Technical field
[0001]
　The present invention (1) relates to a thermoplastic elastomer composition, more particularly, to a lightweight, high strength, it relates to a thermoplastic elastomer composition capable of providing a molded article excellent in oil resistance and mechanical properties.
[0002]
　The present invention (2) is an ethylene-alpha-olefin-nonconjugated polyene copolymer and uses thereof.
Background technique
[0003]
　Olefinic thermoplastic elastomers, since light recycling is easy, the energy saving, as a thermoplastic elastomer resource saving type, especially as the vulcanized rubber alternative, for an automobile, hoses, pipes and boot (blow molding) such as are widely used in automotive parts and the like (e.g., Patent documents 1 and 2).
[0004]
　However, these automobile parts, has a constant need for weight reduction for fuel economy improvement, thermoplastic elastomers which are used for containing a large amount of filler, tend density is increased, inhibiting component weight Was. These automobile parts is used at locations in contact, such as a lubricating oil or grease, in general, the olefinic thermoplastic elastomer has low oil resistance against paraffinic process oil, an olefinic heat in these automobile parts obtained include thermoplastic elastomers, low oil resistance, a further improvement has been desired.
[0005]
　Further, since the ethylene-alpha-olefin rubber such as ethylene-propylene copolymer rubber (EPR) and ethylene-propylene-diene copolymer rubber (EPDM) they are, have no unsaturated bond in the main chain of the molecular structure, compared with general-purpose conjugated diene rubber, heat aging resistance, weather resistance, excellent ozone resistance, automobile parts, electric wire materials, electric and electronic parts, civil construction materials, are widely used in applications such as industrial material parts.
[0006]
　Recently, excellent heat resistance of the ethylene · alpha-olefin rubber, as needs utilizing weatherability and flexibility, material development of transparent crosslinked sheet for, product development has been actively conducted.
[0007]
　Applications of EPDM for example, ethylene-propylene-diene copolymer rubber (EPDM), it is known to use as the rubber component of the hose forming composition (Patent Document 3). Application hose is used, for example, automobiles, etc., since the use in cold areas envisaged, in addition to the mechanical properties at room temperature (tensile strength, etc.), rubber characteristics at low temperature (rubber elasticity, etc.) required It is.
[0008]
　Low-temperature flexibility of the ethylene-propylene-diene copolymer rubber (EPDM), as a method of improving the thermal aging resistance, as α- olefins, using α- olefin having 4 to 10 carbon atoms, ethylene and α- olefin ethylene-alpha-olefin-nonconjugated polyene copolymer excellent in randomness has been proposed (Patent Document 4). The Example 4 of Patent Document 4, the B value represented by the following formula is an index showing the quality of randomness, at maximum, the ethylene-1-butene-ENB copolymer 1.12 was obtained There has been described.
[0009]
　　B value = [EX] / (2 [ E] × [X]) ··· (i)
　(In the formula (i), [E] and [X] is an ethylene-alpha-olefin-nonconjugated polyene copolymerization It represents ethylene and α- olefin molar fraction of 4 to 20 carbon atoms in the polymer, respectively, [EX] is a fraction of dyad sequence of α- olefins ethylene having 4 to 20 carbon atoms.)
　On the other hand, patent the embodiment of the document 5, a specific transition metal compound (bridged metallocene compound) with, B value indicating the randomness (where the B value described in Patent Document 2, somewhat different definitions), 1.11 can give ethylene-propylene-ENB copolymer ~ 1.24 is disclosed. Incidentally, Patent Document 5, the mechanical properties of the ethylene-propylene-ENB copolymer is not described.
[0010]
　　[B value = (c + d) / [2 × a × (e + f)] ‥ [IV]
(wherein [IV], a, e and f are respectively the ethylene / alpha-olefin / nonconjugated polyene copolymer ethylene mole fraction, an α- olefin mole fraction and a non-conjugated Porienmoru fraction, c is an ethylene -α- olefin dyad molar fraction, d is an ethylene -. nonconjugated polyene dyad molar fraction)
　also, olefinic thermoplastic elastomers, since light recycling is easy, the energy saving, as a thermoplastic elastomer resource saving type, especially as the vulcanized rubber alternative, hoses for automobiles, pipes and boot (blow molding) such as are widely used in automobile parts or the like (e.g., Patent documents 6 and 7).
[0011]
　However, these automobile parts, has a constant need for weight reduction for fuel economy improvement, thermoplastic elastomers which are used for containing a large amount of filler, tend density is increased, inhibiting component weight Was. These automobile parts is used at locations in contact, such as a lubricating oil or grease, in general, the olefinic thermoplastic elastomer has low oil resistance against paraffinic process oil, an olefinic heat in these automobile parts obtained include thermoplastic elastomers, low oil resistance, a further improvement has been desired.
CITATION
Patent Literature
[0012]
Patent Document 1: JP 2001-294714 Patent Publication
Patent Document 2: JP 2011-202136 Patent Publication
Patent Document 3: JP-A-9-67485 Publication
Patent Document 4: JP-A 9-71617 Patent Publication
Patent Document 5: International Publication No. 2009/081794
Patent Document 6: JP 2001-294714 Patent Publication
Patent Document 7: JP 2011-202136 JP
Summary of the Invention
Problems that the Invention is to Solve
[0013]
　The present invention (1), there has been made in order to solve the above problems, a light weight, has excellent oil resistance than conventional crosslinked thermoplastic elastomers, and conventional cross-linked heat an object equal to or larger than that of the thermoplastic elastomer, and hardness, to provide tensile strength and tensile elongation thermoplastic elastomer composition which can be a molded article having mechanical properties, such as.
