JP2019127543A - Bellows-like molding composed of thermoplastic elastomer composition - Google Patents

Abstract

To provide a bellows-like molding that is composed of a thermoplastic elastomer composition and prevents oil bleeding and has bending properties and oil resistance.SOLUTION: A bellows-like molding has a thermoplastic elastomer composition (X) that contains a crystalline polyolefin (A) 60-200 pts.mass with a melt flow rate (230°C, 2.16 kg load) of 0.01-100 g/10 minutes and a melting point (Tm) of 100°C or more, an ethylene α-olefin (C3-20) nonconjugated polyene copolymer (B) 100 pts.mass with a Mooney viscosity ML(125°C) of 10-250, and a filler (C) 20-70 pts.mass. The filler (C) contains a magnesium silicate filler (C-α) and at least one filler (C-β) selected from a carbonate filler (C-β1) and an aluminum silicate filler (C-β2), with a mass ratio between the magnesium silicate filler (C-α) and the filler (C-β) ((C-α)/(C-β)) of 100/30-100/1200, wherein, in the thermoplastic elastomer composition (X), an initial flexural modulus at 23°C is 50-180 MPa, and a type D hardness (after 5 seconds) in accordance with JIS K6253 is 20-50 or a type A hardness (instantaneous value) in accordance with JIS K6253 is 80-95. There are also provided a sealant and an automobile dust cover composed of the molding.SELECTED DRAWING: None

Description

  The present invention relates to a bellows-like molded product comprising a thermoplastic elastomer composition.

  Thermoplastic elastomers are lightweight and easy to recycle, so they are widely used as energy- and resource-saving elastomers, especially as an alternative to vulcanized rubber, in automobile parts, industrial machine parts, electrical / electronic parts, building materials, etc. Yes.

  Among them, olefin-based thermoplastic elastomers are made of crystalline polyolefins such as ethylene / propylene / non-conjugated diene copolymer (EPDM) and polypropylene (PP) as raw materials, so they have specific gravity compared to other thermoplastic elastomers. Although it is light and excellent in durability such as heat aging resistance and weather resistance, further improvement is required depending on the application.

  On the other hand, a bellows is a repeated structure of a mountain fold and a valley fold made of a film or plate-like member such as plastic. A dust cover is known as a bellows-shaped molded body. Ball joints are used as joint mechanisms in agricultural machines such as automobiles and tractors, suspension devices such as construction machines represented by forklifts, and steering devices, etc. A lubricant (grease for protecting the smooth surface of the ball joints is used The dust cover is used for the purpose of preventing the outflow of) and the intrusion of mud and dust from the outside.

  Patent Document 1 describes that an olefinic thermoplastic elastomer composition is suitably used as a dust cover forming material because of its excellent weather resistance, moldability, and the like.

  However, Patent Document 1 does not mention at all a filler blended in the olefin-based thermoplastic elastomer composition.

  Patent Document 2 describes fillers such as talc, clay, graphite, and calcium silicate as optional components used for vulcanized rubber (NBR / EPDM) dust covers, but they are used in the examples. No mention is made of the effects of differences in filler types.

  Patent Document 3 describes a thermoplastic elastomer for extrusion / injection molding comprising EPDM / PP / styrene-based elastomer / filler / oil and having improved relaxation performance at low temperature. The thermoplastic elastomer contains a filler selected from calcium carbonate, talc and / or kaolin and contains a styrenic elastomer as an essential component, and no mention is made of a bellows-like molded article such as a dust cover. .

JP 2017-133550 A (paragraph 0034) Unexamined-Japanese-Patent No. 2007-31609 (Claim 1, Paragraph 0014) German Patent Application Publication No. 102006002759

  The present inventors have studied to create a dust cover for automobiles by blow molding using a thermoplastic elastomer composition, and the dust cover for automobiles having a bellows shape is once compressed in the direction of folding the bellows and opened. Then, there is a problem that the bellows is slowly returned, and by adding a carbonate filler such as calcium carbonate or an aluminum silicate filler such as clay to the thermoplastic elastomer composition, the bellows can be deformed and returned. It became faster, but it was found that oil bleed occurred when left at high temperature. Although it is usually possible to solve the oil bleed by reducing the amount of oil added, the oil resistance of the molded article is deteriorated.

  An object of the present invention is to provide a bellows-like molded body which is made of a thermoplastic elastomer composition and in which oil bleeding, bending characteristics and oil resistance are compatible.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies. As a result, the thermoplastic elastomer composition has a magnesium silicate filler such as talc and a carbonate filler such as calcium carbonate and / or By blending an aluminum silicate-based filler such as clay at a specific ratio, it has been found that both oil bleed and flex characteristics and oil resistance can be achieved, and the present invention has been completed.

That is, the gist of the present invention is as follows.
(1) 60 to 200 parts by mass of a crystalline polyolefin (A) having a melt flow rate (230 ° C., 2.16 kg load) of 0.01 to 100 g / 10 min and a melting point (Tm) of 100 ° C. or higher,
100 parts by mass of ethylene / α-olefin (3 to 20 carbon atoms) / non-conjugated polyene copolymer (B) having a Mooney viscosity ML _{(1 + 4)} (125 ° C.) of 10 to 250,
And 20 to 70 parts by mass of filler (C),
The filler (C) is at least one selected from magnesium silicate filler (C-α), carbonate filler (C-β1) and aluminum silicate filler (C-β2). The filler (C-β) and the mass ratio of the magnesium silicate based filler (C-α) to the filler (C-β) ((C-α) / (C-β)) 100/30 to 100 Including at / 1200,
The initial flexural modulus at 23 ° C. is 50 to 180 MPa, the type D hardness (after 5 seconds) according to JIS K6253 is 20 to 50, or the type A hardness (instantaneous value) according to JIS K6253 is 80 to 95. A bellows-shaped molded article comprising the thermoplastic elastomer composition (X).
(2) The molded article according to (1), wherein at least a part of the thermoplastic elastomer composition (X) is crosslinked with the phenol resin-based crosslinking agent (D).
(3) The molded article according to the above (1) or (2), wherein the thermoplastic elastomer composition (X) further contains 105 to 150 parts by mass of a softening agent (E).
(4) The sealing material which consists of a molded object in any one of said (1)-(3).
(5) The dust cover for motor vehicles which consists of a molded object in any one of said (1)-(3).

  The bellows-like molded product of the present invention is made of a thermoplastic elastomer composition, and can be balanced at high levels with oil bleed, bending characteristics (flexible deformation return) and oil resistance. A bellows-shaped component may be used, for example, as a cover of a movable or deformable component in a car, so it is preferable that the component be rapidly deformed or deformed following the movement of the movable part to be covered. . When the deformation return is slow, a large load is applied to the cover, and tearing or abnormal noise may occur.

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

  The crystalline polyolefin (A) may be obtained by synthesis according to a conventionally known method, or a commercially available product may be used.

  The crystalline polyolefin (A) may be used alone or in combination of two or more.

  As monoolefins to be a raw material of the crystalline polyolefin (A), ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 2-methyl-1-propene, 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 crystalline polyolefin (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 a propylene copolymer, the content of structural units derived from propylene is preferably 40 mol% or more, more preferably 50 mol% or more, and as a monoolefin to be a structural unit derived from a monomer other than propylene Is preferably the above-mentioned monoolefin other than propylene, more preferably ethylene, butene.

  The polymerization mode may be random type or block type, and any polymerization mode may be adopted as long as a crystalline resin can be obtained.

  The crystalline polyolefin (A) has an MFR (ASTM D 1238-65 T, 230 ° C., 2.16 kg load) of 0.01 to 100 (g / 10 min), preferably 0.05 to 50 (g / 10). Min). When the MFR is less than 0.01 (g / 10 min), the flowability of the thermoplastic elastomer is reduced and the moldability is poor, and when it exceeds 100 (g / 10 min), the flowability is high, and the drawdown is And the occurrence of burrs and the mechanical properties of the thermoplastic elastomer also deteriorate.

  The crystalline polyolefin (A) has a melting point (Tm) obtained by differential scanning calorimetry (DSC) of 100 ° C. or more, preferably 105 ° C. or more. The oil resistance and heat resistance of a thermoplastic elastomer fall that the said melting | fusing point (Tm) is less than 100 degreeC.

  Differential scanning calorimetry is performed, for example, as follows. About 5 mg of the sample is packed in a special aluminum pan, heated to 320 ° C./min from 30 ° C. to 200 ° C. using DSCPyris 1 or DSC 7 manufactured by Perkin Elmer Co., Ltd., held at 200 ° C. for 5 minutes, and then 200 ° C. The temperature is lowered from 10 ° C. to 30 ° C. at 10 ° C./min, held at 30 ° C. for further 5 minutes, and then the melting point is determined from the endothermic curve when raising the temperature at 10 ° C./min. In addition, when a several peak is detected at the time of DSC measurement, the peak temperature detected in the highest temperature side is defined as melting | fusing point (Tm).

  The crystalline polyolefin (A) plays a role of improving the flowability and heat resistance of the thermoplastic elastomer composition.

  The blending amount of the crystalline polyolefin (A) is 60 to 200 parts by mass, preferably 100 to 180 parts by mass with respect to 100 parts by mass of the copolymer (B). When the content of the crystalline polyolefin (A) is less than 60 parts by mass, the mechanical strength of the thermoplastic elastomer is decreased, and when it exceeds 200 parts by mass, the surface hardness is increased and the bellows is hardened.

<Ethylene .alpha.-olefin (3 to 20 carbon atoms) non-conjugated polyene copolymer (B)>
The ethylene / α-olefin (carbon number 3 to 20) / nonconjugated polyene copolymer (B) (also referred to as copolymer (B) in the present invention) used in the present invention is at least one structural unit derived from ethylene. Ethylene / α-olefin / non-conjugated polyene copolymer comprising a structural unit derived from an α-olefin having 3 to 20 carbon atoms and a structural unit derived from at least one non-conjugated polyene; Mooney viscosity ML _{(1 + 4) )} (125 ° C) is 10-250.

