JP2017019890A - ETHYLENE/α-OLEFIN/NON-CONJUGATED POLYENE COPOLYMER - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ethylene/α-olefin/non-conjugated polyene copolymer capable of forming a crosslinked body excellent in fatigue resistance.SOLUTION: An ethylene/α-olefin/non-conjugated polyene copolymer satisfies the following requirements (1) and (2). (1) A nonuniform structure amount c and a blended amount of peroxide satisfy the formula (1a) and (2) nonuniform structure size b and the blended amount of peroxide satisfy the formula (2a) when crosslinking the copolymer using peroxide, and calculating the nonuniform structure amount c and nonuniform structure size b by a small angle neutron scattering method on the resulting crosslinked body.SELECTED DRAWING: None

Description

  The present invention relates to an ethylene / α-olefin / non-conjugated polyene copolymer.

  The cross-linked network structure of the cross-linked product is one of the important factors that determine the performance of the cross-linked product. In general, it is known that the crosslinked network structure is non-uniform. As a method for grasping the crosslinked network structure, a method of measuring the average value of the crosslinking density by swelling the crosslinked body with a solvent (for example, the Flory-Rehner method) has been conventionally used.

  However, in the above method, even though it is possible to grasp the number of cross-linking points in a unit volume, how uniformly the cross-linking points exist, that is, the non-uniformity of the cross-linking network structure, I can not grasp to the point.

  From past studies, it is speculated that the uniform distribution of cross-linking points in the cross-linked body is related to the strength and fatigue resistance of the cross-linked body (see, for example, Patent Document 1). In a crosslinked product obtained from a diene rubber such as natural rubber, an example in which a heterogeneous structure is measured by neutron scattering has been reported (for example, see Non-Patent Documents 1 and 2). However, there is no report on a crosslinked product obtained from an ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer.

JP 2012-126866 A

M. Takenaka. NIPPON GOMU KYOKAISHI 87 (7), 299 (2014) M. Shibayama. NIPPON GOMU KYOKAISHI 84 (1), 14 (2011)

  By examining the cross-linked structure (non-uniformity of cross-linking points) of the cross-linked product obtained from the ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer, the fatigue resistance of the cross-linked product is improved. It is considered possible. An object of the present invention is to provide an ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer capable of forming a crosslinked product having excellent fatigue resistance.

  The present inventors have intensively studied to solve the above problems. As a result, an ethylene / carbon number α-olefin / non-conjugated polyene copolymer that forms a crosslinked product having a heterogeneous structure amount and a heterogeneous structure size measured by a small-angle neutron scattering method in a specific range is the above-mentioned problem. As a result, the present invention has been completed.

That is, the present invention relates to the following [1] to [5], for example.
[1] An ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer satisfying the following requirements (1) and (2):

  When the copolymer is crosslinked with a peroxide and the heterogeneous structure amount c and the heterogeneous structure size b are determined by the small-angle neutron scattering method for the obtained crosslinked product, (1) the heterogeneous structure amount c And the peroxide blending amount satisfies the formula (1a), and (2) the heterogeneous structure size b and the peroxide blending amount satisfy the formula (2a).

[2] The heterogeneous structure size b and the heterogeneous structure amount c are obtained by crosslinking the above-mentioned copolymer with a peroxide, and the scattering intensity curve I obtained by the small-angle neutron scattering method for the obtained crosslinked product. (Q) is a value obtained by using equations (2) and (3) from parameters Ξ, I _ξ (0) and I _Ξ (0) obtained by curve fitting according to equation (A). The ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer described in [1].

［式（Ａ）および（１）〜（３）中、θは散乱角（ｒａｄ）であり、λは中性子線の波長（ｎｍ）であり、Ｉ_ξ（０）、Ｉ_Ξ（０）、ξ、ΞおよびＩ_incはフィッティングパラメーターである。］

[In the formulas (A) and (1) to (3), θ is the scattering angle (rad), λ is the wavelength (nm) of the neutron beam, and I _ξ (0), I _Ξ (0), ξ , Ξ and I _inc are fitting parameters. ]

  [3] The ethylene / carbon according to the above [1] or [2], wherein in the above requirements (1) and (2), the peroxide used for crosslinking the copolymer is dicumyl peroxide. An α-olefin / non-conjugated polyene copolymer having a number of 3 to 20.