[0014]
　Obtained contains thermoplastic elastomer composition has a better oil resistance, molded, in particular, an object of automotive hoses, providing auto parts such as pipes and boot (blow molding).
[0015]
　Another object of the present invention (2) is compared with the previously proposed an ethylene-alpha-olefin-nonconjugated polyene copolymer, further, small compression set at low temperature, and has flexibility, It is to obtain the ethylene-alpha-olefin-non-conjugated polyene copolymer having an excellent balance between tensile strength of rubber elasticity and cold at low temperatures.
[0016]
　In view of the possibility of the hose in cold regions is used, the hose having both low-temperature properties and mechanical properties are desired. For example, the use of hose forming composition comprising ethylene content is kept low EPDM, low temperature properties of the resulting hose is improved, tensile strength is known to decrease.
[0017]
　Another object of the present invention (2) is to provide a hose forming composition capable of forming an excellent hose low temperature characteristics and mechanical properties, and a hose formed from the composition .
[0018]
　Further, the present invention (2) is a light-weight, has excellent oil resistance than conventional crosslinked thermoplastic elastomers, and, of equal to or more than the conventional cross-linked thermoplastic elastomer, and hardness, tensile strength and it aims to provide a thermoplastic elastomer composition which can be a molded article having mechanical properties such as tensile elongation. Furthermore, the resulting comprise thermoplastic elastomer compositions have better oil resistance, molded, in particular, an object of the automotive, the provision of automotive parts such as hoses and boots (blow molding).
Means for Solving the Problems
[0019]
　The present inventors have conducted extensive studies to solve the above problems. As a result, a crystalline olefin polymer, and specific ethylene-alpha-olefin-nonconjugated polyene copolymer, a thermoplastic elastomer composition obtained by dynamically crosslinking a mixture comprising a phenolic resin-based crosslinking agent found that it is possible to solve the above problems, and have completed the present invention (1).
[0020]
　(In the present invention, also referred to as composition (I)) The present invention (1) The thermoplastic elastomer composition according to the ethylene to satisfy crystalline olefin polymer (A), the following requirements (1) and (2) · alpha-olefin (having 4 to 20 carbon atoms), non-conjugated polyene copolymer (1B), and the mixture characterized in that it is obtained by dynamically crosslinking comprising phenolic resin-based crosslinking agent (C).
[0021]
　(1) B value represented by the following formula (i) is from 1.20 to 1.80.
[0022]
　B value = ([EX] +2 [Y ]) / [2 × [E] × ([ X] + [Y]) ] · · · (i)
　where [E], [X] and [Y] is , respectively, show the molar fraction of the structural unit derived from ethylene, the molar fraction of the structural unit derived from an α- olefin having 4 to 20 carbon atoms, the molar fraction of the structural unit derived from non-conjugated polyene, [EX] is ethylene structural units derived from - showing dyad sequence fraction of the structural unit derived from an α- olefin having 4 to 20 carbon atoms.
[0023]
　(2) a copolymer of (1B), the molar ratio of the structural units derived from structural units and α- olefin derived from ethylene (number of carbon atoms of from 4 to 20), is 40 / 60-90 / 10.
[0024]
　alpha-olefin of the ethylene-alpha-olefin-non-conjugated polyene copolymer (1B) is preferably 1-butene.
[0025]
　The above mixture is further softening agent (D), per 100 parts by weight of the crystalline olefin polymer (A) and the copolymer (1B), preferably contains 2 to 100 parts by weight .
[0026]
　The phenolic resin-based crosslinking agent (C) is preferably a halogenated phenolic resin crosslinking agent.
[0027]
　The above mixture, the crystalline olefin polymer (A) and the ethylene-alpha-olefin-nonconjugated polyene copolymer and (1B), the weight of (A) / (1B) = 90/10 ~ 10/90 It contains a ratio phenol resin-based crosslinking agent (C) is an ethylene-alpha-olefin-non-conjugated polyene copolymer (1B) with respect to 100 parts by weight, preferably 0.1 to 20 parts by weight.
[0028]
　Molding of the present invention (1) is characterized in that it is obtained including the thermoplastic elastomer composition of the present invention (1).
[0029]
　Automobile parts of the present invention (1) is characterized in that it is obtained including the thermoplastic elastomer composition of the present invention (1).
[0030]
　Automotive hose of the present invention (1) is characterized in that it is obtained including the thermoplastic elastomer composition of the present invention (1).
[0031]
　Automotive boot of the invention (1) is characterized in that it is obtained including the thermoplastic elastomer composition of the present invention (1).
[0032]
　Method for producing a thermoplastic elastomer composition (I) of the present invention, crystalline olefin polymer (A), the ethylene-alpha-olefin (4-20 carbon atoms), non-conjugated polyene copolymer (1B) When, characterized in that it comprises a step of a mixture comprising a phenolic resin-based cross-linking agent (C), to dynamic crosslinking.
[0033]
　The present inventors have conducted extensive studies to solve the above problems. As a result, already compared with the ethylene-alpha-olefin-non-conjugated polyene copolymer has been proposed, further, small compression set at low temperature, and has a flexibility, rubber elasticity and cold at low temperatures tensile specific ethylene-alpha-olefin-nonconjugated polyene copolymer and compositions comprising the copolymer excellent in balance between strength (in the present invention, the composition (IIA) and also referred) heading the present invention (2) it has led to the completion of the.
