the copolymer (B). The amount is usually about 0.0001 to 10 parts by weight, preferably about 0.01 to 5 parts by weight with respect to 100 parts by weight.

  As the softening agent (D), a softening agent usually used for rubber can be used. As the softening agent (D), petroleum-based softening agents such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt and petroleum jelly; coal tar-based softening agents such as coal tar and coal tar pitch; castor oil and linseed oil Oil oil softeners such as rapeseed oil, soybean oil, coconut oil; tall oil; sub (factis); waxes such as beeswax, carnauba wax, lanolin; ricinoleic acid, palmitic acid, stearic acid, barium stearate, stear Fatty acids or fatty acid salts such as calcium phosphate and zinc laurate; naphthenic acid; pine oil, rosin or derivatives thereof; synthetic polymer substances such as terpene resin, petroleum resin, atactic polypropylene, coumarone indene resin; dioctyl phthalate, dioctyl adipate, Esters such as dioctyl sebacate Agent; microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, liquid Thiokol, and a hydrocarbon-based synthetic lubricating oils.

  The softening agent (D) is not particularly limited as long as the effect of the present invention is exhibited, but it is usually 2 to 100 parts by weight, preferably 5 with respect to 100 parts by weight of the total of the polymer (A) and the copolymer (B). Used in an amount of ˜80 parts by weight. When the softening agent (D) is used in such an amount, the fluidity at the time of preparation and molding of the thermoplastic elastomer composition is excellent, the dispersibility of carbon black and the like is improved, and the mechanical properties of the resulting molded body are improved. It is difficult to lower, and the obtained molded article is excellent in heat resistance and heat aging resistance.

  As inorganic filler (E), calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, disulfide Examples include molybdenum, graphite, carbon black, glass fiber, glass sphere, shirasu balloon, basic magnesium sulfate whisker, calcium titanate whisker, and aluminum borate whisker.

These inorganic fillers (E) are usually 1 to 100 parts by weight, preferably 1 to 50 parts by weight, based on 100 parts by weight of the total amount of the polymer (A) and the copolymer (B). Used.
When a rubber other than the copolymer (B) is used, the rubber is usually 2 to 200 parts by weight with respect to 100 parts by weight of the total amount of the polymer (A) and the copolymer (B). Preferably, it is used in an amount of 5 to 150 parts by weight.

[Dynamic cross-linked thermoplastic elastomer]
The dynamically crosslinked thermoplastic elastomer of the present invention (hereinafter also referred to as “composition (II)”) is obtained by dynamically crosslinking the thermoplastic elastomer composition (I). More specifically, the composition (II) comprises a polymer (A), a copolymer (B), and a mixture containing additives that are blended as necessary, a crosslinking agent, preferably a crosslinking agent (C). Is obtained by dynamically heat-treating and crosslinking (dynamic crosslinking).

  A composition that is lightweight and high in strength, has excellent oil resistance, and has excellent mechanical properties only by dynamically crosslinking the polymer (A) and the copolymer (B) with a crosslinking agent. (II) is obtained.

  In the present invention, “dynamically heat-treating” refers to kneading the mixture in a molten state in the presence of a crosslinking agent. “Dynamic crosslinking” refers to crosslinking while applying a shearing force to the mixture.

The composition (II) may be a composition in which the polymer components including the polymer (A) and the copolymer (B) are partially crosslinked, or may be a completely crosslinked composition. Good.
The dynamic heat treatment is preferably performed in a non-open type apparatus, and is preferably performed in an inert gas atmosphere such as nitrogen or carbon dioxide. The temperature of the heat treatment is usually in the range of the melting point of the polymer (A) to 300 ° C, preferably 150 to 280 ° C, more preferably 170 to 270 ° C. The kneading time is usually 1 to 20 minutes, preferably 1 to 10 minutes. Further, the shear force applied is typically 10～100,000Sec ^-1 at the highest shear rate, preferably 100～50,000Sec ^-1, more preferably 1,000～10,000Sec ^-1, more preferably 2,000 It is in the range of ˜7,000 sec ⁻¹ .

  Examples of the kneading apparatus for kneading include a mixing roll, an intensive mixer (for example, a Banbury mixer, a kneader), a single screw extruder, a twin screw extruder, and the like. These kneading devices are preferably non-open type devices.