  [4] A composition containing the ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer according to any one of [1] to [3].

  [5] A crosslinked product obtained by crosslinking the composition according to [4].

  ADVANTAGE OF THE INVENTION According to this invention, the ethylene-C3-C20 alpha olefin and nonconjugated polyene copolymer which can form the crosslinked body excellent in fatigue resistance can be provided.

FIG. 1 is an example of curve fitting for a scattering intensity curve obtained by neutron scattering measurement of a crosslinked product obtained from an ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer. FIG. 2 is a graph in which the heterogeneous structure amount c is plotted with respect to the amount of peroxide blended in a crosslinked product obtained from an ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer. FIG. 3 is a graph in which the heterogeneous structure size b is plotted with respect to the amount of peroxide blended with respect to a crosslinked product obtained from an ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer.

Hereinafter, embodiments for carrying out the present invention will be described in detail.
[Ethylene / α-olefin / non-conjugated polyene copolymer]
The ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer of the present invention is characterized by satisfying the following requirements (1) and (2). In the following description, the ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer is also simply referred to as “ethylene / α-olefin / non-conjugated polyene copolymer”. The α-olefin / non-conjugated polyene copolymer of ˜20 is also referred to as “the ethylene-based copolymer of the present invention”.

  When the ethylene copolymer of the present invention is obtained by crosslinking the copolymer with a peroxide and obtaining the heterogeneous structure amount c and the heterogeneous structure size b by the small-angle neutron scattering method for the obtained crosslinked product. In requirement (1), the heterogeneous structure amount c and the peroxide blending amount satisfy the formula (1a), and the requirement (2) heterogeneous structure size b and the peroxide blending amount satisfy the formula (2a).

式（１ａ）および（２ａ）において、過酸化物配合量は、エチレン・α−オレフィン・非共役ポリエン共重合体１００質量部を架橋する際に用いる過酸化物の量（質量部）である。

In the formulas (1a) and (2a), the peroxide content is the amount (parts by mass) of peroxide used when 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer is crosslinked.

  The fact that the ethylene / α-olefin / non-conjugated polyene copolymer satisfies the formula (1a) means that the amount of heterogeneous structure in the copolymer is small. The fact that the ethylene / α-olefin / non-conjugated polyene copolymer satisfies the formula (2a) means that the heterogeneous structure size is small. Therefore, the crosslinked body formed from the ethylene-based copolymer of the present invention has uniform crosslinking points in the crosslinked structure. As described in the examples described later, the crosslinked product formed from the ethylene copolymer of the present invention is excellent in fatigue resistance.

  The formation conditions of the crosslinked body for determining whether the ethylene / α-olefin / non-conjugated polyene copolymer satisfies the requirements (1) and (2) are, for example, as follows. The following formation conditions are for determining whether or not the copolymer satisfies the requirements (1) and (2), and when the crosslinked product is obtained using the ethylene copolymer of the present invention. The conditions are not limited to the following formation conditions.

  The ethylene / α-olefin / non-conjugated polyene copolymer and the peroxide dicumyl peroxide were kneaded for 1 to 30 minutes in a roll kneader (roll temperature: 30 to 80 ° C., for example), and then kneaded. The material is press-molded at 50 to 200 ° C. for 1 to 120 minutes to obtain a sheet-like sample having a thickness of about 1 mm. Particularly preferably, the ethylene / α-olefin / non-conjugated polyene copolymer and the peroxide dicumyl peroxide are used in a 6-inch roll, and the roll temperature is set to the front roll / rear roll = 50 ° C./50° C. Roll peripheral speed: front roll / rear roll = 18 rpm / 15 rpm, roll gap is 2.5 mm, kneading time is kneaded for 8 minutes, and the kneaded material is press-molded at 180 ° C. for 10 minutes. Thus, a sheet-like sample having a thickness of about 1 mm is obtained.