  Examples of the α-olefin having 3 to 20 carbon atoms include propylene (3 carbon atoms), 1-butene (4 carbon atoms), 1-nonene (9 carbon atoms), 1-decene (10 carbon atoms) and 1-nonadecene C19), 1-eicosene (carbon number 20) or other linear α-olefin having no side chain; 4-methyl-1-pentene, 9-methyl-1-decene, 11-methyl having a side chain Examples include α-olefins having side chains such as -1-dodecene and 12-ethyl-1-tetradecene. These α-olefins may be used alone or in combination of two or more. Among these, C3-C10 alpha-olefin is preferable and a propylene, 1-butene, 1-hexene, 1-octene is more preferable. You may use these alpha-olefins individually or in combination of 2 or more types.

  Non-conjugated polyenes include chains such as 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, etc. Non-conjugated dienes; 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.

  As the copolymer (B), 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.

  The ethylene / α-olefin (carbon number 3 to 20) / non-conjugated polyene copolymer (B) is a molar ratio of the structural unit [A] derived from ethylene to the structural unit [B] derived from α-olefin [ [A] / [B]] is usually in the range of 40/60 to 90/10. The lower limit of the molar ratio [A] / [B] is preferably 45/55, more preferably 50/50, and particularly preferably 55/45. The upper limit of the molar ratio [A] / [B] is preferably 80/20, more preferably 75/25, still more preferably 70/30, and particularly preferably 65/35.

The copolymer (B) is obtained by measurement according to JIS K 6300 (1994), and the Mooney viscosity ML _{(1 + 4)} (125 ° C.) at 125 ° C. is 10 to 250, preferably 30 to 230, and further Preferably it exists in the range of 50-200. When the Mooney viscosity is less than 10, mechanical strength and heat resistance are inferior, and when it exceeds 250, moldability of the thermoplastic elastomer is deteriorated.

  In the copolymer (B), the content of the structural unit [C] derived from the non-conjugated polyene is preferably 100% by mole of the total of the structural units of [A], [B] and [C]. 0.1 to 6.0 mol%, more preferably 0.5 to 4.0 mol%, still more preferably 0.5 to 3.5 mol%, particularly preferably 0.5 to 3.0 mol% It is in. When the content of the structural unit [C] derived from the nonconjugated polyene is in the above range, an ethylene-based copolymer having sufficient crosslinkability and flexibility tends to be obtained.

(Production method of copolymer (B))
The copolymer (B) can be obtained, for example, by the following production method.

  Specifically, (a-3) a transition metal compound represented by the following general formula [VII] (in the following description, it may be abbreviated as "bridged metallocene compound") and (b) (b- 1) At least one selected from the group consisting of an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) a compound which reacts with a transition metal compound (a-3) to form an ion pair It can manufacture by copolymerizing ethylene, a C3-C20 alpha-olefin, and nonconjugated polyene in the presence of the olefin polymerization catalyst containing a compound. When ethylene, an α-olefin having 3 or more carbon atoms and a nonconjugated polyene are copolymerized in the presence of an olefin polymerization catalyst containing the bridged metallocene compound, further polymerization of the copolymer c can be achieved. The advantage is obtained.

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

  The M is a titanium atom, a zirconium atom or a hafnium atom, preferably a hafnium atom.

R ⁵ and R ⁶ are each a substituted aryl group formed by substituting one or more hydrogen atoms of an aryl group with an electron donating substituent having a Hammett's substituent constant σ of −0.2 or less. In the case of having a plurality of electron donating substituents, each of the electron donating substituents may be the same or different, and is a hydrocarbon group having 1 to 20 carbon atoms other than the electron donating substituent, silicon-containing It 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 in the case of having 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”).

  Examples of the aryl group include 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 And substituents derived from aromatic compounds such as, and the like. As said aryl group, a phenyl group or 2-naphthyl group is preferable. Examples of the aromatic compound include aromatic hydrocarbons such as benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, pyrene, indene, azulene, pyrrole, pyridine, furan, thiophene and the like, heterocyclic aromatic compounds, etc. Is mentioned.

  An electron donating group having a Hammett's substituent constant σ of −0.2 or less is defined and exemplified as follows. The Hammett rule is a rule of thumb proposed by 1935 L.P. Hammett to quantitatively discuss the effects 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 document 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 have slightly different values depending on the documents 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 the page are defined as Hammett's substituent constants σp and σm. In the present invention, an electron donating group having a Hammett's substituent constant σ of −0.2 or less means that σ p is −0 when the electron donating group is substituted at the para position (4 position) of a phenyl group. .2 An electron donating group having 2 or less and an electron donating group having .sigma.m of -0.2 or less when substituted at the meta position (3 position) of the phenyl group. When the electron donating group is substituted at the ortho position (2-position) of the phenyl group or at any position of the aryl group other than the phenyl group, σp is -0.2 or less Electron donating group of

  As an electron donating substituent having a Hammett's 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 as defined in the present invention of −0.2 or less is described in the literature by Hansch and Taft [Chem. Rev., 91, 165 (1991)]. It is not limited to the substituents 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 the Hammett's rule is within the range thereof is the Hammett's rule substituent defined in the present invention. It is included in the electron donating group whose constant σ p or σ m is −0.2 or less. As such a substituent, p-N-morpholinyl group (4-N-morpholinyl group), m-N-morpholinyl group (3-N-morpholinyl group), etc. may be mentioned.

  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, and carbon number other than the electron donating substituent The substituent selected from the group consisting of a hydrocarbon group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group of 1 to 20 may be substituted; In each case, each substituent may be the same or different, but the sum of the Hammett's substituent constants σ of the electron-donating substituent and the substituents contained in one substituted aryl group is -0. It is preferable that it is .15 or less. 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.

  The hydrocarbon group having 1 to 20 carbon atoms which the electron donating group-containing substituted aryl group may have includes 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. In the case where a plurality of hydrocarbon groups having 1 to 20 carbon atoms are included and the hydrocarbon groups having 1 to 20 carbon atoms are adjacent to each other, they may be bonded to each other to form a ring. As a group in this case, a C1-C20 alkylene group, a C6-C20 arylene group, etc. are illustrated.

  As a C1-C20 alkyl group, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 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, 1,1-dimethylbutyl, 1-methyl-1-propylbutyl, 1,1-dipropylbutyl, 1,1-dimethyl-2-methylpropyl, 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. A substituted cyclic saturated hydrocarbon group; a hydrogen atom of an unsubstituted cyclic saturated hydrocarbon group such as 3-methylcyclopentyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 4-cyclohexylcyclohexyl group, 4-phenylcyclohexyl group and the like Are groups substituted with a hydrocarbon group having 1 to 17 carbon atoms. The carbon number of the cyclic saturated hydrocarbon group is preferably 5 to 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). And ethynyl group which is an alkynyl group, 1-propynyl group, 2-propynyl group (propargyl group) and the like can be mentioned. The carbon number of the chain unsaturated hydrocarbon group is preferably 2 to 4.

  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, The hydrogen atom of the 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 substituted with a hydrocarbon group; a hydrogen atom of a linear hydrocarbon group such as a benzyl group and a cumyl group or a branched saturated hydrocarbon group has 3 to carbon atoms Such groups which are replaced by 9 cyclic saturated hydrocarbon group or a cyclic unsaturated hydrocarbon group. The carbon number of the cyclic unsaturated hydrocarbon group is preferably 6 to 10.

  Examples of the alkylene group having 1 to 20 carbon atoms include methylene group, ethylene group, dimethylmethylene group (isopropylidene group), ethylmethylene group, 1-methylethylene group, 2-methylethylene group, 1,1-dimethylethylene group, A 1,2-dimethyl ethylene group, n-propylene group etc. are illustrated. Preferably carbon number of an alkylene group is 1-6.

  As a C6-C20 arylene group, o-phenylene group, m-phenylene group, p-phenylene group, 4,4'- biphenylylene group etc. are illustrated. The number of carbon atoms of the arylene group is preferably 6-12.

  Examples of the silicon-containing group that the electron-donating group-containing substituted aryl group may have include alkylsilyl groups such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, and triisopropylsilyl group; dimethylphenylsilyl group, methyl Arylsilyl groups such as diphenylsilyl group and t-butyldiphenylsilyl group; groups having 1 to 20 carbon atoms such as pentamethyldisiranyl group and trimethylsilylmethyl group, wherein carbon atoms are replaced by silicon atoms, 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. A group in which a CH-structural unit is replaced by a nitrogen atom, a group in which a —CH ₂ — structural unit is replaced by a nitrogen atom having a hydrocarbon group of 1 to 20 carbon atoms bonded, or a CH ₃ structural unit has 1 carbon atom And a dimethylamino group, a diethylamino group, a dimethylaminomethyl group, a cyano group, a pyrrolidinyl group, a piperidinyl group, a pyridinyl group and the like 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.

The oxygen-containing group which the electron donating group-containing substituted aryl group may have is a -CH ₂ -structural unit in a hydroxyl group, the above-mentioned hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or a nitrogen-containing group A methoxy group, an ethoxy group, a t-butoxy group, which is a group in which is substituted by an oxygen atom or a carbonyl group, or a group in which a CH ₃ structural unit is substituted by an oxygen atom having a hydrocarbon group of 1 to 20 carbon atoms bonded 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-hydroxy Ethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, n-2-oxabutylene group, n-2-oxapentylene group 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, carbamoyl A methyl 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 which may be possessed by the electron donating group-containing substituted aryl group include fluorine, chlorine, bromine and iodine which are Group 17 elements.