[0034]
　Further, by using a specific ethylene-alpha-olefin-nonconjugated polyene copolymer, low-temperature properties and mechanical properties superior hose forming composition capable of forming a hose (in the present invention, the composition and (IIB) and also referred to), found that it is possible to provide a hose which is formed from the composition, and have completed the present invention (2).
[0035]
　Further, a crystalline olefin polymer, and specific ethylene-alpha-olefin-nonconjugated polyene copolymer, a thermoplastic elastomer composition obtained by dynamically crosslinking a mixture comprising a phenolic resin-based crosslinking agent (the the invention, also referred to as composition (IIC)) has a better oil resistance than conventional crosslinked thermoplastic elastomers, and, of equal to or more than the conventional cross-linked thermoplastic elastomer, and hardness, tensile strength and found that can be a molded article having mechanical properties such as tensile elongation, also the thermoplastic elastomer composition (IIC) is molded with better oil resistance, especially for a motor vehicle, hose and boots ( It found that it is possible to provide an automobile part, such as blow molding), and completed the present invention (2).
[0036]
　The present invention (2), for example relates to the following [1] to [18].
[0037]
　　[1]
　Ethylene [A] a structural unit derived from, includes a structural unit derived from structural units derived from 4 to 20 carbon atoms α- olefin [B], and the non-conjugated polyene [C], the following (1) ~ (4) ethylene-alpha-olefin-nonconjugated polyene copolymer satisfying (2B).
[0038]
　(1) ethylene and structural units derived from [A], the molar ratio of the structural units derived from α- olefin [B] [[A] / [B]] is a 40 / 60-90 / 10,
　(2) the content of structural units derived from the nonconjugated polyene [C] is, [a], [B] and 100 mol% of the total of the structural units of [C], 0.1 ~ 6.0 mol% , and
　the (3) Mooney viscosity ML at ° C. 125 (1 + 4) 125 ° C. is 200 or less exceed
　100, (4) B value represented by the following formula (i) is from 1.20 to 1 it is .80.
[0039]
　B value = ([EX] +2 [Y ]) / [2 × [E] × ([ X] + [Y]) ] · · (i)
[where [E], [X] and [Y] is , respectively, ethylene [a], of 4 to 20 carbon atoms α- olefin [B], and indicates the mole fraction of the non-conjugated polyene [C], [EX] ethylene [a] - of 4 to 20 carbon atoms It shows the α- olefin [B] dyad sequence fraction. ]
[0040]
　　[2]
　having 4 to ~ 20 alpha-olefin carbon [B], characterized in that 1-butene [1] Ethylene-alpha-olefin-nonconjugated polyene copolymer according to (2B).
[0041]
　　[3]
(a) a transition metal compound represented by the following general formula
[VII], (b) (b-1) organometallic compound,
　　　(b-2) an organoaluminum oxy-compound, and
　　　(b-3) Transition in the presence of an olefin polymerization catalyst comprising at least one compound selected from the compounds in which the metal compound reacts with (a) to form an ion pair, ethylene, α- olefin and non-conjugated polyene of 4 to 20 carbon atoms obtained by copolymerizing, [1] or the ethylene-alpha-olefin-nonconjugated polyene copolymer according to [2] (2B).
[0042]
[Formula 1]

[0043]
(In the formula [VII],
　M is titanium atom, zirconium atom or hafnium atom,
　R 5 and R 6 are one or more hydrogen atoms of the aryl group is σ substituent constant Hammett rule -0.2 following e a substituted aryl group formed by substituted by donating substituents, each electron donor substituent when having a plurality of electron-donating substituents may be the same or different, electron donor other than the substituent include a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group may have a substituent selected from halogen atoms and halogen-containing groups, the substituent each substituent when having a plurality is a substituted aryl group which may be the same or different,
　Q is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand and a lone pair of electrons in a coordination Possible Chosen by the same or different combination from a neutral ligand,
　j is an integer of 1-4.)
[0044]
　　[4]
　[1] to [3] compositions containing ethylene-alpha-olefin-nonconjugated polyene copolymer according (2B) to any one of.
[0045]
　　[5]
　a shaped article formed by crosslinking a composition according to [4].
[0046]
　　[6]
　[1] to [3] hose forming composition containing the ethylene-alpha-olefin-nonconjugated polyene copolymer according (2B) to any one of.
[0047]
　　[7]
　a hose having a layer formed by crosslinking the hose forming composition as described in [6].
[0048]
　　[8]
　for the automotive, motorcycle, industrial machinery, used in any of the applications for construction equipment or agricultural machinery, hose according to [7].
[0049]
　　[9]
　crystalline olefin polymer (A),
　the ethylene-alpha-olefin-non-conjugated polyene copolymer (2B), and
　the mixture containing the phenolic resin-based crosslinking agent (C)
obtained by dynamic crosslinking,
　ethylene-alpha-olefin-non-conjugated polyene copolymer (2B) is, [1] to the thermoplastic elastomer composition is an ethylene-alpha-olefin-nonconjugated polyene copolymer according to any one of [3] Stuff.
[0050]
　　[10]
　The said mixture, additionally, a softening agent (D), relative to the total 100 parts by weight of the crystalline olefin polymer (A) and the copolymer (2B), comprising 2 to 100 parts by weight the thermoplastic elastomer composition according to [9].
[0051]
　　[11]
　phenol resin-based crosslinking agent (C) is a halogenated phenolic resin crosslinking agent, [9] or a thermoplastic elastomer composition according to [10].