Regarding the requirements (1) and (2), the amount of peroxide is usually 0.1 to 20 parts by mass, preferably 0.1 to 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer. It is 15-10 mass parts, More preferably, it is 0.15-5.0 mass part, Most preferably, it is 0.15-1.0 mass part. In addition, peroxides other than dicumyl peroxide can also be used, for example, the organic peroxide illustrated as a content component in the composition mentioned later. When using a peroxide other than dicumyl peroxide, the blending amount of the other peroxide is converted into a dicumyl peroxide equivalent, and the sufficiency of the above formulas (1a) and (2a) is determined. Dicumyl peroxide equivalent amount of other peroxides means that the amount of dicumyl peroxide necessary for generating one mole of peroxide radical during peroxide crosslinking is N ¹ parts by mass, If the amount of peroxide is N ² parts by mass, it means an amount obtained by multiplying the amount of other peroxides by N ¹ / N ² . When using other peroxides, the dicumyl peroxide equivalent is substituted into the above formulas (1a) and (2a).

  Before the neutron scattering measurement of the crosslinked body using the obtained sheet-like sample, it is preferable to treat the crosslinked body with a thermal solvent. By performing the pretreatment with a thermal solvent, the low molecular weight co-polymer generated by the decomposition of the polymer chain at the time of crosslinking of the uncrosslinked molecule of the ethylene-based copolymer or the peroxide, which is considered to be present in the crosslinked product. The polymer can be removed from the crosslinked body. For this reason, noise derived from components such as these uncrosslinked molecules during neutron scattering measurement can be greatly reduced.

  Therefore, by performing neutron scattering measurement on the crosslinked product after the thermal solvent treatment, a scattering intensity curve can be obtained with high accuracy even in the crosslinked product of the ethylene copolymer. For this reason, the non-uniform structure size b and the non-uniform structure amount c of the crosslinked network structure of the crosslinked body can be obtained by curve fitting described below.

  Examples of the solvent that can be used in the thermal solvent treatment include aromatic hydrocarbon solvents such as toluene, xylene, and benzene, alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, and methylcyclopentane, pentane, hexane, heptane, Examples thereof include organic solvents such as aliphatic hydrocarbons such as octane, decane, and dodecane. Among these, aromatic hydrocarbon solvents are preferable, and xylene and toluene are more preferable because components such as uncrosslinked molecules can be efficiently removed.

  In the thermal solvent treatment, the solvent can be used in an amount of preferably 50 mL or more, more preferably 70 to 130 mL, and more preferably 90 to 110 mL with respect to 1 g of the crosslinked product.

  The thermal solvent treatment is performed, for example, after immersing the crosslinked product in a solvent, preferably at 80 ° C. or more, more preferably at 130 to 150 ° C., and further preferably by refluxing the solvent. The heat solvent treatment time (particularly preferably the reflux operation time) is preferably 0.5 hours or more, more preferably 1 to 5 hours, and even more preferably 2 to 4 hours.

  After the thermal solvent treatment, the crosslinked product is preferably dried. The drying conditions are such that the drying temperature is preferably 10 to 40 ° C., more preferably 20 to 30 ° C., and the drying time is preferably 1 hour or more, more preferably 10 to 100 hours, and further preferably 60 to 80 hours. . Drying may be performed under vacuum.

  The neutron scattering measurement is preferably performed by a solvent swelling method using a deuterated solvent or a mixed solvent containing a deuterated solvent. Hereinafter, “deuterated solvent” and “mixed solvent containing deuterated solvent” are also collectively referred to as “deuterated solvent”. That is, it is preferable to irradiate a sample obtained by swelling a crosslinked product obtained from an ethylene copolymer with a deuterated solvent, and measure the scattering intensity. It is particularly preferable to perform neutron scattering measurement by a solvent swelling method for the crosslinked product after the thermal solvent treatment. By performing the swelling, the degree of swelling in the microscopic order can be uneven due to the density of the crosslink density, so that the scattering can be observed well.

Examples of the deuterated solvent include deuterated water, deuterated hexane, deuterated benzene, deuterated toluene, deuterated xylene, deuterated methanol, deuterated DMSO ((D ₃ C) ₂ S═O. ), Deuterated tetrahydrofuran, deuterated dichloromethane, deuterated chloroform, deuterated acetonitrile, deuterated N, N-dimethylformamide.

  Examples of the non-deuterated solvent that can be mixed with the deuterated solvent include water, hexane, benzene, toluene, xylene, methanol, dimethyl sulfoxide, tetrahydrofuran, dichloromethane, chloroform, acetonitrile, and N, N-dimethylformamide. Can be mentioned. In the mixed solvent, the content of the deuterated solvent is preferably 20% by mass or more, more preferably 50% by mass or more, and further preferably 80% by mass or more.