  As the halogen-containing group which the electron donating group-containing substituted aryl group may have, in the above-mentioned hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group or an oxygen-containing group, a hydrogen atom is a halogen A trifluoromethyl group which is a group substituted by an atom, a tribromomethyl group, a pentafluoroethyl group, a pentafluorophenyl group and the like can be mentioned.

  Q is an atom 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 capable of coordinating with a lone electron pair, a substituent or a ligand, When there are a plurality of Q's, they may be the same or different.

  Specific examples of the halogen atom as 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 which may be possessed by the electron donating group-containing substituted aryl group. 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, t-butoxy and phenoxy; carboxylates such as acetate and benzoate; and sulfonates such as mesylate and tosylate.

  Organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine as neutral ligands which can be coordinated by a lone electron pair; tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane and the like Ether compounds and the like can be mentioned.

  j is an integer of 1 to 4, preferably 2.

  The 2,3,6,7-tetramethylfluorenyl group contained in the bridged metallocene compound (a) represented by the general formula [VII] has four substituents at the 2, 3, 6 and 7 positions. Therefore, it is presumed that an electronic effect is large, and thereby a high molecular weight ethylene copolymer having high polymerization activity and high molecular weight is formed. 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. It is estimated that it leads to the performance improvement. Since the four methyl groups contained in the 2,3,6,7-tetramethylfluorenyl group are not bulky compared to other hydrocarbon groups etc., this contributes to the high non-conjugated polyene copolymerization performance. It is thought that. From the above, the bridged metallocene compound represented by the above general formula [VII] containing a 2,3,6,7-tetramethylfluorenyl group, in particular, has a high molecular weight and a high non-conjugated ethylene copolymer to be produced. It is presumed that polyene copolymerization performance and high polymerization activity are simultaneously realized at a high level and in a well-balanced manner.

  The bridged metallocene compound (a-3) can be synthesized by a simple method such as the following formula [VIII].

（式［VIII］において、Ｍ、Ｒ^５、Ｒ^６の定義、具体例及び好適例は式［VII］の場合と同様である。）

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

In the above-mentioned formula [VIII], R ⁵ and R ⁶ are as described above, but various ketones satisfying such conditions, represented by the general formula R ⁵ —C (RO) —R ⁶ are generally Since it is commercially available from reagent manufacturers, it is easy to obtain the raw material for the bridged metallocene compound (a-3). Also, even if such ketones are not commercially available, the ketones can be easily synthesized, for example, according to the method by Olah et al. [Heterocycles, 40, 79 (1995)]. Thus, the crosslinked metallocene compound (a-3) has a relatively simple and easy production process, the production cost is further reduced, and by using this crosslinked metallocene compound, the production cost of the ethylene-based copolymer is thereby achieved. Has the advantage of being reduced. Furthermore, when ethylene, an α-olefin having 3 or more carbon atoms and an unconjugated polyene are copolymerized in the presence of an olefin polymerization catalyst containing the bridged metallocene compound (a-3), a further copolymer is produced. The advantage that high molecular weight formation is possible is also acquired.

In the bridged metallocene compound (a-3) represented by the above general formula [VII], 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 3 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 is further improved. The advantage that high molecular weight formation is possible is acquired. At the same time, there is also the 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-3) represented by the above general formula [VII], it is more preferable that R ⁵ and R ^{6 be} 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. In addition, the production cost of the copolymer is reduced by using the bridged metallocene compound. The advantage of being obtained. In addition, when copolymerizing ethylene, an α-olefin having 3 or more carbon atoms and a non-conjugated polyene in the presence of an olefin polymerization catalyst containing the bridged metallocene compound, it is possible to further increase the molecular weight of the resulting copolymer. The advantage that it is is obtained.

As a result of intensive investigations by the applicant of various bridged metallocene compounds (a), in the bridged metallocene compound (a-3) represented by the above general formula [VII], when R ⁵ and R ⁶ are the above groups In particular, the bridged metallocene compound (a-3) is obtained by forming an electron donating group-containing substituted aryl group in which one or more electron donating substituents having a Hammett's substituent constant σ of −0.2 or less are substituted. It has been found for the first time that the molecular weight of the resulting copolymer can be further increased when copolymerizing ethylene and an α-olefin having 3 or more carbon atoms with a nonconjugated polyene in the presence of an olefin polymerization catalyst containing

In the coordination polymerization of olefins using an organometallic complex catalyst such as the bridged metallocene compound (a-3), the olefin polymer is repeatedly polymerized on the central metal of the catalyst, whereby the molecular chain of the resulting olefin polymer grows ( It is known that the molecular weight of the olefin polymer increases. On the other hand, in a reaction called chain transfer, when the molecular chain of the olefin polymer dissociates from the central metal of the catalyst, the growth reaction of the molecular chain is stopped, and thus the molecular weight increase of the olefin polymer is also stopped. Are known. Thus, the molecular weight of the olefin polymer is characterized by the ratio of the frequency of the growth reaction to the frequency of the chain transfer reaction inherent in 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 produced olefin polymer, and conversely, the lower the molecular weight, the lower the molecular weight. 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 can be considered that 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. There is. Therefore, 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) becomes positive, and the larger this value, the higher 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 carried out in this way is also supported, for example, by the calculation results of Laine et al. [Organometallics, 30, 1350 (2011)]. In the bridged metallocene compound (a-3) represented by the above general formula [VII], R ⁵ and R ⁶ are selected, in particular, one electron donating substituent having a Hammett's substituent constant σ of −0.2 or less. In the case of an electron donating group-containing substituted aryl group substituted by at least one, the ΔEc is increased, and ethylene and an α having a carbon number of 3 or more in the presence of an olefin polymerization catalyst containing the crosslinked metallocene compound (a-3) -It is presumed that when the olefin and the non-conjugated polyene are copolymerized, the molecular weight of the resulting copolymer increases.

In the bridged metallocene compound (a-3) represented by the above general formula [VII], the electron donating substituent contained in R ⁵ and R ⁶ is a group selected from the group consisting of a nitrogen-containing group and an oxygen-containing group It is further preferred that These substituents have a particularly low σ in Hammett's rule, and can increase the molecular weight of ethylene / α-olefin / nonconjugated polyene copolymer, and can increase the molecular weight particularly in high temperature polymerization which generally causes a decrease in molecular weight.

In the bridged metallocene compound (a-3) represented by the above general formula [VII], R ⁵ and R ^{6 each} represent a group selected from the group consisting of a nitrogen-containing group and an oxygen-containing group as the electron-donating substituent More preferably, it is a substituted phenyl group. For example, in the case of synthesis according to the method of the above formula [VIII], since various benzophenones as raw materials are commercially available from general reagent manufacturers, the raw materials can be easily obtained, the production process is simplified, and the production cost is further improved. The advantage is obtained that the cost is reduced, and by using this bridged metallocene compound, the production cost of the copolymer (B) is 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 (2- (diethylamino) phenyl), p- (diethylamino) phenyl (4- (diethylamino) phenyl), m- (diethylamino) phenyl (3- (diethylamino) phenyl), o- Methoxyphenyl group (2-methoxyphenyl group), p-methoxyphenyl group (4-methoxyphenyl group), o-ethoxy Phenyl 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) Groups), 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- - methylphenyl), p-methoxy -m, m-dimethylphenyl group (4-methoxy-3,5-dimethylphenyl group).

In the bridged metallocene compound (a-3) represented by the above general formula [VII], R ⁵ and R ⁶ are the electron donating substituents at the meta position and / or para position to the bond with the carbon atom as the Y More preferably, it is a substituted phenyl group containing a group selected from the group consisting of a nitrogen-containing group and an oxygen-containing group as a group. For example, when synthesis is carried out according to the method of the above formula [VIII], synthesis becomes easier, the production process is simplified, the production cost is reduced, and thus this bridged metallocene is compared to the case where the group is substituted at the ortho position. The advantage that the production cost of the ethylene copolymer is reduced is obtained by using the compound.

In the bridged metallocene compound (a-3) represented by the above general formula [VII], R ⁵ and R ⁶ are the above-mentioned electron-donating substituents in the meta-position and / or para-position relative to the bond with the carbon atom as Y. When it is a substituted phenyl group containing a nitrogen-containing group as a group, the nitrogen-containing group is more preferably a group represented by the following general formula [II].

（式［II］において、Ｒ^７及びＲ^８は水素原子、炭素数１から２０の炭化水素基、ケイ素含有基、酸素含有基及びハロゲン含有基からなる群より選ばれる原子又は置換基であり、それぞれ同一でも異なっていてもよく、互いに結合して環を形成していてもよく、Ｎの右に描かれた線はフェニル基との結合を表す。）

(In Formula [II], R ⁷ and R ^{8 each} represent an atom or a substituent selected from the group consisting of 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, 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 the bond with the phenyl group.)

Specific examples and preferable examples of the hydrocarbon group having 1 to 20 carbon atoms as R ⁷ and R ⁸ , the silicon-containing group, the oxygen-containing group, and the halogen-containing group are the same as in the case of the formula [VII].

  Such a bridged metallocene compound (a-4) is represented by the following general formula [IX].

（式［IX］において、Ｍ、Ｑ及びｊの定義、具体例及び好適例は式［VII］の場合と同様である。Ｒ^７、Ｒ^８及びＲ^１０は水素原子、炭素数１から２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子及びハロゲン含有基からなる群より選ばれる置換基であり、それぞれ同一でも異なっていてもよく、Ｒ^７、Ｒ^８及びＲ^１０のうちの隣接した置換基は互いに結合して環を形成していてもよく、ＮＲ^７Ｒ^８はハメット則の置換基定数σが−０．２以下の窒素含有基であり、該窒素含有基が複数個存在する場合にはそれぞれの窒素含有基は互いに同一でも異なっていてもよく、ｎは１から３の整数であり、ｍは０から４の整数である。）

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

Specific examples of these substituents can be given as examples of the hydrocarbon group having 1 to 20 carbon atoms, silicon-containing group, oxygen-containing group and halogen-containing group as R ¹⁰ .