Since the composition (II) of the present invention has hardness and mechanical properties (tensile strength, elongation, etc.) equal to or higher than those of conventional cross-linked thermoplastic elastomers, it can be used in various applications. Further, since the composition (II) of the present invention has excellent oil resistance as compared with conventional cross-linked thermoplastic elastomers, it is particularly difficult to use conventional cross-linked thermoplastic elastomers, For example, it can be suitably used for automobile parts such as hoses, pipes and boots (blow-molded products) for automobiles that require superior oil resistance because they come into contact with grease or lubricating oil.
The composition (II) of the present invention is excellent in lightness, heat resistance, flexibility, rubber elasticity, weather resistance, and compatibility.

  Moreover, since the composition (II) of the present invention is excellent in molding processability, it can be molded by various molding methods. Examples of the molding include extrusion molding, injection molding, compression molding, calendar molding, vacuum molding, press molding, stamping molding, and blow molding. Examples of blow molding include breath blow molding, direct blow molding, injection blow molding, and the like.

[Molded body]
The molded product of the present invention can be obtained by molding the composition (II) of the present invention. For example, it can be obtained by molding the composition (I) or (IIC) by a conventional plastic molding method such as extrusion molding, injection molding or compression molding. In addition, scraps and burrs generated by such a molding method can be recovered and reused.

  Examples of the molded body of the present invention include bumper parts, body panels, side shields, glass run channels, instrument panel skins, door skins, ceiling skins, weatherstrip materials, hoses, steering wheels, boots, wire harness covers, seat adjuster covers. Automotive parts such as electric wire coverings, connectors, cap plugs, etc .; footwear such as shoe soles and sandals; leisure items such as swimming fins, underwater glasses, golf club grips, baseball bat grips, gaskets, waterproof cloth, Belts, garden hoses; various civil engineering and architectural gaskets and sheets. The molded body is particularly suitable for applications requiring oil resistance, and automotive parts such as automobile hoses, boots, wire harness covers, and sheet adjuster covers are particularly preferred applications.

As described above, an automobile part is preferable as the molded body, and more detailed examples of the automobile part include a mechanism member, an interior member, an exterior member, and other members.
Mechanical members include CVJ boots, suspension boots, rack and pinion boots, steering rod covers, AT cushions, AT slide covers, leaf spring bushes, ball joint retainers, timing belts, V belts, engine room hoses, air ducts, air Examples include a bag cover and a propeller shaft cover material.

  Interior materials include various skin materials (instrumental panel, door trim, ceiling, rear pillar), console box, armrest, airbag case lid, shift knob, assist grip, side step mat, reclining cover, trunk seat, seat belt buckle, Examples include lever slide plates, door latch strikers, seat belt parts, and switches.

  As exterior members, various molding materials (inner / outer window moldings, roof moldings, belt moldings, side trim moldings), door seals, body seals, glass run channels, mudguards, kicking plates, step mats, number plate housings, silencer gears , Control cable covers and emblems.

  Other members include air duct packing, air duct hose, air duct cover, air intake pipe, air dam skirt, timing belt cover seal, opening seal / trunk seal member, bonnet cushion, fuel tank band, cable and the like.

  The molded article of the present invention may be sundries, daily necessities, or these members. Miscellaneous goods, daily necessities or these components include grips (eg, ballpoint pens, mechanical pencils, toothbrushes, cups, disposable razors, handrails, cutters, power tools, screwdrivers, power cables, door grips), assist grips, shift knobs, toys , Notebook skins, gaskets (for example, gaskets for tableware, tappers, etc.), various rubber feet, sports equipment (for example, sheathed soles, ski boots, skis, ski bindings, ski soles, golf balls, goggles members, snowboard members, snowboard shoes) , Snowboard bindings, surfboard members, body boards, banana boats, kiteboards, snorkeling members, water ski members, parasailing members, wakeboard members and other sports equipment), belts (examples) If, belts and watches belt, fashion belt), hairbrush, bath panel button sheet, cap, shoes of the inner sole, and the like health equipment member.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples at all. In the following, “part” means “part by weight” or “part by mass” unless otherwise specified. In the present invention, parts by weight and parts by mass are treated synonymously.