[0052]
　　[12]
　Crystalline olefin polymer (A) and the ethylene-alpha-olefin-nonconjugated polyene copolymer and (2B), at (A) / (2B) = 90/10 mass ratio of ~ 10/90 containing,
　phenolic resin crosslinking agent (C), the ethylene-alpha-olefin-non-conjugated polyene copolymer (2B) relative to 100 parts by weight, 0.1 to 20 parts by weight, [9] - [ thermoplastic elastomer composition according to any one of 11.
[0053]
　　[13] [9]
　to obtain contain a thermoplastic elastomer composition according to any one of [12], the molded body.
[0054]
　　[14] [9]
　- [12] contains a thermoplastic elastomer composition obtained, automotive parts according to any one of.
[0055]
　　[15] [9]
　to obtain contain a thermoplastic elastomer composition according to any one of [12], a hose for automobiles.
[0056]
　　[16] [9]
　to obtain contain a thermoplastic elastomer composition according to any one of [12], boots for automobiles.
[0057]
　　[17]
　(a) a transition metal compound represented by the general formula
　[VII], (b) (b-1) organometallic compound,
　　　　(b-2) an organoaluminum oxy-compound, and
　　　　(b-3) Transition and at least one compound selected from the compounds in which the metal compound reacts with (a) to form an ion pair
in the presence of an olefin polymerization catalyst comprising ethylene, an α- olefin and non-conjugated polyene of 4 to 20 carbon atoms obtained by including a step of copolymerizing method of the ethylene-alpha-olefin-non-conjugated polyene copolymer (2B).
[0058]
　　[18]
　comprising crystalline olefin polymer (A), and the ethylene-alpha-olefin-non-conjugated polyene copolymer (having 4 to 20 carbon atoms) (2B), a phenol resin-based crosslinking agent and (C) the mixture is characterized in that it comprises a step of dynamic crosslinking, the manufacturing method of the thermoplastic elastomer composition.
Effect of the invention
[0059]
　According to the present invention (1), a light-weight, it has a conventional crosslinked thermoplastic elastomer excellent oil resistance than, and conventional crosslinking type thermoplastic elastomer and equal to or higher than that, and hardness, tensile strength and thermoplastic elastomer composition which can be a molded article having mechanical properties such as tensile elongation is obtained.
[0060]
　Ethylene-alpha-olefin-non-conjugated polyene copolymer (2) has a smaller compression set at low temperature, and has a flexibility, and tensile strength of rubber elasticity and cold at low temperatures excellent in balance, the composition containing ethylene-alpha-olefin-nonconjugated polyene copolymer, taking advantage of such properties, can be suitably used in various applications.
[0061]
　According to the present invention (2), and low-temperature properties such as rubber elasticity at low temperatures, and tensile strength and mechanical properties and capable of forming an excellent hose hose forming composition at room temperature, the it is possible to provide a hose which is formed from the composition.
[0062]
　According to the present invention (2), a light-weight, it has a conventional crosslinked thermoplastic elastomer excellent oil resistance than, and conventional crosslinking type thermoplastic elastomer and equal to or higher than that, and hardness, tensile strength and thermoplastic elastomer composition which can be a molded article having mechanical properties such as tensile elongation is obtained.
DESCRIPTION OF THE INVENTION
[0063]
　
　crystalline olefin polymer (A) (also referred to as a polymer in the present invention (A)) is not particularly limited as long as it is a crystalline polymer obtained from olefin , one or more monoolefins, is preferably a polymer comprising a crystalline high molecular weight solid product obtained by polymerizing by either high-pressure or low-pressure process. Examples of such polymers, isotactic monoolefin polymers, syndiotactic monoolefin polymers, and the like.
[0064]
　Polymer (A) may be obtained by synthesis by a conventional method, it may be a commercially available product.
[0065]
　Polymer (A) may be used singly or may be used in combination of two or more.
[0066]
　The monoolefin as a raw material of the polymer (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. These olefins may be used singly or may be used by mixing two or more.
[0067]
　Among of the polymer (A), heat resistance, from the viewpoint of oil resistance, a propylene homopolymer obtained from monoolefins which propylene as the main or propylene copolymer and a propylene-based (co) polymers are preferred. In the case of propylene copolymer, the content of the structural unit derived from propylene preferably is 40 mol%, more preferably at least 50 mol%, a monoolefin which is a structural unit derived from a monomer other than propylene is preferably the mono-olefins other than propylene, more preferably ethylene, butene.
[0068]
　Polymerization mode is also a block type in a random type, no problem be adopted any polymerization mode as long resulting crystalline resin like material.
[0069]
　The crystalline olefin polymer (A), MFR (ASTM D1238-65T, 230 ℃, 2.16kg load) of usually 0.01 ~ 100 (g / 10 min), preferably 0.05-50 ( g is a / 10 minutes).
[0070]
　Polymer (A), the melting point obtained by differential scanning calorimetry (DSC) (Tm) of usually 100 ° C. or higher, preferably 105 ° C. or higher. Differential scanning calorimetry is carried out, for example, in the following manner. Packed about specimen 5mg dedicated aluminum pan, then holding with Corporation Perkin Elmer DSCPyris1 or DSC7, heated up to 200 ° C. from 30 ° C. at 320 ° C. / min, at 200 ° C. 5 min, 200 ° C. up to 30 ° C. and cooled at 10 ° C. / min from and held for a further 5 minutes at 30 ° C., then determine the melting endothermic curve at the time of raising the temperature at 10 ° C. / min. At the time of DSC measurement, if multiple peaks are detected, to define the peak temperature detected by the highest temperature side as the melting point (Tm).