Since the bridged metallocene compound (transition metal compound) represented by the general formula [IX] has a particularly low σ in Hammett's rule of NR ⁷ R ⁸ represented by the general formula [II], ethylene · α-olefin · non- The molecular weight of the conjugated polyene copolymer can be increased, and in particular, the molecular weight can be increased even in high temperature polymerization that generally causes a decrease in molecular weight.

In the bridged metallocene compound (a-3) represented by the above general formula [VII], R ⁵ and R ⁶ are the above-mentioned electron-donating substituents in the meta-position and / or para-position relative to the bond with the carbon atom as Y. When it is a substituted phenyl group containing an oxygen-containing group as a group, the oxygen-containing group is more preferably a group represented by the following general formula [III].

R ⁹ -O- ... [III]
(In the formula [III], R ⁹ represents an atom or a 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 line drawn in represents a bond with a phenyl group.)

Specific examples and preferable 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 in the case of the formula [VII].
Such a bridged metallocene compound (a-5) is represented by the following general formula [X].

（式［Ｘ］において、Ｍ、Ｑ及びｊの定義、具体例及び好適例は式［VII］の場合と同様である。Ｒ^９及びＲ^１０は水素原子、炭素数１から２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子及びハロゲン含有基からなる群より選ばれる原子又は置換基であり、それぞれ同一でも異なっていてもよく、Ｒ^１０の隣接した置換基は互いに結合して環を形成していてもよく、ＯＲ^９はハメット則の置換基定数σが−０．２以下の酸素含有基であり、該酸素含有基が複数個存在する場合にはそれぞれの酸素含有基は互いに同一でも異なっていてもよく、ｎは１から３の整数であり、ｍは０から４の整数である。）

(In formula [X], the definitions, specific examples and preferred examples of M, Q and j are the same as in formula [VII]. R ⁹ and R ^{10 each} represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms Or an atom or a substituent selected from the group consisting of a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group, which may be the same or different, and adjacent substituents of R ¹⁰ OR ⁹ may be bonded to form a ring, OR ⁹ is an oxygen-containing group having a Hammett's substituent constant σ of −0.2 or less, and when there are a plurality of such oxygen-containing groups, the respective oxygens The 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.)

Specific examples of these substituents can be given as examples of the hydrocarbon group having 1 to 20 carbon atoms, silicon-containing group, oxygen-containing group and halogen-containing group as R ¹⁰ .

Since the bridged metallocene compound (transition metal compound) represented by the general formula [X] has a further lower σ in Hammett's rule of OR ⁹ represented by the above general formula [III], the ethylene • α-olefin • nonconjugated polyene The molecular weight of the copolymer can be increased, and in particular, the molecular weight can be increased even in high temperature polymerization that generally causes a decrease in molecular weight.

  The bridged metallocene compound (a-3) of the present invention represented by the above-mentioned general formula [VII], the bridged metallocene compound (a-4) of the present invention represented by the above-mentioned general formula [IX] In the bridged metallocene compound (a-5) of the present invention represented by the formula, M is more preferably a hafnium atom. When copolymerization is carried out with ethylene and an α-olefin having 3 or more carbon atoms and a nonconjugated polyene in the presence of an olefin polymerization catalyst containing the above-mentioned bridged metallocene compound in which M is a hafnium atom, the height of the produced copolymer is higher Molecular weight can be obtained, and the advantage of improving the copolymerization performance of the nonconjugated polyene can be obtained.

As such a bridged metallocene compound (a),
[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-tetramethyl-fluorenyl)] hafnium dichloride, [bis (4-methylphenyl) Styrene (eta 5 ^- cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [bis (3,4-dimethylphenyl) methylene (eta 5 ^- Shikuropentaji Enyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis (4-n-hexylphenyl) methylene ( ^{5 5} -cyclopentadienyl) ( ^{5 5} -2, 3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis (4-cyclohexylphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorene) Nyl)] hafnium dichloride, [bis (4-t-butylphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis (3-methoxyphenyl) methylene (eta 5 ^- cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-full} Reniru)] hafnium dichloride, [bis (4-methoxyphenyl) methylene (eta 5 ^- cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [bis (3 2,4-Dimethoxyphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis (4-methoxy-3-methylphenyl) methylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [bis (4-methoxy-3,4-dimethylphenyl) methylene (eta 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-phenoxy Shifeniru) methylene (eta 5 ^- cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [bis {4- (trimethylsiloxy) phenyl} methylene (eta ^{5 -} cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [bis {3- (dimethylamino) phenyl} methylene (eta 5 ^- cyclopentadienyl) (eta ⁵ -2,3,6,7-tetramethyl-fluorenyl)] hafnium dichloride, [bis {4- (dimethylamino) phenyl} methylene (eta 5 ^- cyclopentadienyl) (eta ⁵ -2,3,6 , 7-tetramethylfluorenyl)] hafnium dichloride, [bis (4-N-morpholinylphenyl) (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorene) yl)] hafnium dichloride, [bis {4- (trimethylsilyl) phenyl} methylene (eta 5 ^- cyclopentyl Tajieniru) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [bis (3-chlorophenyl) methylene (eta 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-tetramethylfluorenyl)] hafnium dichloride, [bis {3- (trifluoromethyl) phenyl} methylene (( ⁵ -cyclo Pentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium di Chloride, [Bis {4- (trifluoromethyl) phenyl} methylene ( ^{5 5} -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [methylphenyl methylene (η ⁵ -cyclopentadienyl) () ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [methyl (4-methylphenyl) methylene (η ⁵ -cyclopentadienyl) ( 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-tetramethylfluorenyl) ] Hafnium dichloride, [methyl (4-N-morpholinylphenyl) methylene (η ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [dimethylsilylene (eta 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 (レ ン⁵ -cyclopentadienyl) (η ⁵ -2,3, 6,7-Tetramethylfluorenyl)] hafnium dichloride, [di (4-methylphenyl) silylene (η ⁵ -cyclopentadienyl) (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, and compounds in which the hafnium atom of these compounds is replaced by a zirconium atom, or a chloro ligand is a methyl group Substituting the compound. Among these catalysts, [bis (4-methylphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride is preferable.

  The bridge | crosslinking metallocene compound used for manufacture of the said copolymer (B) can be manufactured by a well-known method, and a manufacturing method in particular is not necessarily limited. As a manufacturing method, for example, J. 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.

  Next, the preferable form in the case of using the said bridge | crosslinking metallocene compound as a catalyst (olefin polymerization catalyst) for manufacture of an ethylene * alpha-olefin (C3-C20) * nonconjugated polyene copolymer (B) is demonstrated.

  When a bridged metallocene compound is used as an olefin polymerization catalyst component, the catalyst comprises (a) a bridged metallocene compound represented by the above general formula [VII], (b) (b-1) an organometallic compound, (b-2) At least one compound selected from the group consisting of an organoaluminum oxy compound, and (b-3) a compound which reacts with the bridged metallocene compound (a) to form an ion pair, and, if necessary, (c) And a particulate carrier.

  Each component will be specifically described below.

<(B-1) Organometallic compound>
Specific examples of the (b-1) organic metal compound used for the production of the copolymer (B) include Group 1, 2 and 12 of the periodic table such as the following general formulas [X] to [XII]. And Group 13 organometallic compounds are used.

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

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

(B-1b) 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, preferably 1 to 4 carbon atoms.) Periodic Table 1 Complex alkylated products of group metals and aluminum.

Examples of the compound represented by the above general formula [XI] include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

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

  Among the organic metal compounds (b-1), organic aluminum compounds such as triethylaluminum, triisobutylaluminum and tri n-octylaluminum are preferable. Moreover, these organometallic compounds (b-1) may be used singly or in combination of two or more.

<(B-2) Organoaluminum oxy compound>
The (b-2) organoaluminum oxy compound used for the production of the copolymer (B) may be a conventionally known aluminoxane, or benzene insoluble as exemplified in JP-A-2-78687. The organic aluminum oxy compound may be used. (B-2) An organoaluminum oxy compound may be used alone or in combination of two or more.

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

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

  Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the above (b-1a).

  Among these, trialkylaluminum and tricycloalkylaluminum are preferable, and among them, trimethylaluminum and triisobutylaluminum are particularly preferable.

  The organoaluminum compounds as described above are used singly or in combination of two or more.

  In the benzene-insoluble organoaluminum oxy compound which is one aspect of the (b-2) organoaluminum oxy compound, the Al component dissolved in benzene at 60 ° C. is usually 10 mass% or less based on 100 mass% of benzene in terms of Al atom , Preferably not more than 5% by mass, particularly preferably not more than 2% by mass, that is, those which are insoluble or poorly soluble in benzene.

  Examples of the (b-2) organoaluminum oxy compound include an organoaluminum oxy compound containing boron represented by the following general formula [X].

（式［Ｘ］中、Ｒ^１は炭素数が１〜１０の炭化水素基を示し、Ｒ^２〜Ｒ^５は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素数が１〜１０の炭化水素基を示す。）

(In formula [X], R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms, and R ^{2 to} R ⁵ may be the same as or different from each other, and a hydrogen atom, a halogen atom, or a carbon 10 hydrocarbon groups are shown.)

The organoaluminumoxy compound containing boron represented by the general formula [X] includes an alkyl boronic acid represented by the following general formula [XI],
R ¹ -B (OH) ₂ ... [XI]
(In formula [XI], R ¹ represents the same group as R ¹ in the general formula [X].)
It can be produced by reacting an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours.

  Specific examples of the alkyl boronic acid represented by the general formula [XI] include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, and n-hexyl boron. Examples include acid, cyclohexyl boronic acid, phenyl boronic acid, 3,5-difluorophenyl boronic acid, pentafluorophenyl boronic acid, 3,5-bis (trifluoromethyl) phenyl boronic acid and the like.

  Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid and pentafluorophenylboronic acid are preferable. These may be used alone or in combination of two or more.

  Specific examples of the organoaluminum compound to be reacted with the alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the above (b-1a).

  Among these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more. The (b-2) organoaluminum oxy compounds as described above are used singly or in combination of two or more.

<(B-3) Compound that reacts with transition metal compound (a) to form an ion pair>
The compound (b-3) (hereinafter referred to as "ionizing ionic compound") which reacts with the bridged metallocene compound (a) used for the production of the copolymer (B) to form an ion pair is disclosed in JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321106. And Lewis acids, ionic compounds, borane compounds and carborane compounds described in the above. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned. Such ionized ionic compounds (b-3) are used singly or in combination of two or more.

Specifically, examples of the Lewis acid include compounds represented by BR ₃ (R is a phenyl group which may have a substituent such as fluorine, a methyl group or a trifluoromethyl group, or fluorine). For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris ( p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like.

  As an ionic compound, the compound represented, for example by the following general formula [XII] is mentioned.

（式［XII］中、Ｒ^１＋としては、Ｈ^＋、カルボニウムカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオン、遷移金属を有するフェロセニウムカチオンなどが挙げられる。Ｒ^２〜Ｒ^５は、互いに同一でも異なっていてもよく、有機基、好ましくはアリール基又は置換アリール基である。）

(Wherein [XII], as the R ^1+, H ^+, carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and a ferrocenium cation having a transition metal .R ² ˜R ⁵ may be the same as or different from each other, and is an organic group, preferably an aryl group or a substituted aryl group.

  Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenyl carbonium cation, tri (methyl phenyl) carbonium cation and tri (dimethyl phenyl) carbonium cation.

Specific examples of the ammonium cation include trialkyl ammonium cations such as trimethyl ammonium cation, triethyl ammonium cation, tripropyl ammonium cation, tributyl ammonium cation and tri (n-butyl) ammonium cation;
N, N-dialkylanilinium cations such as N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N, 2,4,6-pentamethylanilinium cation;
Examples thereof include dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation.

  Specific examples of the phosphonium cation include triaryl phosphonium cations such as triphenyl phosphonium cation, tri (methyl phenyl) phosphonium cation and tri (dimethyl phenyl) phosphonium cation.

As R ^<1+> , a carbonium cation, an ammonium cation, etc. are preferable, and a triphenyl carbonium cation, a N, N- dimethylanilinium cation, and a N, N-diethylanilinium cation are particularly preferable.

  Moreover, a trialkyl substituted ammonium salt, a N, N- dialkyl anilinium salt, a dialkyl ammonium salt, a triaryl phosphonium salt etc. can also be mentioned as an ionic compound.

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

  Specific examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N, 2,4,6. -Pentamethylanilinium tetra (phenyl) boron etc. are mentioned.

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

  Further, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Examples thereof include a cyclopentadienyl complex, an N, N-diethylanilinium pentaphenylcyclopentadienyl complex, and a boron compound represented by the following formula [XIII] or [XIV].

（式［XIII］中、Ｅｔはエチル基を示す。）

(In the formula [XIII], Et represents an ethyl group.)

（式［XIV］中、Ｅｔはエチル基を示す。）

(In the formula [XIV], Et represents an ethyl group.)

  Specific examples of the borane compound include decaborane; bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis Salts of anions such as [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate; Salts of metal borane anions such as -butyl) ammonium bis (dodeca hydride dodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodeca hydride dodecaborate) nickelate (III), etc. Can be mentioned.

  Specific examples of the carborane compound include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride- 1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane, Undecahydride-7,8-dimethyl-7,8-dicarboundecarborane, dodecahydride-11-methyl-2,7-dicarboundecarborane, tri (n-butyl) ammonium 1-carbadecaborate, tri ( n-butyl) ammonium-1-carbaundecaborate, tri (n-butyl) ammonium-1-carba Decaborate, tri (n-butyl) ammonium-1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium-6-carbadecaborate, tri (N-butyl) ammonium-7-carbaundecaborate, tri (n-butyl) ammonium-7,8-dicarboundeborate, tri (n-butyl) ammonium-2,9-dicarboundeborate, tri ( n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate, tri (n-butyl) ) Ammonium undecahydride-8-butyl-7 9-Dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8- Salts of anions such as dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate; tri (n-butyl) ammonium bis (nonahydride-1,3- Dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) ironate (III), tri (n-butyl) ammonium bis ( Undecahydride-7,8-dicarboundeborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8- Dicarbaundecaborate) cuprate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) aurate (III), tri (n-butyl) ammonium bis ( Nonahydride-7,8-dimethyl-7,8-dicarbundecaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundeca) (Borate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbaundeca) Rate) cobaltate (III), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (Undecahydride-7-carbaundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) cobaltate (III), bis Salts of metal carborane anions such as [tri (n-butyl) ammonium] bis (undecahydride-7-carbundecaborate) nickelate (IV) and the like can be mentioned.

  The heteropoly compound is composed of atoms selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germano-tungstovanadic acid, phosphomolybdo-tungstovanadic acid, germano-molybdo-tungstovanadic acid, phosphomolybdotungstic acid , Phosphomolybniobic acid, and salts of these acids, such as metals of Group 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium Salt with etc Organic salts such as triphenylethyl salt can be used but not limited thereto.

  (B-3) Among the ionized ionic compounds, the above-mentioned ionic compounds are preferable, and among them, triphenylcarbenium tetrakis (pentafluorophenyl) borate and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate are preferable. More preferred.

  When the transition metal compound (a) represented by the above general formula [VII] is used as a catalyst, an organic metal compound (b-1) such as triisobutylaluminum, an organic aluminum oxy compound (b-2) such as methylaluminoxane, or When an ionized ionic compound (b-3) such as triphenylcarbenium tetrakis (pentafluorophenyl) borate is used in combination, an ethylene / α-olefin (3 to 20 carbon atoms) / non-conjugated polyene copolymer (B) is produced. Show very high polymerization activity.

  Moreover, the catalyst for olefin polymerization used for manufacture of a copolymer (B) is the said transition metal compound (a), (b-1) organometallic compound, (b-2) organoaluminum oxy compound, and ( b-3) A carrier (c) may be used as necessary together with at least one compound (b) selected from the group consisting of ionized ionic compounds.

<(C) Carrier>
The carrier (c) is an inorganic compound or an organic compound, and is a granular or particulate solid.

  Among the inorganic compounds, porous oxides, inorganic halides, clays, clay minerals, or ion-exchangeable layered compounds are preferable.

As porous oxides, inorganic oxides such as SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ or composites containing these inorganic oxides Or a porous material containing a mixture as a main component. Specific examples of the porous oxide include natural or synthetic zeolites; SiO ₂ -MgO, SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , porous oxide composed mainly of such _{SiO 2 -V 2 O 5, SiO} 2 -Cr 2 O 3, SiO 2 -TiO 2 -MgO and the like. Of these, porous oxides whose main component is SiO ₂ and / or _Al 2 _{O 3} is 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. Moreover, after dissolving an inorganic halide in solvent, such as alcohol, what was made to precipitate in fine particle shape with a precipitation agent can also be used.

  The clay used as the carrier (c) is usually composed mainly of clay minerals. 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, ion crystalline compound having a layered crystal structure such as hexagonal close packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. It 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.

As the ion exchangeable layered compound, 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 acid salts of polyvalent metals such as NH ₄ PO ₄ ) ₂ .H ₂ O and the like.

  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 as 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, organic matter treatment and the like. 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. The 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 a state where the layers are expanded by exchanging the exchangeable ions between the layers with other large and bulky ions using the ion-exchangeability. May be Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. Also, 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, etc .; metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ etc. It can be mentioned. These compounds can be used alone or in combination of two or more. Also, when intercalating these compounds, they are obtained by hydrolyzing metal alkoxides (R is a hydrocarbon group etc.) such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ etc. Polymers, colloidal inorganic compounds such as SiO _2, and the like can also coexist. Moreover, as a pillar, the oxide etc. which are produced | generated by heat-dehydrating after intercalating the said metal hydroxide ion between layers are mentioned.

  The clay, clay mineral and ion exchangeable layered compound may be used as they are, or may be used after processing such as ball milling and sieving. Further, it may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. The substance 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, (co) polymer, vinylcyclohexane, and styrene, which are mainly composed of α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, are used. Examples include (co) polymers produced as main components, and their modified products.

  The catalyst for olefin polymerization used for the production of the copolymer (B) is a crosslinked metallocene compound (a), (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b- 3) At least one compound (b) selected from the group consisting of ionized ionic compounds and a carrier (c) used as necessary may be included.

<Method of polymerizing monomers in the presence of a catalyst for ethylene / α-olefin / non-conjugated polyene copolymer>
When ethylene, an alpha-olefin, and a nonconjugated polyene are copolymerized, usage of each component which comprises a polymerization catalyst, addition order are chosen arbitrarily, The following methods are illustrated.

(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 a polymerization vessel in an arbitrary order.
(3) A method in which the catalyst component having the compound (a) supported on the carrier (c) and the compound (b) added to the polymerizer in any order.
(4) A method in which the catalyst component having the compound (b) supported on the carrier (c) and the compound (a) added to the polymerizer in any order.
(5) A method of adding a catalyst component having the compound (a) and the compound (b) supported on the carrier (c) to a polymerization vessel.

  In each of the 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. The catalyst component may further be supported on the prepolymerized solid catalyst component.

  The ethylene / α-olefin (3 to 20 carbon atoms) / non-conjugated polyene copolymer (B) is prepared in the presence of the above-described catalyst for ethylene / α-olefin / non-conjugated polyene copolymer. It can be produced by copolymerizing olefins and non-conjugated polyenes.