[Synthesis of transition metal compounds]
Synthesis of [bis (4-methoxyphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride (catalyst-a1) (i) 6 Synthesis of 1,6-bis (4-methoxyphenyl) fulvene Under a nitrogen atmosphere, 8.28 g (115 mmol) of lithium cyclopentadienide and 200 ml of dehydrated THF (tetrahydrofuran) were added to a 500 ml three-necked flask. While cooling in an ice bath, 13.6 g (119 mmol) of DMI (1,3-dimethyl-2-imidazolidinone) was added and stirred at room temperature for 30 minutes. Thereafter, 25.3 g (105 mol) of 4,4′-dimethoxybenzophenone was added, and the mixture was stirred for 1 week under heating under reflux. While cooling in an ice bath, 100 ml of water was gradually added, and further 200 ml of dichloromethane was added and stirred at room temperature for 30 minutes. The resulting bilayer solution was transferred to a 500 ml separatory funnel and the organic layer was washed 3 times with 200 ml of water. After drying over anhydrous magnesium sulfate for 30 minutes, the solvent was distilled off under reduced pressure to obtain an orange brown solid. Separation by silica gel chromatography (700 g, hexane: ethyl acetate = 4: 1) was performed to obtain a red solution. The solvent was distilled off under reduced pressure to obtain 9.32 g (32.1 mmol, 30.7%) of 6,6-bis (4-methoxyphenyl) fulvene as an orange solid. Identification of 6,6-bis (4-methoxyphenyl) fulvene was performed by ¹ H-NMR spectrum. The measured values are shown below.
¹ H-NMR spectrum (270 MHz, CDCl ₃ ): δ / ppm 7.28-7.23 (m, 4H), 6.92-6.87 (m, 4H), 6.59-6.57 (m , 2H), 6.30-6.28 (m, 2H), 3.84 (s, 6H)

(Ii) Synthesis of bis (4-methoxyphenyl) (cyclopentadienyl) (2,3,6,7-tetramethylfluorenyl) methane In a nitrogen atmosphere, 2,3,6,7- Tetramethylfluorene 500 mg (2.25 mmol) and dehydrated t-butyl methyl ether 40 ml were added. While cooling in an ice bath, 1.45 ml (2.36 mmol) of n-butyllithium / hexane solution (1.63 M) was gradually added, and the mixture was stirred at room temperature for 18 hours. After adding 691-bis (4-methoxyphenyl) fulvene (591 mg, 2.03 mmol), the mixture was heated to reflux for 3 days. While cooling in an ice bath, 50 ml of water was gradually added, and the resulting solution was transferred to a 300 ml separatory funnel. After adding 50 ml of dichloromethane and shaking several times, the aqueous layer was separated, and the organic layer was washed 3 times with 50 ml of water. After drying over anhydrous magnesium sulfate for 30 minutes, the solvent was distilled off under reduced pressure. The obtained solid was washed with a small amount of diethyl ether to obtain a white solid. Further, the solvent of the washing solution was distilled off under reduced pressure, and the obtained solid was washed with a small amount of diethyl ether to collect a white solid, which was combined with the previously obtained white solid. The solid was dried under reduced pressure and 793 mg (1.55 mmol, 76.0%) bis (4-methoxyphenyl) (cyclopentadienyl) (2,3,6,7-tetramethylfluorenyl) methane was added. Obtained. Bis (4-methoxyphenyl) (cyclopentadienyl) (2,3,6,7-tetramethylfluorenyl) methane was identified by FD-MS spectrum. The measured values are shown below.
FD-MS spectrum: M / z 512 (M ⁺ )