[0071]
　Polymer (A), it plays a role of improving the fluidity and heat resistance of the thermoplastic elastomer composition.
[0072]
　
　The present invention (1) ethylene using alpha-olefin-non-conjugated polyene copolymer (1B) (the copolymer in the present invention (1B) both referred) is a structural unit derived from ethylene, the ethylene-alpha-olefin containing structural units derived from structural units, and at least one non-conjugated polyene derived from at least one alpha-olefin having 4 to 20 carbon atoms a non-conjugated polyene
　copolymer, (1) a B value of 1.20 to 1.80 of the following formula (i),
　　　B value = ([EX] +2 [Y ]) / [2 × [E] × ([X] + [Y]) ] · · · (i)
　(where [E], [X] and [Y] are each mole fractions of structural units derived from ethylene, carbon atoms 4 ~ 20 alpha-olefin-derived molar fraction of the structural unit of the non-conjugated poly Shows the molar fraction of the structural unit derived from emissions, [EX] is a structural unit derived from ethylene - showing dyad sequence fraction of the structural units derived from α- olefin to 4 carbon atoms 20),
　(2) copolymers the (1B), the molar ratio of the structural units derived from structural units and α- olefin derived from ethylene (number of carbon atoms of from 4 to 20), is 40 / 60-90 / 10.
[0073]
　The α- olefin having 4 to 20 carbon atoms, 1-butene (4 carbon atoms), 1-nonene (9 carbon atoms), 1-decene (10 carbon atoms), nonadecene (19 carbon atoms), 1- eicosene side chain of (number of 20 carbon atoms) such as not linear α- olefin; with a side chain 4-methyl-1-pentene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12- such as α- olefin having side chains of ethyl-1-tetradecene, and the like. These α- olefins may be used in combination of two or more kinds may be used alone. Of these, alpha-olefin is preferably 4 to 10 carbon atoms, 1-butene, 1-hexene, and more preferably 1-octene, 1-butene, in addition to the effect of the present invention, in particular, the molding obtained body, oil resistance, specifically to relatively oil resistance at high temperatures, it is possible to improve the flexibility and impact resistance, more preferably.
[0074]
　As the non-conjugated polyene, 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, chains such as 7-methyl-1,6-octadiene Jo nonconjugated diene; cyclohexadiene, dicyclopentadiene, methyl tetrahydroindene, 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-isopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl -2, 5-norbornadiene, 1,3,7-octatriene, 1,4,9- Dekatorie , 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 in combination of two or more kinds may be used alone. Among these, cyclic nonconjugated dienes such as 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, mixtures of 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene preferably, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene is more preferable.
[0075]
　As the copolymer (1B), an ethylene-1-butene-1,4-hexadiene copolymer, ethylene-1-pentene, 1,4-hexadiene copolymer, ethylene-1-hexene-1,4-hexadiene copolymers, heptene-1,4-hexadiene copolymer to ethylene-1, 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 · To 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, heptene-5-ethylidene ethylene to 1-2- nor Runen-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- ethylidene -2
[0076]
　Copolymer (1B) may be used alone or may be used in combination of two or more.
[0077]
　Copolymer (1B) is, (1) B value represented by the above formula (i) is 1.20 or more, preferably from 1.20 to 1.80, particularly preferably in the 1.22 to 1.40 range is there.
[0078]
　Copolymer B value is less than 1.20 (1B) is compression set becomes large, the thermoplastic elastomer composition excellent in balance between tensile strength and rubber elasticity may not be obtained.
[0079]
　Incidentally, B value is an index indicating the randomness of the copolymerized monomer sequence distribution in the copolymer (1B), in the formula (i) [E], [ X], [Y], [EX] is 13 measures the C-NMR spectrum, JCRandall [Macromolecules, 15, 353 (1982)], J. Ray [Macromolecules, 10, 773 (1977)] can be determined based on these reports.
[0080]
　Ethylene-alpha-olefin-non-conjugated polyene copolymer (1B) is (2) the molar ratio of the structural units [A] derived from ethylene, a structural unit [B] derived from the alpha-olefin [[A] / [B]] is in the range of 40 / 60-90 / 10. The lower limit of the molar ratio [A] / [B], preferably 45/55, more preferably 50/50, particularly preferably 55/45. The upper limit of the molar ratio [A] / [B], preferably 80/20, more preferably 75/25, more preferably 70/30, particularly preferably 65/35.
[0081]
　And the structural units [A] derived from ethylene, the molar ratio of the structural units [B] derived from α- olefin is in the above range, oil resistance, particularly relatively good oil resistance at high temperatures, and rubber elasticity thermoplastic elastomer composition having excellent balance between tensile strength at room temperature (I).
[0082]
　Copolymer (1B), the following requirements (3) and (4) of it is desirable to satisfy at least one.
[0083]
　Copolymer (1B) is, (3) JIS K6300 were obtained by measuring according to (1994), Mooney viscosity ML at 125 ° C. (1 + 4) (125 ° C.) is, as long as the effect of the present invention is not particularly limited, preferably 5 to 100, more preferably 20 to 95, more preferably in the range of 50 to 90.
[0084]
　When the Mooney viscosity is in the above range tends to have excellent rubber properties with showing good post-processing properties (ribbon handling properties).