  In order to obtain a swollen crosslinked body, for example, a method of immersing the crosslinked body in a deuterated solvent at a temperature of 10 to 40 ° C. for 1 day or more, preferably 2 to 5 at a temperature of 20 to 30 ° C. Soak in the sun. The swollen crosslinked body in an equilibrium state in the deuterated solvent is taken out from the deuterated solvent, and neutron scattering measurement is performed.

  For neutron scattering measurement, an accelerator or a neutron source of a research reactor can be used. For example, an industry installed in the MLF, Materials and Life Science Research Facility, J-PARC (Ibaraki Prefecture) The beam line SANS-J of the research reactor JRR-3 owned by the Japan Atomic Energy Agency can be used. The cross-linked product is irradiated with neutron beams, and the neutron scattering intensity is measured. The measurement temperature is usually 10 to 40 ° C, more preferably 20 to 30 ° C.

Obtained by obtaining a scattering intensity curve I (q) in which the scattering intensity I is plotted against the wave number q (the vertical axis is I (q) and the horizontal axis is q), and the curve is curve-fitted by the equation (A). It is preferable to obtain the heterogeneous structure size b and the heterogeneous structure amount c of the crosslinked network structure from the parameters Ξ, I _ξ (0) and I _Ξ (0) obtained using the equations (2) and (3). The reason why the formula (A) is preferable in the curve fitting is that the speed at which the crosslinking reaction proceeds due to the fact that the radical concentration is increased only in the vicinity of the peroxide molecule that is the reaction start point when the ethylene copolymer is crosslinked. It is considered that the phenomenon that spatial non-uniformity occurs is occurring.

  M. Takenaka. NIPPON GOMU KYOKAISHI 87 (7), 299 (2014) and Y. Ikeda, N. Higashitani, K. Hijikata, Y. Kokubo, Y. Morita, M. Shibayama, N. Osaka, T. See Suzuki, H. Endo, and S. Kohjiya. Macromolecules 42 (7), 2741 (2009).

式（Ａ）および（１）〜（３）中、θは散乱角（ｒａｄ）であり、λは中性子線の波長（ｎｍ）であり、Ｉ_ξ（０）、Ｉ_Ξ（０）、ξ、ΞおよびＩ_incはフィッティングパラメーターである。式（Ａ）の右辺第１項はOrnstein-Zernike-Debye（ＯＺＤ）型関数であって、架橋網目からの散乱を記述する関数であり、右辺第２項はDebye-Bueche（ＤＢ）型関数であって、架橋網目の不均一構造からの散乱を記述する関数であり、右辺第３項は架橋網目構造以外からのインコヒーレント散乱強度である。

In equations (A) and (1)-(3), θ is the scattering angle (rad), λ is the wavelength of the neutron beam (nm), and I _ξ (0), I _Ξ (0), ξ, Ξ and I _inc are fitting parameters. The first term on the right side of equation (A) is an Ornstein-Zernike-Debye (OZD) type function, which describes the scattering from the bridging network, and the second term on the right side is a Debye-Bueche (DB) type function. The function describing the scattering from the heterogeneous structure of the crosslinked network, and the third term on the right side is the incoherent scattering intensity from other than the crosslinked network structure.

ξ is a length (unit: Å) characterizing the cross-linking network size, and Ξ is a length (unit: Å) characterizing the non-uniform structure size of the cross-linking network. I _ξ (0) is the weight of the first term on the right side of Equation (A), I _Ξ (0) is the weight of the second term on the right side of Equation (A), and the ratio I _Ξ (0) / I _ξ (0) means the non-uniform structure amount c.

It is preferable to obtain a scattering intensity curve by performing at least neutron scattering measurement in the region where the wave number q represented by the formula (1) is as follows. Note that “perform at least neutron scattering measurement” means that neutron scattering measurement is performed in a range including at least the following region, and neutron scattering measurement may be performed in a wider range than the following region. range of q is preferably 0.001～10Nm ^-1, more preferably 0.01～7Nm ^-1, more preferably a 0.2~5nm ^-1. Further, measurement in a larger q region, that is, wide-angle neutron scattering measurement may be performed.