  The copolymer (B) can be produced by either a liquid phase polymerization method such as solution (solution) polymerization or suspension polymerization, or a gas phase polymerization method.

  As an inert hydrocarbon medium used in the liquid phase polymerization method, 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; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane. The inert hydrocarbon medium may be used alone or in combination of two or more. Also, olefin itself can be used as a solvent.

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

  In the organometallic compound (b-1), the molar ratio [(b-1) / M] of the compound (b-1) to all transition metal atoms (M) in the bridged metallocene compound (a) is usually 0. 0.1 to 50000, preferably 0.05 to 10000, is used. In the organoaluminum oxy compound (b-2), the molar ratio [(b-2) / M] of the aluminum atom in the compound (b-2) to the total transition metal (M) in the compound (a) is The amount is usually 10 to 50000, preferably 20 to 10000. In the ionizing ionic compound (b-3), the molar ratio [(b-3) / M] of the compound (b-3) to the transition metal atom (M) in the compound (a) is usually 1 to 20. The amount is preferably 1 to 15.

  The polymerization temperature of the copolymer (B) is usually in the range of -50 to + 200 ° C, preferably in the range of 0 to + 200 ° C, and more preferably in the range of +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. Further, the polymerization reaction type of the copolymer (B) may be any of a batch system, a semi-continuous system, and a continuous system. 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. In the case where 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).

<Filler (C)>
The filler (C) is at least one filler selected from a magnesium silicate filler (C-α), a carbonate filler (C-β1), and an aluminum silicate filler (C-β2). Agent (C-.beta.), And the mass ratio ((C-.alpha.) / (C-.beta.)) 100/30 to 100/100 of the magnesium silicate-based filler (C-.alpha.) And the filler (C-.beta.) Preferably, it contains in the range of 100/100 to 100/1200.

  Examples of magnesium silicate fillers include talc and florisil. Examples of carbonate fillers include calcium carbonate, basic magnesium carbonate and dolomite. Examples of the aluminum silicate-based filler include clay, kaolin, mica and pyrophyllite.

  When the mass ratio ((C-α) / (C-β)) of the magnesium silicate-based filler (C-α) to the filler (C-β) was less than 100/1200, it was left under high temperature. In the case where oil bleeding is likely to occur, if it exceeds 100/30, deformation of the bellows will be delayed.

  As the filler (C-β), either a carbonate filler (C-β1) or an aluminum silicate filler (C-β2) may be used alone or in combination.

  The total blending amount of the filler (C) is 20 to 70 parts by mass, preferably 30 with respect to 100 parts by mass of ethylene / α-olefin (carbon number 3 to 20) / non-conjugated polyene copolymer (B) -60 mass parts. When the total blending amount of the filler (C) is less than 20 parts by mass, the vibration stability of the dust cover is reduced, and when it exceeds 70 parts by mass, the mechanical properties are reduced.

<Phenolic resin crosslinking agent (D)>
In the present invention, a phenol resin-based crosslinking agent (D) is preferably used as the crosslinking agent.

  The phenol resin based crosslinking agent (D) (also referred to as the crosslinking agent (D) in the present invention) is a resole resin, which is a condensation of an alkyl substituted phenol or an unsubstituted phenol with an aldehyde in an alkaline medium, preferably with formaldehyde. It is also preferred to be prepared by condensation of difunctional phenolic dialcohols. The alkyl-substituted phenol is preferably an alkyl group-substituted product having 1 to 10 carbon atoms. Furthermore, dimethylol phenols 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.

  The following general formula (I) can be mentioned as an example of a phenol resin type cured resin (phenol resin type crosslinking agent).

（式中、Ｑは、−ＣＨ_２−及び−ＣＨ_２−Ｏ−ＣＨ_２−から成る群から選ばれる二価の基であり、ｍは０又は１〜２０の正の整数であり、Ｒ'は有機基である）。

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

Preferably, Q is a divalent radical _-CH 2 -O-CH ₂ - and is, m is 0 or 1 to 10 a positive integer, R 'is an organic radical 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 hydroxyl groups at the ends. An example of a phenol resin-based cured resin whose terminal is brominated is shown in the following general formula (II).

（式中、ｎは０〜１０の整数、Ｒは炭素数１〜１５の飽和炭化水素基である。）

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

  As a product example of the said phenol resin-type cured resin, Takiroll (trademark) 201 (alkyl phenol formaldehyde resin, Taoka Chemical Industry Co., Ltd. product made), Takiroll (trademark) 250-I (the bromination rate is 4% of bromination) Alkylphenol formaldehyde resin, manufactured by Taoka Chemical Industry Co., Ltd., Tackiroll (registered trademark) 250-III (brominated alkylphenol formaldehyde resin manufactured by Taoka Chemical Industry Co., Ltd.), PR-4507 (Gunei Chemical Industry Co., Ltd.) Vulkaresat 510E (Hoechst), Vulkaresat 532E (Hoechst), Vulkaresen E (Hoechst), Vulkaresen 105E (Hoechst), Vulkaresen 130E (Hoechs) Vulkaresol 315E (Hoechst), Amberol ST 137X (Rohm & Haas), Sumilight Resin (registered trademark) PR-22193 (Sumitomo Durez Co., Ltd.), Symphorm-C-100 (Anchor Chem.) Made, Symphorm-C-1001 (Anchor Chem.), Tamanor (registered trademark) 531 (Arakawa Chemical Co., Ltd.), Schenectady SP 1059 (Schenectady Chem.), Schenectady SP 1045 (Schenectady Chem.) ), CRR-0803 (manufactured by U.C. C.), Schenectady SP 1055F (manufactured by Schenectady Chem., Brominated alkylphenol formaldehyde) De resin), Schenectady SP1056 (Schenectady Chem. Companies made), CRM-0803 (Showa Union Synthesis Co., Ltd.), Vulkadur A (Bayer Corporation). Among them, halogenated phenol resin-based crosslinking agents are preferable, and brominated alkylphenol-formaldehyde resins such as Tackiroll (registered trademark) 250-I, Tackyroll (registered trademark) 250-III, and Schenectady SP 1055F 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 composed 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 alkaline media, 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 consisting of a methylolphenol curable resin, a halogen donor and a metal compound is particularly recommended, the details of which are described in US Pat. Nos. 3,287,440 and 3,709,840. It is done. Non-halogenated phenolic resin-based crosslinkers are used simultaneously with the halogen donor, preferably with a hydrogen halide scavenger. Usually, a halogenated phenolic resin-based crosslinking agent, preferably a brominated phenolic resin-based crosslinking agent containing 2 to 10% by mass of bromine does not require a halogen donor. For example, iron oxide, titanium oxide, oxidation It is used simultaneously with hydrogen halide scavengers such as magnesium, magnesium silicate, silicon dioxide and zinc oxide, preferably metal oxides such as zinc oxide. These hydrogen halide scavengers such as zinc oxide are usually used in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the phenol resin-based crosslinking agent. Although the presence of such a scavenger accelerates the crosslinking action of the phenolic resin crosslinking agent, in the case of a rubber which is not easily vulcanized by the phenolic resin crosslinking agent, it is desirable to share a halogen donor and zinc oxide. The preparation of halogenated phenolic curable resins and their use in vulcanizing agent 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 along with the disclosures of the aforementioned U.S. Patent Nos. 3,287,440 and 3,709,840. Examples of suitable halogen donors include, for example, stannous chloride, ferric chloride or halogen donating heavy 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 material that substantially increases the crosslinking efficiency of the phenolic resin based crosslinking agent, and includes metal oxides and halogen donors, which are It is 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 crosslinking agents and brominated phenolic resin based crosslinking agents are commercially available, such as such crosslinking agents from Schenectady Chemicals, Inc. under the trade designation "SP-1045", "CRJ-352", It can be purchased as "SP-1055F" and "SP-1056". Similar functionally equivalent phenolic resin based crosslinkers can also be obtained from other suppliers.

  The crosslinking agent (D) is a suitable vulcanizing agent from the viewpoint of preventing fogging because generation of decomposition products is small. The crosslinking agent (D) 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 (D), sulfur, p-quinonedioxime, p, p′-dibenzoylquinonedioxime, N-methyl-N, 4-dinitrosoaniline, nitrosobenzene, Peroxy crosslinking aids such as diphenyl guanidine, trimethylolpropane-N, N'-m-phenylenedimaleimide, divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane Auxiliary agents 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.

Moreover, in order to accelerate | stimulate decomposition | disassembly of a crosslinking agent (D), 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.

<Other ingredients>
In the composition of the present invention, in addition to the crystalline polyolefin (A), the copolymer (B), the filler (C) and the crosslinking agent (D), additives may be added insofar as the effects of the present invention are not impaired. You may mix | blend. Although it does not specifically limit as an additive, An inorganic filler (F) other than a softener (E) and a filler (C) etc. are mentioned. As additives, rubbers other than copolymer (B) (for example, polyisobutylene, butyl rubber, propylene / ethylene copolymer rubber, propylene / butene copolymer rubber, propylene / butene / ethylene copolymer rubber, etc.) Propylene elastomers, ethylene elastomers such as ethylene / propylene copolymer rubber, styrene thermoplastic elastomers); resins other than crystalline polyolefins (A) such as thermosetting resins and thermoplastic resins such as polyolefins; Used in the field of polyolefins such as lubricants such as waxes, lubricants, anti-oxidants, anti-aging agents, anti-aging agents, anti-aging agents, anti-light stabilizers, weathering stabilizers, antistatic agents, metal soaps, aliphatic amides, and waxes. And known additives.

  Each of these additives may be used alone or in combination of two or more.