[0085]
　Copolymer (1B) is (4) the content of the structural unit [C] from a non-conjugated polyene, [A], with respect to 100 mole% of the total of the structural units of [B] and [C] , preferably 0.1 to 6.0 mol%, more preferably 0.5-4.0 mol%, more preferably 0.5 to 3.5 mol%, particularly preferably 0.5 to 3.0 moles It is located in the% of range. When the content of the structural unit [C] from a non-conjugated polyene is in the above range, there is a tendency sufficient to crosslinkable, and ethylene copolymer having a flexibility.
[0086]
　
　also referred to as the present invention the ethylene-alpha-olefin-non-conjugated polyene copolymer (2) (2B) (the copolymer in the present invention (2B) ) are structural units derived from ethylene [a], include structural units derived from structural units derived from 4 to 20 carbon atoms α- olefin [B], and the non-conjugated polyene [C], the following (1) ~ satisfy (4). Incidentally, such a specific ethylene-alpha-olefin-nonconjugated polyene copolymer, also referred to as "ethylene copolymer 2A".
[0087]
　In the present invention (1) and (2), respectively as the α- olefin [B] and a non-conjugated polyene [C] having 4 to 20 carbon atoms, be used alone, it is used two or more good. Copolymer (1B) or (2B), the structural units derived from ethylene [A], at least one carbon 4 ~ 20 alpha-olefin [B] derived from the structural units, and at least one non a structural unit derived from a conjugated polyene [C].
[0088]
　(1) ethylene and structural units derived from [A], the molar ratio of the structural units derived from α- olefin [B] [[A] / [B]] is a 40 / 60-90 / 10,
　(2) the content of structural units derived from the nonconjugated polyene [C] is, [a], [B] and 100 mol% of the total of the structural units of [C], 0.1 ~ 6.0 mol% , and
　the (3) Mooney viscosity ML at ° C. 125 (1 + 4) 125 ° C. is, is 200 greater than 100 or
　less, with (4) B value represented by the above formula (i) is 1.20 or more is there.
[0089]
　Formula (i) are the same as the formula of the copolymer (1B) (i).
[0090]
　The carbon number of 4 to 20 alpha-olefin [B], can refer to the example of alpha-olefin having 4 to 20 carbon atoms in the copolymer (1B). In the copolymer (2B), as the alpha-olefin [B], alpha-olefin is preferably 4 to 10 carbon atoms, in particular 1-butene, 1-hexene, are preferred and 1-octene, particularly 1-butene it is preferred.
[0091]
　Ethylene-propylene-non-conjugated polyene copolymer olefin α- is propylene tend to be insufficient rubber elasticity at low temperatures, there is a case where use is limited. On the other hand, the copolymer (2B), since a structural unit derived from 4 to 20 carbon atoms α- olefin [B], has excellent rubber elasticity at low temperatures.
[0092]
　The non-conjugated polyene [C], can refer to exemplary non-conjugated polyene in the copolymer (1B). In the copolymer (2B), as the non-conjugated polyene [C], a chain nonconjugated dienes such as 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl - 2-norbornene cyclic non-conjugated dienes such as preferable, preferably a cyclic non-conjugated diene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene is particularly preferred.
[0093]
　As the copolymer (2B), you can refer to the above illustration copolymer (1B). Copolymer (2B) is one if necessary, or two or more may be used.
[0094]
　In the copolymer (2B), (1) the molar ratio of the structural units derived from ethylene [A], the structural unit derived from an α- olefin [B] [[A] / [B]] is the co the molar ratio of the requirements in the polymer (1B) (2) and [[a] / [B]], is the same, including the preferred ranges of the molar ratio.
[0095]
　In the copolymer (2B), ethylene and structural units derived from [A], the molar ratio of the structural units derived from α- olefin [B] is in the above range, the rubber elasticity and cold at low temperatures ethylene copolymer having excellent balance between tensile strength.
[0096]
　In the copolymer (2B), (2) the content of structural units derived from the nonconjugated polyene [C] has a content requirements (4) in the copolymer (1B), the same, including the preferred ranges it is.
[0097]
　In the copolymer (2B), the content of structural units derived from the nonconjugated polyene [C] is in the above range, the ethylene copolymer having a sufficient crosslinking and flexibility.
[0098]
　Copolymer (2B) is, (3) 125 Mooney viscosity ML in ° C. (1 + 4) 125 ° C. is 200 or less than 100, 120 or less preferably 150 or less than 100, particularly preferably more than 100 It is in the range of.
[0099]
　When the Mooney viscosity is in the above range, a composition containing a copolymer (2B) of (2) is preferable because the sealing property and low-temperature characteristics become good.
[0100]
　(4) B value of the copolymer (2B) has a B value of requirement (1) in the copolymer (1B), is the same, including the preferred ranges.

The scope of the claims
[Claim 1]
　Crystalline olefin polymer (A),
　the following requirements (1) and (2) an ethylene-alpha-olefin (carbon number 4 to 20) that satisfies the non-conjugated polyene copolymer (1B), and
　phenolic resin crosslinking agent (C) mixture containing
thermoplastic elastomer composition obtained by dynamic crosslinking.
　(1) B value represented by the following formula (i) is from 1.20 to 1.80.
　B value = ([EX] +2 [Y ]) / [2 × [E] × ([ X] + [Y]) ] · · · (i)
　where [E], [X] and [Y] is , respectively, show the molar fraction of the structural unit derived from ethylene, the molar fraction of the structural unit derived from an α- olefin having 4 to 20 carbon atoms, the molar fraction of the structural unit derived from non-conjugated polyene, [EX] is ethylene structural units derived from - showing dyad sequence fraction of the structural unit derived from an α- olefin having 4 to 20 carbon atoms.