The conditions for neutron scattering measurement are particularly preferably as follows. The sheet-like sample is cut into a round shape having a diameter of 1.2 mm, and then placed in a round bottom flask with a sufficient amount of xylene. Here, a sufficient amount of xylene means 100 mL of xylene per gram of sample. Then, reflux operation is performed at 140 ° C. for 3 hours. After completion of the reflux operation, the sample is taken out, left on a petri dish and dried at room temperature for 1 day. Thereafter, the sample is transferred to a desiccator kept in a vacuum and dried at room temperature under vacuum for 43 hours. After completion of drying, the sample is transferred to a fluororesin container, and a sample that is immersed in deuterated xylene at room temperature for 3 days to swell is used as a sample for small-angle neutron scattering measurement. A sample swollen with deuterated xylene is fixed to a sample holder, and the sample is irradiated with a neutron beam under the following conditions to perform small-angle neutron scattering measurement.
-Incident neutron beam: pulsed neutron beam-Measurement range: q = 0.2 nm ^-1 to q = 5 nm ^-1
・ Measurement temperature: Room temperature (25 ℃)

Curve fitting, for example, a range of at least including wavenumber q a 0.001～10Nm ^-1, is preferably carried out at least including a range at least including a range of 0.01～7Nm ^-1, or 0.2～4Nm ^-1 . Each fitting parameter is preferably obtained by regression analysis such as a least square method.
By the above method, the non-uniform structure size b and the non-uniform structure amount c can be obtained.

  The ethylene-based copolymer of the present invention includes a structural unit derived from ethylene, a structural unit derived from an α-olefin having 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene. ) And (2) are satisfied.

  Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1- Examples include tetradecene, 1-hexadecene, 1-eicocene, 4-methyl-1-pentene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene. The ethylene-based copolymer may have a structural unit derived from one kind of α-olefin, or may have a structural unit derived from two or more kinds of α-olefin.

  Among the α-olefins having 3 to 20 carbon atoms, α-olefins having 3 to 8 carbon atoms are preferable, and at least one selected from propylene, 1-butene, 1-hexene and 1-octene is more preferable, and propylene is particularly preferable. preferable.

  Specific examples of the non-conjugated polyene include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, and 7-methyl-1,6. -Chain non-conjugated dienes such as octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene- Cyclic non-conjugated dienes such as 2-norbornene and 6-chloromethyl-5-isopropylenyl-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 Decatriene, 4,8-dimethyl-1,4,8-decatriene, and a triene such as 4-ethylidene-8-methyl-1,7-nonadiene. The ethylene-based copolymer may have a structural unit derived from one type of non-conjugated polyene, or may have a structural unit derived from two or more types of non-conjugated polyene.

  Among non-conjugated polyenes, linear non-conjugated dienes such as 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, or 5-ethylidene-2-norbornene and 5-vinyl-2- Cyclic non-conjugated dienes such as combinations with norbornene are preferred, with 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, or combinations thereof being particularly preferred.

  Examples of the ethylene copolymer include an ethylene / propylene / 1,4-hexadiene copolymer, an ethylene / 1-butene / 1,4-hexadiene copolymer, and an ethylene / 1-pentene / 1,4-hexadiene copolymer. Polymer, 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 / propylene / 5-vinyl-2-norbornene copolymer, ethylene / 1-butene / 5-vinyl-2-norbornene copolymer, ethylene / 1-pentene / 5-vinyl-2-norbornene copolymer, ethylene / 1-hexene -Vinyl-2-norbornene copolymer, ethylene / 1-heptene / 5-vinyl-2-norbornene copolymer, ethylene / 1-octene / 5-vinyl-2-norbornene copolymer, ethylene / 1-nonene・ 5-vinyl-2-norbornene copolymer, ethylene / 1-decene, 5-vinyl-2-norbornene copolymer, ethylene / propylene / 5-ethylidene-2-norbornene 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-he Copolymers of putene and 5-ethylidene-2-norbornene and ethylene / 1-octene and 5-ethylidene-2-norbornene Polymer, ethylene / 1-nonene / 5-ethylidene-2-norbornene copolymer, ethylene / 1-decene / 5-ethylidene-2-norbornene copolymer, ethylene / propylene / 5-ethylidene-2-norbornene / 5- Vinyl-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-norbornene / 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 -A 5-vinyl-2-norbornene copolymer is mentioned.