(Iii) Synthesis of [bis (4-methoxyphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride 100 ml Schlenk under nitrogen atmosphere Pipe bis (4-methoxyphenyl) (cyclopentadienyl) (2,3,6,7-tetramethylfluorenyl) methane 272 mg (0.531 mmol), dehydrated toluene 20 ml and THF 90 μl (1.1 mmol) Added. While cooling in an ice bath, 0.68 ml (1.1 mmol) of n-butyllithium / hexane solution (1.63M) was gradually added and stirred at 45 ° C. for 5 hours to obtain a red solution. The solvent was distilled off under reduced pressure, and 20 ml of dehydrated diethyl ether was added to make a red solution again. 164 mg (0.511 mmol) of hafnium tetrachloride was added while cooling in a methanol / dry ice bath, and the mixture was stirred for 16 hours while gradually warming to room temperature, whereby a yellow slurry was obtained. The solid obtained by distilling off the solvent under reduced pressure was brought into a glove box, washed with hexane, and extracted with dichloromethane. The solid obtained by distilling off the solvent under reduced pressure was dissolved in a small amount of dichloromethane, hexane was added, and recrystallization was carried out at -20 ° C. The precipitated solid was collected, washed with hexane, and dried under reduced pressure to give [bis (4-methoxyphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2, ^3, 6 as a yellow solid. , 7-tetramethylfluorenyl)] hafnium dichloride (275 mg, 0.362 mmol, 70.8%). [Bis (4-methoxyphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] Hafnium dichloride was identified by ¹ H-NMR spectrum and FD- The MS spectrum was used. The measured values are shown below.
¹ H-NMR spectrum (270 MHz, CDCl ₃ ): δ / ppm 7.87 (s, 2H), 7.80-7.66 (m, 4H), 6.94-6.83 (m, 4H), 6.24 (t, J = 2.6 Hz, 2H), 6.15 (s, 2H), 5.65 (t, J = 2.6 Hz, 2H), 3.80 (s, 6H), 2. 47 (s, 6H), 2.05 (s, 6H)
FD-MS spectrum: M / z 760 (M ⁺ )
The chemical formula of the obtained catalyst-a1 is shown below.

[Synthesis Example 1]
The polymerization reaction of ethylene, 1-butene, and 5-ethylidene-2-norbornene (ENB) was continuously carried out at 95 ° C. using a 300 L polymerization vessel equipped with a stirring blade.

  Using hexane (feed amount: 33 L / h) as a polymerization solvent, ethylene feed amount is continuously 3.4 kg / h, 1-butene feed amount is 11.0 kg / h, ENB feed amount is 450 g. / H and hydrogen were continuously fed to the polymerization vessel so that the feed amount was 0.2 NL / h.

While maintaining the polymerization pressure at 1.6 MPaG and the polymerization temperature at 95 ° C., the catalyst-a1 as a main catalyst was continuously supplied to the polymerization vessel so that the feed amount was 0.020 mmol / h. Further, as co-catalysts, (C ₆ H ₅ ) ₃ CB (C ₆ F ₅ ) ₄ was fed in a polymerizer so that the feed amount was 0.10 mmol / h and triisobutylaluminum (TIBA) was fed in a feed amount of 10 mmol / h. Continuously fed.

  Thus, a solution containing 13% by mass of an ethylene / 1-butene / ENB copolymer formed from ethylene, 1-butene and ENB was obtained. A small amount of methanol was added to the polymerization reaction liquid extracted from the lower part of the polymerization vessel to stop the polymerization reaction, and the ethylene / 1-butene / ENB copolymer was separated from the solvent by steam stripping treatment, and then at 80 ° C. It was dried under reduced pressure all day and night.

  By the above operation, an ethylene / 1-butene / ENB copolymer (EBDM-1) formed from ethylene, 1-butene and ENB was obtained at a rate of 5.0 kg / hour. The physical properties of the obtained EBDM-1 were measured by the method described later. The results are shown in Table 1.

[Measurement method of physical properties]
<Composition of copolymer>
The molar amount and mass of the structural unit derived from ethylene, the structural unit derived from α-olefin having 4 to 20 carbon atoms, and the structural unit derived from non-conjugated polyene were determined by intensity measurement using a ¹ H-NMR spectrometer.

<Iodine number>
The iodine value of the copolymer was determined by a titration method. Specifically, 0.5 g of the obtained copolymer was dissolved in 60 ml of carbon tetrachloride, a small amount of a Wis reagent and a 20% potassium iodide solution were added, and it was determined with a 0.1 mol / L sodium thiosulfate solution. . In the vicinity of the end point, a starch indicator was added, and the mixture was well-stirred until the light purple color disappeared, and the number of g of iodine consumed was calculated as the amount of halogen consumed per 100 g of the sample.

<B value>
A ¹³ C-NMR spectrum (100 MHz, JEOL ECX400P) was measured at a measurement temperature of 120 ° C. using o-dichlorobenzene-d ₄ / benzene-d ₆ (4/1 [v / v]) as a measurement solvent. The B value of the copolymer was calculated based on the following formula (i).
B value = ([EX] +2 [Y]) / [2 × [E] × ([X] + [Y])] (i)

  Here, [E], [X], and [Y] represent the mole fraction of the structural unit derived from ethylene, the structural unit derived from α-olefin having 4 to 20 carbon atoms, and the structural unit derived from non-conjugated polyene, respectively. , [EX] represents the dyad chain fraction of the structural unit derived from ethylene-the structural unit derived from an α-olefin having 4 to 20 carbon atoms.