　(2) a copolymer of (1B), the molar ratio of the structural units derived from structural units and α- olefin derived from ethylene (4-20 carbon atoms) is 40 / 60-90 / 10.
[Claim 2]
　Ethylene-alpha-olefin-non-conjugated polyene copolymer (1B) alpha-olefin is 1-butene, thermoplastic elastomer composition as claimed in claim 1.
[Claim 3]
　Wherein the mixture further, softening agent (D), relative to the total 100 parts by weight of the crystalline olefin polymer (A) and the copolymer (1B), comprising 2 to 100 parts by weight, claim 1 or a thermoplastic elastomer composition according to 2.
[Claim 4]
　Phenolic resin crosslinking agent (C) is a halogenated phenolic resin crosslinking agent, a thermoplastic elastomer composition according to any one of claims 1 to 3.
[Claim 5]
　Crystalline olefin polymer (A) and the ethylene-alpha-olefin-nonconjugated polyene copolymer and (1B), and in a weight ratio of (A) / (1B) = 90/10 ~ 10/90,
　phenolic resin crosslinking agent (C) is an ethylene-alpha-olefin-non-conjugated polyene copolymer (1B) with respect to 100 parts by weight, 0.1 to 20 parts by weight, any one of claims 1 to 4, thermoplastic elastomer composition according to.
[Claim 6]
　Obtained contains a thermoplastic elastomer composition according to any one of claims 1 to 5, moldings.
[Claim 7]
　Thermoplastic contain elastomer composition obtained, automotive parts according to any one of claims 1 to 5.
[8.]
　Thermoplastic elastomer compositions comprise obtained, hoses for automobiles according to any one of claims 1 to 5.
[Claim 9]
　Obtained contains a thermoplastic elastomer composition according to any one of claims 1 to 5, the boot for an automobile.
[Claim 10]
　Crystalline olefin polymer (A), the following requirements (1) and (2) satisfy the ethylene-alpha-olefin (carbon number 4-20) and non-conjugated polyene copolymer (1B), phenolic resin the mixture containing the cross-linking agent (C), characterized in that it comprises a step of dynamic crosslinking, the manufacturing method of the thermoplastic elastomer composition.
　(1) B value represented by the following formula (i) is from 1.20 to 1.80.
　B value = ([EX] +2 [Y ]) / [2 × [E] × ([ X] + [Y]) ] · · · (i)
　where [E], [X] and [Y] is , respectively, show the molar fraction of the structural unit derived from ethylene, the molar fraction of the structural unit derived from an α- olefin having 4 to 20 carbon atoms, the molar fraction of the structural unit derived from non-conjugated polyene, [EX] is ethylene structural units derived from - showing dyad sequence fraction of the structural unit derived from an α- olefin having 4 to 20 carbon atoms.
　(2) a copolymer of (1B), the molar ratio of the structural units derived from structural units and α- olefin derived from ethylene (4-20 carbon atoms) is 40 / 60-90 / 10.
[Claim 11]
　Comprising structural units derived from ethylene [A], the structural unit derived from structural units derived from 4 to 20 carbon atoms α- olefin [B], and the non-conjugated polyene [C], the following (1) to (4 ethylene-alpha-olefin-nonconjugated polyene copolymer satisfying) (2B).
　(1) ethylene and structural units derived from [A], the molar ratio of the structural units derived from α- olefin [B] [[A] / [B]] is a 40 / 60-90 / 10,
　(2) the content of structural units derived from the nonconjugated polyene [C] is, [a], [B] and 100 mol% of the total of the structural units of [C], 0.1 ~ 6.0 mol% , and
　the (3) Mooney viscosity ML at ° C. 125 (1 + 4) 125 ° C. is 200 or less exceed
　100, (4) B value represented by the following formula (i) is from 1.20 to 1 it is .80.
　B value = ([EX] +2 [Y ]) / [2 × [E] × ([ X] + [Y]) ] · · (i)
[where [E], [X] and [Y] is , respectively, ethylene [a], of 4 to 20 carbon atoms α- olefin [B], and indicates the mole fraction of the non-conjugated polyene [C], [EX] ethylene [a] - of 4 to 20 carbon atoms It shows the α- olefin [B] dyad sequence fraction. ]
[Claim 12]
　Carbon atoms 4 ~ 20 alpha-olefin [B] is an ethylene according to claim 11, wherein the 1-butene-alpha-olefin-non-conjugated polyene copolymer (2B).
[Claim 13]
　(A) a transition metal compound represented by the following general formula
　[VII], (b) (b-1) organometallic compound,
　　　　(b-2) an organoaluminum oxy-compound, and
　　　　(b-3) a transition metal compound ( at least one compound to react with a) is selected from compounds to form an ion pair
in the presence of an olefin polymerization catalyst comprising, copolymerizing ethylene, an α- olefin and non-conjugated polyene of 4 to 20 carbon atoms obtained by the ethylene-alpha-olefin-nonconjugated polyene copolymer according to claim 11 or 12 (2B).
[Formula 1]

In (formula [VII],
　M is titanium atom, zirconium atom or hafnium atom,
　R 5 and R 6 are substituent constant Hammett rule one or more hydrogen atoms of the aryl group σ is - a substituted aryl group obtained by substitution with 0.2 following electron-donating substituents, each electron donor substituent when having a plurality of electron-donating substituents may be the same or different, other than electron donor substituent, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group may have a substituent selected from halogen atoms and halogen-containing groups, the respective substituents in the case of having a plurality of substituents are substituent aryl group which may be the same or different,
　Q is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand and a lone coordination in pairs Chosen by the same or different combination from ability neutral ligand,
　j is an integer of 1-4.)