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

  As the softener (E), softeners usually used for rubber can be used. As the softening agent (E), 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 Fatty oil-based softeners such as rapeseed oil, soybean oil, coconut oil; tall oil; sub (factice); 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 polymers such as terpene resin, petroleum resin, atactic polypropylene, coumarone indene resin; dioctyl phthalate, dioctyl adipate, Ester softening such as dioctyl sebacate ; Microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, liquid Thiokol, and a hydrocarbon-based synthetic lubricating oils.

  These softeners (E) are not particularly limited as long as the effects of the present invention are exerted, but are preferably 105 to 150 parts by mass, more preferably 110 to 130 parts by mass with respect to 100 parts by mass of the copolymer (B). Used in quantity. When the softening agent (E) is used in such an amount, the fluidity at the time of preparation and molding of the composition is excellent, the dispersibility of carbon black and the like is improved, and it is difficult to reduce the mechanical properties of the obtained molded body. Moreover, the molded object obtained is excellent in heat resistance and heat aging resistance.

  As the inorganic filler (F) other than the filler (C), calcium silicate, silica, diatomaceous earth, asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, molybdenum disulfide, graphite, carbon black, glass fiber, Examples thereof include glass spheres, shirasu balloons, basic magnesium sulfate whiskers, calcium titanate whiskers, and aluminum borate whiskers.

  These inorganic fillers (F) are usually used in an amount of 1 to 8 parts by mass, preferably 1 to 7 parts by mass, with respect to 100 parts by mass of the copolymer (B).

As an acid acceptor, oxides or hydroxides of divalent metals such as ZnO, MgO, CaO, Mg (OH) ₂ , Ca (OH) ₂ or hydrotalcite Mg ₆ Al ₂ (OH) ₁₆ CO ₃ NH ₂ O is used. These acid acceptors are usually used in an amount of 20 parts by mass or less, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the copolymer (B).

  Examples of the antioxidant include aromatic secondary amine antioxidants such as phenylbutylamine and N, N-di-2-naphthyl-p-phenylenediamine; dibutylhydroxytoluene, tetrakis [methylene (3,5-di- -T-butyl-4-hydroxy) hydrocinnamate] phenolic antioxidants such as methane; bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl] sulfide Thioether-based anti-aging agents; dithiocarbamate-based anti-aging agents such as nickel dibutyldithiocarbamate; 2-mercaptobenzoylimidazole, zinc salts of 2-mercaptobenzimidazole, dilaurylthiodipropionate, distearylthiodipropionate, etc. There is a sulfur-based anti-aging agent.

  When rubber other than the copolymer (B) is used, the rubber is usually used in an amount of 5 to 80 parts by mass, preferably 10 to 60 parts by mass with respect to 100 parts by mass of the copolymer (B). . It is preferable not to contain a styrene-based thermoplastic elastomer from the viewpoint of heat resistance.

[Thermoplastic Elastomer Composition and Method for Producing the Same]
The thermoplastic elastomer composition (X) constituting the molded article of the present invention is preferably a crystalline polyolefin (A), a copolymer (B), a filler (C) and a crosslinking agent, preferably a crosslinking agent (D) ), And a mixture containing an additive that is blended as necessary is dynamically heat-treated and crosslinked (dynamic crosslinking). The thermoplastic elastomer composition thus obtained is at least partially crosslinked.

  It is light in weight and has high strength, and has excellent oil resistance and mechanical properties, only by dynamically crosslinking the crystalline polyolefin (A), the copolymer (B) and the filler (C) with a crosslinking agent. In addition, a thermoplastic elastomer composition having a low coefficient of linear expansion and excellent dimensional stability can be 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.

  In the thermoplastic elastomer composition (X), the crosslinking agent (D) is usually 0.1 to 20 parts by mass, preferably 1 to 12 parts by mass, more preferably 100 parts by mass of the copolymer (B). The amount used is 1 to 10 parts by mass. By setting the blending amount of the crosslinking agent (D) 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 It has heat resistance and mechanical properties.

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 from the melting point of the crystalline polyolefin (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.

[Molded body of the present invention]
The bellows-shaped molded article of the present invention is produced using the thermoplastic elastomer composition (X). Molded articles produced using the thermoplastic elastomer composition (X) can be balanced at high levels with oil bleed, bending characteristics (deformability of bellows) and oil resistance.

  Examples of the bellows-shaped molded body of the present invention include a sealing material such as an automobile dust cover, an air duct hose, and a rack and pinion boot.

  The dust cover has a thin cylindrical shape as a whole. As a method of forming the dust cover, blow molding is suitably adopted, but injection molding can also be adopted.

  EXAMPLES The present invention will next be described in more detail by way of examples, which should not be construed as limiting the invention thereto. In the following description of Examples and the like, “parts” means “parts by mass” unless otherwise specified. In the present invention, parts by weight and parts by mass are treated synonymously.

[Measuring method]
[Ethylene / α-olefin / non-conjugated polyene copolymer]
[Molar amount and mass of each structural unit]
The molar amount and the mass of the structural unit derived from ethylene [A], the structural unit derived from α-olefin [B] and the structural unit derived from non-conjugated polyene [C] are measured by intensity measurement with ¹ H-NMR spectrometer. Asked.

[Mooney viscosity]
Mooney viscosity ML _{(1 + 4)} 125 ° C. was measured according to JIS K6300 (1994) using a Mooney viscometer (SMV202 type, manufactured by Shimadzu Corporation).

[Physical Properties of Thermoplastic Elastomer Composition and Molded Body]
The thermoplastic elastomer compositions and the methods for evaluating the physical properties of the molded articles in the following examples and comparative examples are as follows.

[Shore D hardness]
In accordance with ISO7619 (JIS K6253), an injection-molded square plate having a thickness of 3 mm was used, and measurement was performed using a Shore D hardness tester using a laminated sheet having a thickness of 6 mm (two pieces each having a thickness of 3 mm). For Shore D hardness, an instantaneous value was determined.

[Shore A hardness]
The pellets of the obtained thermoplastic elastomer composition are press molded for 6 minutes at 230 ° C. using a 100 t electrothermal automatic press (manufactured by Shoji), and then cold pressed for 5 minutes at room temperature to obtain a 3 mm-thick press sheet Made. Using the sheet, a scale was read immediately after contact with a needle using an A-type measuring device in accordance with JIS K6253.

[density]
The density was calculated from the weight of each sample measured in water and in air using ALFA MIRAGE's electronic hydrometer MD-300S according to ASTM D1505 (submersion method).

[Compression set (CS)]
The pellets of the obtained thermoplastic elastomer composition are press molded for 6 minutes at 230 ° C. using a 100 t electrothermal automatic press (manufactured by Shoji Co., Ltd.), and then cold pressed for 5 minutes at room temperature to obtain a 2 mm-thick press sheet Made.

The 2 mm-thick press sheets produced as described above were laminated in accordance with JIS K 6250, and a compression set test was conducted in accordance with JIS K 6262.
Test conditions were measured using a laminated sheet with a thickness of 12 mm (four pieces of 3 mm thick pieces) under conditions of 25% compression, 70 ° C., 22 hours, and 30 minutes after strain removal (compression). did.

[Initial flexural modulus]
An injection molded square plate with a width of 12.4 mm and a thickness of 3 mm was carried out at a span distance of 48 mm and a speed of 5 mm / minute under an atmosphere of 23 ° C. using a 5-bond bending tester (AG-1 kNX plus).

[Tensive properties]
It measured according to the method of JIS K6301.
The test piece used was a No. 3 dumbbell piece punched out of a 2 mm thick press sheet.
Measurement temperature: 23 ° C
M100: Stress at 100% elongation (MPa)
TB: tensile breaking strength (MPa)
EB: tensile elongation at break (%)

[Oil resistance test: Weight change rate]
A 2 mm pressed sheet was immersed at 80 ° C. for 24 hours using liquid paraffin (soft) (Nacalai Tesque, Inc. Code number: 26132-35) as a test oil. After that, the sample surface was wiped off, and the weight change rate was measured at n number = 2.

[Crystallization temperature]
An exothermic / endothermic curve of DSC was obtained, and the temperature at the maximum exothermic peak position when the temperature was lowered was defined as the crystallization temperature. In the above values, the sample is packed in an aluminum pan, heated to 200 ° C. at 100 ° C./min and held at 200 ° C. for 5 minutes, then cooled to -150 ° C. at 30 ° C./min and then 30 ° C./min It calculated | required from the exothermic and endothermic curve at the time of temperature rising.

[Degree of crystallinity]
The degree of crystallinity can be determined by wide angle X-ray diffraction (hereinafter referred to as "WAXD"). WAXD measurement can be carried out using a general wide-angle X-ray diffraction measurement apparatus, for example, it is measured using a polymer dedicated beamline BL03XU installed in a large synchrotron radiation facility SPring-8 (Hyogo Prefecture) be able to.

Scattering intensity curve I (2θ) obtained by plotting scattering intensity I obtained by WAXD measurement against scattering angle 2θ (vertical axis is I (2θ), horizontal axis is 2θ) or scattering intensity I is defined by equation (1) The peak of the scattering intensity curve I (q) [vertical axis is I (q), horizontal axis q] plotted against the size q of the scattering vector to be separated is When the scattering intensity S _c derived from γ and the scattering intensity S _a derived from the amorphous phase of the polymer are obtained, the crystallinity φ _C can be calculated by the equation (2). λ is the wavelength of the incident X-ray.

(measuring device)
The WAXD measurement was carried out with the polymer-dedicated beamline BL03XU installed at the large radiation facility SPring-8 (Hyogo Prefecture).

(Measurement condition)
As the X-ray, an X-ray having a wavelength of 1 Å (0.1 nm) was used.
The detector used was a flat panel detector.
The measurement was performed at room temperature (25 ° C.).

(Example crystallinity analysis conditions)
With a 0.5 mm extruded sheet, peak separation is performed using a scattering intensity curve I (q) (the vertical axis is I (q), the horizontal axis is q) with q ranging from 6 nm ^-1 to 17.5 nm ^-1 After the crystallization, the degree of crystallinity was calculated.