<Mooney viscosity>
Mooney viscosity ML _{(1 + 4)} 125 ° C. and Mooney viscosity ML _{(1 + 4)} 150 ° C. were measured according to JIS K6300 (1994) using a Mooney viscometer (SMV202 type manufactured by Shimadzu Corporation). .

<Intrinsic viscosity>
The intrinsic viscosity [η] of the copolymer is a value measured at 135 ° C. using a decalin solvent. Specifically, about 20 mg of the copolymer was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to the decalin solution for dilution, the specific viscosity ηsp was measured in the same manner. This dilution operation was further repeated twice, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity (see the following formula).
[Η] = lim (ηsp / C) (C → 0) ”

[Example 1]
Using a lab plast mill manufactured by Toyo Seiki Seisakusho [model: R-100H, capacity: about 100 cc (effective kneading volume: 80 cc)], the kneading temperature was set to 170 ° C., and EBDM-1 obtained in Synthesis Example 1 was obtained. 100 parts by weight of polypropylene (trade name: Prime Polypro (trademark) E-200GP, prime polymer) having a melt flow rate (ASTM-D-1238-65T; 230 ° C., 2.16 kg load) of 2.0 g / 10 min 71 parts by weight) was added at a rotation speed of 10 rpm. Subsequently, the number of revolutions was rapidly increased from 10 rpm (10 seconds) → 30 rpm (10 seconds) → 50 rpm (10 seconds) → 70 rpm (10 seconds) → 90 rpm (10 seconds), and this was repeated three sets. Next, 114 parts of a softening agent (Diana Process PW-100, paraffin oil, manufactured by Idemitsu Kosan Co., Ltd.) was added dropwise little by little at a rotation speed of 10 rpm so that the rotor did not idle. The number of revolutions was rapidly increased from 10 rpm → 30 rpm → 50 rpm → 70 rpm → 90 rpm, then the number of revolutions was set to 10 rpm, and the resin temperature was lowered to 170 ° C. Next, 8 parts of brominated alkylphenol / formaldehyde resin (trade name: SP-1055F, manufactured by Schenectady) and 0.5 part of zinc oxide (2 types of zinc oxide, manufactured by Hakusuitec Co., Ltd.) were added as a phenolic resin-based crosslinking agent. Thereafter, the number of revolutions was rapidly increased from 10 rpm → 30 rpm → 50 rpm → 70 rpm → 90 rpm. Kneading was performed at 90 rpm for 3 minutes after the torque reached the peak. Through the above operation, a dynamically crosslinked thermoplastic elastomer (hereinafter also referred to as “composition (II-1)”) was obtained.

  The obtained composition (II-1) was pre-pressed at 190 ° C. for 6 minutes using a 50-ton electric heating semi-automatic press (“KMF100-1E” manufactured by Kotaki Co., Ltd.). The sheet was cooled and pressed for 5 minutes to prepare a press sheet having a thickness of 2 mm. Evaluation was performed by the following method using the obtained composition (II-1) and sheet. The results are shown in Table 2.

[Evaluation method]
<MFR>
Using the obtained composition (II-1), measurement was performed at 230 ° C. under a load of 10 kg in accordance with ASTM D 1238.

<Hardness>
The 2 mm-thick sheets obtained above were stacked to a thickness of 12 mm, and the hardness (JIS-A) was measured according to JIS K6253.

<Tensile test>
Using the sheet obtained above, according to JIS K6251, a tensile test was performed under the conditions of a measurement temperature of 23 ° C. and a tensile speed of 500 mm / min, and the modulus, strength at break (TB), and elongation at break (EB) were measured.

<Compression set (CS)>
Using the sheet obtained above, the compression set after treatment for 22 hours at a predetermined temperature was measured in accordance with JIS K6262 (2013) according to JIS K6250 6.5.

<Oil resistance (volume change rate)>
Using the sheet obtained above, according to JIS K6258, IRM903 was used as a test lubricating oil, and the volume change rate after the treatment at a predetermined temperature and time was measured.