[Claim 14]
　Compositions containing ethylene-alpha-olefin-nonconjugated polyene copolymer according (2B) to any one of claims 11 to 13.
[Claim 15]
　Molded body formed by crosslinking a composition according to claim 14.
[Claim 16]
　11. Ethylene-alpha-olefin-non-conjugated polyene copolymer (2B) hose forming composition containing a according to any one of to 13.
[Claim 17]
　Hoses having a layer formed by crosslinking the hose forming composition of claim 16.
[Claim 18]
　For the automotive, motorcycle, industrial machinery, used in any of the applications for construction equipment or agricultural machinery, hose according to claim 17.
[Claim 19]
　Crystalline olefin polymer (A),
　the ethylene-alpha-olefin-non-conjugated polyene copolymer (2B), and
　phenolic resin crosslinking agent a mixture containing (C)
obtained by dynamic crosslinking,
　the ethylene-alpha - olefin-non-conjugated polyene copolymer (2B) is, according to claim 11 thermoplastic elastomer composition is an ethylene-alpha-olefin-nonconjugated polyene copolymer according (2B) to any one of to 13.
[Claim 20]
　Wherein the mixture further, softening agent (D), relative to the total 100 parts by weight of the crystalline olefin polymer (A) and the copolymer (2B), comprising 2 to 100 parts by weight, claim thermoplastic elastomer composition according to 19.
[Claim 21]
　Phenolic resin crosslinking agent (C) is a halogenated phenolic resin crosslinking agent, a thermoplastic elastomer composition according to claim 19 or 20.
[Claim 22]
　Crystalline olefin polymer (A) and the ethylene-alpha-olefin-nonconjugated polyene copolymer and (2B), contains a mass ratio of (A) / (2B) = 90/10 ~ 10/90,
　phenolic resin crosslinking agent (C), the ethylene-alpha-olefin-non-conjugated polyene copolymer (2B) relative to 100 parts by weight, 0.1 to 20 parts by weight, any one of claims 19-21 thermoplastic elastomer composition according to one.
[Claim 23]
　Obtained contains a thermoplastic elastomer composition according to any one of claims 19-22, moldings.
[Claim 24]
　To any one of claims 19-22 obtained contains a thermoplastic elastomer composition according automobile parts.
[Claim 25]
　Thermoplastic contain elastomer composition obtained, hoses for automobiles according to any one of claims 19-22.
[Claim 26]
　Obtained contains a thermoplastic elastomer composition according to any one of claims 19-22, boots for automobiles.
[Claim 27]
　(A) a transition metal compound represented by the following general formula
　[VII], (b) (b-1) organometallic compound,
　　　　(b-2) an organoaluminum oxy-compound, and
　　　　(b-3) a transition metal compound ( at least one compound to react with a) is selected from compounds to form an ion pair
in the presence of an olefin polymerization catalyst comprising, copolymerizing ethylene, an α- olefin and non-conjugated polyene of 4 to 20 carbon atoms obtained by including a method of manufacturing an ethylene-alpha-olefin-non-conjugated polyene copolymer.
[Formula 2]

In (formula [VII],
　M is titanium atom, zirconium atom or hafnium atom,
　R 5 and R 6 are substituent constant Hammett rule one or more hydrogen atoms of the aryl group σ is - a substituted aryl group obtained by substitution with 0.2 following electron-donating substituents, each electron donor substituent when having a plurality of electron-donating substituents may be the same or different, other than electron donor substituent, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group may have a substituent selected from halogen atoms and halogen-containing groups, the respective substituents in the case of having a plurality of substituents are substituent aryl group which may be the same or different,
　Q is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand and a lone coordination in pairs Chosen by the same or different combination from ability neutral ligand,
　j is an integer of 1-4.)
[Claim 28]
　Crystalline olefin polymer (A), derived from ethylene structural units derived from [A], structural units derived from 4 to 20 carbon atoms α- olefin [B], and a non-conjugated polyene [C] Structure comprises units, a mixture comprising the following (1) to the ethylene-alpha-olefin satisfying (4) (4 to 20 carbon atoms), non-conjugated polyene copolymer (2B), a phenol resin-based crosslinking agent and (C) and characterized in that it comprises a step of dynamic crosslinking, the manufacturing method of the thermoplastic elastomer composition.
　(1) ethylene and structural units derived from [A], the molar ratio of the structural units derived from α- olefin [B] [[A] / [B]] is a 40 / 60-90 / 10,
　(2) the content of structural units derived from the nonconjugated polyene [C] is, [a], [B] and 100 mol% of the total of the structural units of [C], 0.1 ~ 6.0 mol% , and
　the (3) Mooney viscosity ML at ° C. 125 (1 + 4) 125 ° C. is 200 or less exceed
　100, (4) B value represented by the following formula (i) is from 1.20 to 1 it is .80.
　B value = ([EX] +2 [Y ]) / [2 × [E] × ([ X] + [Y]) ] · · (i)
[where [E], [X] and [Y] is , respectively, ethylene [a], of 4 to 20 carbon atoms α- olefin [B], and indicates the mole fraction of the non-conjugated polyene [C], [EX] ethylene [a] - of 4 to 20 carbon atoms It shows the α- olefin [B] dyad sequence fraction. ]