In the ethylene-based copolymer, the molar ratio (ethylene unit / α-olefin unit) of the structural unit derived from ethylene and the structural unit derived from α-olefin having 3 to 20 carbon atoms is usually 40/60 to 99.9. /0.1, preferably 50/50 to 90/10, more preferably 55/45 to 80/20. The molar ratio can be determined by intensity measurement using a ¹³ C-NMR spectrometer.

  When the ethylene unit / α-olefin unit molar ratio is within the above range, the cross-linked product of the ethylene copolymer of the present invention exhibits excellent rubber elasticity and excellent mechanical strength, heat aging resistance and flexibility. This is preferable.

In the ethylene copolymer, the content of the structural unit derived from the non-conjugated polyene is usually 0.1 to 20% by mass, preferably 0.1 to 10% by mass, more preferably 100% by mass of the copolymer. Is 0.1 to 8.0% by mass, particularly preferably 0.5 to 5.0% by mass. The content can be determined by intensity measurement using a ¹³ C-NMR spectrometer.

  When the content of the non-conjugated polyene unit is in the above range, the cross-linked product of the ethylene copolymer of the present invention preferably exhibits excellent mechanical strength. For example, the copolymer may be formed using an organic peroxide. Is preferably used because it exhibits an appropriate crosslinking rate.

  The intrinsic viscosity [η] of the ethylene copolymer measured in decalin at 135 ° C. is usually 0.01 to 13.0 dl / g, preferably 0.1 to 8.0 dl / g, more preferably 0.8. 1 to 5.0 dl / g, more preferably 0.5 to 5.0 dl / g, particularly preferably 0.5 to 4.0 dl / g.

  Since the ethylene-based copolymer of the present invention satisfies the requirements (1) and (2), a crosslinked product having excellent fatigue resistance can be formed. As described above, in the present invention, it is possible to increase the strength of the product by grasping and controlling the heterogeneous structure of the crosslinked body. Therefore, it is possible to expect an improvement in product performance and product life.

[Method for producing ethylene / α-olefin / non-conjugated polyene copolymer]
The ethylene / α-olefin / non-conjugated polyene copolymer (ethylene copolymer) satisfying the requirements (1) and (2) of the present invention is ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated product. It can be obtained by copolymerizing with a polyene. The ethylene copolymer of the present invention is preferably a copolymer obtained by copolymerizing a monomer in the presence of a metallocene compound, and the monomer is copolymerized in the presence of a polymerization catalyst containing a metallocene compound. The obtained copolymer is more preferable.

(Metallocene compound)
Examples of the metallocene compound include compounds represented by the following formula [A1]. When the monomer is copolymerized using the polymerization catalyst containing the metallocene compound, an ethylene copolymer that satisfies the requirements (1) and (2) can be easily synthesized.

式［Ａ１］中の各記号の意味は以下のとおりである。

The meaning of each symbol in the formula [A1] is as follows.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² are each independently a hydrogen atom, hydrocarbon group, halogenated hydrocarbon group, silicon-containing group, or halogenated hydrocarbon. A hetero atom-containing group other than a group and a silicon-containing group is shown. Two adjacent groups among R ^{1 to} R ⁴ may be bonded to each other to form a ring.

R ⁶ and R ¹¹ each independently represent a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing group, or a heteroatom-containing group other than a halogenated hydrocarbon group and a silicon-containing group.

R ⁷ and R ¹⁰ each independently represent a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing group, or a heteroatom-containing group other than a halogenated hydrocarbon group and a silicon-containing group.

R ⁶ and R ⁷ may be bonded to each other to form a ring, and R ¹⁰ and R ¹¹ may be bonded to each other to form a ring. It is preferred that R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms at the same time.

As the hydrocarbon group for R ¹ to R ^12, preferably a hydrocarbon group having 1 to 20 carbon atoms, for example, an alkyl group having 1 to 20 carbon atoms, alicyclic group having 3 to 20 carbon atoms, 6 carbon atoms Examples include 20 aryl groups and C7-20 arylalkyl groups. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, amyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl Group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, Norbornyl group, adamantyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, isopropylphenyl group, t-butyl Phenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group, anthracenyl group, a benzyl group and a cumyl group.