[Oil bleed]
An extruded sheet having a thickness of 0.5 mm was cut into a size of 20 cm × 2 cm, and heated at 80 ° C. for 72 hours using a constant temperature thermostat (DN610H, manufactured by Yamato Scientific Co., Ltd.). After heating, the sample was taken out and the surface gloss change was confirmed.

(Criteria)
○: No gloss change ×: Gloss change on the surface or edge

Synthesis Example 1 Synthesis of Ethylene / Propylene • 5-Ethylidene-2-Norbornene Copolymer (EPDM) Ethylene, propylene as α-olefin, non-continuously using a 300 L volume polymerizer equipped with a stirring blade A polymerization reaction of a terpolymer composed of 5-ethylidene-2-norbornene (ENB) as a conjugated polyene was performed at 90 ° C.

  As a polymerization solvent, hexane (feed amount: 74 L / h) is used continuously, ethylene feed amount is 6.6 Kg / h, propylene feed amount is 3.2 Kg / h, ENB feed amount is 0.56 Kg / h, and Each component was continuously supplied to the polymerization reactor so that the hydrogen feed amount was 10.9 NL / h.

While maintaining the polymerization pressure at 1.8 MPa and the polymerization temperature at 90 ° C., [N- (1,1-dimethylethyl) -1,1-dimethyl-1-[(1,2,3,3A, 8A-η) -1,5,6,7-Tetrahydro-2-methyl-S-indacen-1-yl] silane aminate (2-)-κN] [(1,2,3,4-η)- Using 1,3-pentadiene] -titanium, the main catalyst was continuously supplied so as to have a feed amount of 0.015 mmol / h. In addition, the feed amount of (C ₆ H ₅ ) ₃ CB (C ₆ F ₅ ) ₄ as a co-catalyst is 0.075 mmol / h, and the feed amount of triisobutylaluminum (TIBA) as an organic aluminum compound is 10 mmol / h, Each was supplied continuously.

  Thus, an ethylene / α-olefin / non-conjugated polyene copolymer composed of ethylene, propylene and ENB was obtained in a 9.1 mass% solution state. 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 after the ethylene / α-olefin / non-conjugated polyene copolymer was separated from the solvent by steam stripping treatment, 80 It was dried under reduced pressure overnight at ° C.

  By the above operation, an ethylene / α-olefin / non-conjugated polyene copolymer formed from ethylene, propylene and ENB was obtained at a rate of 5.3 kg / hour.

Example 1 Thermoplastic Elastomer Composition and Molded Article Ethylene-propylene-5 having an ethylene content of 63 mol%, an iodine value of 13 and a Mooney viscosity [ML _{(1 + 4)} 125 ° C.] of 116 obtained in Synthesis Example 1 100 parts by mass of ethylidene-2-norbornene copolymer rubber (EPDM), melt flow rate (ASTM D 1238-65 T; 230 ° C., 2.16 kg load) 0.5 g / 10 min, density 0.91 g / cm ³ Propylene homopolymer (PP-1) of 95 parts by weight, melt flow rate (ASTM D 1238-65 T; 230 ° C., 2.16 kg load) 10 g / 10 min, density 0.91 g / cm ³ propylene homopolymer (PP-2) 20 parts by mass, softener (trade name: Diana Process PW-100, paraffin oil, manufactured by Idemitsu Kosan Co., Ltd.) 120 Parts by mass, brominated alkylphenol formaldehyde resin (trade name: SP-1055F, manufactured by Schenectady) 8 parts by mass as a phenol resin-based crosslinking agent, zinc oxide (zinc oxide 2 types, manufactured by Haxiitec) 0.5 parts by mass, talc ( Brand name: High filler # 5000 PJ, made by Matsumura Sangyo Co., Ltd. 24 parts by mass, calcium carbonate (trade name: Whiteton SB Red, manufactured by Shiroishi Calcium Co., Ltd.) 24 parts by mass, carbon black master batch (trade name: PEONY BLACK) 3 parts by mass of F32387 MM, manufactured by DIC Corporation, as an extruder (Product No. KTX-30, manufactured by Kobe Steel, Ltd., cylinder temperature: C1: 50 ° C., C2: 90 ° C., C3: 100 ° C., C4: 120 ° C. C5: 180 ° C., C6: 200 ° C., C7 to C14: 200 ° C., die temperature: 200 ° C., screen Over rotational speed: 500 rpm, extrusion rate: 40 kg at / h), subjected to dynamic cross-linking of the resulting mixture to obtain pellets of the thermoplastic elastomer composition. The blending and evaluation results are shown in Table 1.

[Example 2] Thermoplastic elastomer composition and molded body Example except that the blending amount of the softener (trade name: Diana Process PW-100, paraffin oil, manufactured by Idemitsu Kosan Co., Ltd.) is changed from 120 parts by weight to 130 parts by weight. 1 was processed. The formulation and evaluation results are shown in Table 1.

[Example 3] Composition of thermoplastic elastomer composition and molded article Talc (trade name: High Filler # 5000PJ, manufactured by Matsumura Sangyo Co., Ltd.) and calcium carbonate (trade name: Whiten SB red, Shiraishi Calcium Co., Ltd.) The same treatment as in Example 1 was conducted except that the amount was changed to 12 parts by mass and 36 parts by mass, respectively. The blending and evaluation results are shown in Table 1.

[Example 4] Composition of thermoplastic elastomer composition and molded article Talc (trade name: High Filler # 5000PJ, manufactured by Matsumura Sangyo Co., Ltd.) and calcium carbonate (trade name: Whiten SB red, Shiraishi Calcium Co., Ltd.) The same treatment as in Example 1 was conducted except that the amount was changed to 36 parts by mass and 12 parts by mass, respectively. The blending and evaluation results are shown in Table 1.

[Example 5] Composition of thermoplastic elastomer composition and molded article Talc (trade name: High Filler # 5000PJ, manufactured by Matsumura Sangyo Co., Ltd.) and calcium carbonate (trade name: Whiten SB red, Shiraishi Calcium Co., Ltd.) The same treatment as in Example 1 was conducted except that the amount was changed to 4 parts by mass and 44 parts by mass, respectively. The formulation and evaluation results are shown in Table 1.

[Example 6] Thermoplastic elastomer composition and molded body Instead of 24 parts by mass of calcium carbonate (trade name: Whiten SB red, manufactured by Shiraishi Calcium Co., Ltd.), clay (trade name: ICECAP K, manufactured by Burgess) The same treatment as in Example 1 was carried out except that 24 parts by mass was used. The formulation and evaluation results are shown in Table 1.

Example 7 Thermoplastic Elastomer Composition and Molded Body The compounding amount of calcium carbonate (trade name: Whiteton SB Red, manufactured by Shiroishi Calcium Co., Ltd.) is changed to 12 parts by mass, clay (trade name: ICECAP K, Bergess) It processed similarly to Example 1 except using 12 mass parts made by corporation. The formulation and evaluation results are shown in Table 1.

Comparative Example 1
Calcium carbonate (trade name: trade name: Hi Filler # 5000 PJ, manufactured by Matsumura Sangyo Co., Ltd.) and 24 parts by weight of calcium carbonate (trade name: Whiteton SB Red, manufactured by Shiroishi Calcium Co., Ltd.) : Whiten SB red, manufactured by Shiraishi Calcium Co., Ltd.) 48 parts by weight were used in the same manner as in Example 1. The formulation and evaluation results are shown in Table 1.

[Comparative Examples 2 to 6]
The same treatment as in Comparative Example 1 was carried out except that the composition was changed as shown in Table 1. The formulation and evaluation results are shown in Table 1.

  From Table 1, oil bleed is generated by using only calcium carbonate as a filler in Comparative Example 1, oil resistance deteriorates due to a decrease in oil content in Comparative Example 2, and Comparative Example 3 has a filler ratio outside the range. Since the initial flexural elasticity is high and the ratio of the filler in Comparative Example 4 is out of the range, oil bleed occurs. In Comparative Example 5, oil bleed occurs when only clay is used as the filler. Since this is a combination of calcium carbonate and clay and talc is not used, oil bleed occurs, and it can be seen that Examples 1-7 balance oil bleed, oil resistance and flexibility at a high level.

Claims (5)

60 to 200 parts by mass of crystalline polyolefin (A) having a melt flow rate (230 ° C., 2.16 kg load) of 0.01 to 100 g / 10 min and a melting point (Tm) of 100 ° C. or higher,
100 parts by mass of ethylene / α-olefin (3 to 20 carbon atoms) / non-conjugated polyene copolymer (B) having a Mooney viscosity ML _{(1 + 4)} (125 ° C.) of 10 to 250,
Including 20 to 70 parts by mass of a filler (C),
The filler (C) is at least one selected from magnesium silicate based filler (C-α), carbonate based filler (C-β1) and aluminum silicate based filler (C-β2) The filler (C-β) and the mass ratio of the magnesium silicate based filler (C-α) to the filler (C-β) ((C-α) / (C-β)) 100/30 to 100 / Include at 1200,
Initial flexural modulus at 23 ° C. is 50 to 180 MPa, and Type D hardness (after 5 seconds) according to JIS K6253 is 20 to 50 or Type A hardness (instantaneous value) according to JIS K6253 is 80 to 95 The bellows-like molded object which consists of a thermoplastic elastomer composition (X).   The molded article according to claim 1, wherein at least a part of the thermoplastic elastomer composition (X) is crosslinked with the phenol resin-based crosslinking agent (D).   The molded article according to claim 1 or 2, wherein the thermoplastic elastomer composition (X) further contains 105 to 150 parts by mass of a softening agent (E).   The sealing material which consists of a molded object as described in any one of Claims 1-3.   The automotive dust cover which consists of a molded object as described in any one of Claims 1-3.