<TEM observation>
Morphological observation was performed with a transmission electron microscope (TEM) [“H-7650” manufactured by Hitachi High-Technologies Corporation] using a sample obtained by pretreating the sheet obtained above by the following method. The results are shown in FIG.
Pre-treatment: Trimming / Surfaceting (frozen) → RuO ₄ staining → Ultrathin section preparation (frozen) → Carbon reinforcement

<X-ray scattering measurement>
Using the sheet obtained above, X-ray scattering measurement was performed with a polymer dedicated beam line BL03XU installed in the large synchrotron radiation facility SPring-8 (Hyogo Prefecture). The obtained scattering intensity curve is shown in FIG. In addition, curve fitting using the following formula (1) was performed on the obtained scattering intensity curve, and parameter A was obtained.

[Comparative Example 1]
In Example 1, instead of EBDM-1 obtained in Synthesis Example 1, “3072EM” (EPDM, ethylene content: 64 wt%, diene content: 5.4 wt%, Mooney viscosity ML _{(1 +4) A} dynamically cross-linked thermoplastic elastomer was prepared in the same manner as in Example 1 except that 125 ° C .: 51, oil extended amount: 40 (PHR)) was used, and a sheet was prepared and evaluated. It was. The results are shown in Table 2, FIG. 2 and FIG.

Claims (10)

A crystalline olefin polymer (A);
A thermoplastic elastomer composition comprising ethylene / C4-C20 α-olefin / non-conjugated polyene copolymer (B) and satisfying the following requirement (1):
(1) A scattering intensity curve obtained by X-ray scattering measurement of a dynamically cross-linked thermoplastic elastomer obtained by dynamically cross-linking the thermoplastic elastomer composition in the presence of a cross-linking agent (where the vertical axis indicates the scattering intensity I (q), the horizontal axis is the scattering vector size q), the parameter A obtained by curve fitting using the following formula (1) is in the range of 10 to 125 nm.
[In formula (1), I (0) is the scattering intensity when extrapolated to q = 0, and q is the following formula between the wavelength λ (nm) of incident light and the scattering angle 2θ (rad): 2). ]
λq = 4πsinθ (2) The thermoplastic elastomer composition according to claim 1, wherein the copolymer (B) satisfies the following requirements (2) and (3):
(2) B value represented by following formula (i) is 1.20 or more;
B value = ([EX] +2 [Y]) / [2 × [E] × ([X] + [Y])] (i)
[In the formula (i), [E], [X] and [Y] are the molar fraction of the structural unit (B1) derived from ethylene and the structural unit derived from α-olefin having 4 to 20 carbon atoms (B2 ), And the molar fraction of the structural unit (B3) derived from non-conjugated polyene, [EX] is the structural unit derived from ethylene (B1) -the structural unit derived from α-olefin having 4 to 20 carbon atoms ( B2) shows the dyad chain fraction. ]
(3) The molar ratio [(B1) / (B2)] of the structural unit (B1) derived from ethylene and the structural unit (B2) derived from an α-olefin having 4 to 20 carbon atoms is 40/60 to 90 / 10 range.   The thermoplastic elastomer composition according to claim 1 or 2, wherein the α-olefin in the copolymer (B) is 1-butene.   The thermoplastic elastomer composition according to any one of claims 1 to 3, further comprising a phenol resin-based crosslinking agent (C).   The thermoplastic elastomer composition according to claim 4, wherein the phenol-based crosslinking agent (C) is a halogenated phenol resin-based crosslinking agent. The weight ratio [(A) / (B)] of the crystalline olefin polymer (A) and the copolymer (B) is in the range of 90/10 to 10/90,
The content of the phenol resin-based crosslinking agent (C) is in the range of 0.1 to 20 weights with respect to 100 parts by weight of the copolymer (B). A thermoplastic elastomer composition.   Furthermore, the softener (D) is contained in a range of 2 to 100 parts by weight with respect to 100 parts by weight of the total of the crystalline olefin polymer (A) and the copolymer (B). The thermoplastic elastomer composition according to any one of claims 1 to 6.   A dynamically crosslinked thermoplastic elastomer obtained by dynamically crosslinking the thermoplastic elastomer composition according to claim 1.   A method for producing a dynamically crosslinked thermoplastic elastomer, wherein the thermoplastic elastomer composition according to any one of claims 1 to 7 is dynamically crosslinked.   A molded article comprising the dynamically crosslinked thermoplastic elastomer according to claim 8.