Examples of the halogenated hydrocarbon group for R ^{1 to} R ¹² include a trifluoromethyl group, a trifluoromethylphenyl group, a pentafluorophenyl group, and a chlorophenyl group.

Examples of the silicon-containing group in R ^{1 to} R ¹² include a silyl group, a siloxy group, a hydrocarbon group-substituted silyl group, a hydrocarbon group-substituted siloxy group, a halogenated hydrocarbon group-substituted silyl group, and a halogenated hydrocarbon group-substituted siloxy Groups. For example, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group, dimethyl (pentafluorophenyl) ) A silyl group is mentioned.

Examples of the hetero atom-containing group in R ^{1 to} R ¹² include oxygen-containing groups such as a methoxy group, ethoxy group, and phenoxy group, nitro group, cyano group, N-methylamino group, N, N-dimethylamino group, N -Nitrogen-containing groups such as phenylamino groups, boron-containing groups such as boranetriyl groups and diboranyl groups, and sulfur-containing groups such as sulfonyl groups and sulfenyl groups.

R ¹³ and R ¹⁴ each independently represents an aryl group or a halogenated aryl group.
As the aryl group and the halogenated aryl group in R ¹³ and R ^14, an aryl group having 6 to 20 carbon atoms and a halogenated aryl group are preferable, for example, a phenyl group, an o-tolyl group, an m-tolyl group, p- Examples include tolyl group, xylyl group, isopropylphenyl group, t-butylphenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group, anthracenyl group, trifluoromethylphenyl group, pentafluorophenyl group, and chlorophenyl group. Among these, a p-tolyl group and a p-chlorophenyl group are preferable.

M ¹ represents a zirconium atom.
Y ¹ represents a carbon atom or a silicon atom, preferably a carbon atom.
Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or nonconjugated diene having 4 to 20 carbon atoms, an anionic ligand, or a neutral ligand that can be coordinated by a lone pair of electrons. , J represents an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Qs may be the same or different.

As a halogen atom in Q, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example, Preferably it is a chlorine atom.
Examples of the hydrocarbon group in Q include a hydrocarbon group having 1 to 10 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, 2-methylpropyl group, 1, 1-dimethylpropyl group, 2,2-dimethylpropyl group, 1,1-diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, sec-butyl group, Examples include t-butyl group, 1,1-dimethylbutyl group, 1,1,3-trimethylbutyl group, neopentyl group, cyclohexylmethyl group, cyclohexyl group, 1-methyl-1-cyclohexyl group, and benzyl group. A methyl group, an ethyl group, and a benzyl group;

The neutral conjugated or nonconjugated diene having 4 to 20 carbon atoms is preferably a neutral conjugated or nonconjugated diene having 4 to 10 carbon atoms. Neutral conjugated or non-conjugated dienes include, for example, s-cis- or s-trans-η ⁴ -1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4-diphenyl-1 , 3-butadiene, s-cis- or s-trans-η ⁴ -3-methyl-1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4-dibenzyl-1,3-butadiene , S-cis- or s-trans-η ⁴ -2,4-hexadiene, s-cis- or s-trans-η ⁴ -1,3-pentadiene, s-cis- or s-trans-η ⁴ -1 , 4-ditolyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene.

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

  Examples of the neutral ligand that can be coordinated by a lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane. And ethers.

Examples of the cyclopentadienyl group having R ¹ to R ⁴ in the formula [A1] include an unsubstituted cyclopentadienyl group and a 3-t-butylcyclopentadienyl group in which R ¹ to R ⁴ are hydrogen atoms. 3-methylcyclopentadienyl group, 3-trimethylsilylcyclopentadienyl group, 3-phenylcyclopentadienyl group, 3-adamantylcyclopentadienyl group, 3-amylcyclopentadienyl group, 3-cyclohexylcyclo 3-position 1-substituted cyclopentadienyl group such as pentadienyl group, 3-t-butyl-5-methylcyclopentadienyl group, 3-t-butyl-5-ethylcyclopentadienyl group, 3-phenyl- 5-methylcyclopentadienyl group, 3,5-di-t-butylcyclopentadienyl group, 3,5-dimethylcyclopentadiene Group, 3-phenyl-5-methyl-cyclopentadienyl group include 3,5-position disubstituted cyclopentadienyl groups, such as 3-trimethylsilyl-5-methyl-cyclopentadienyl group. From the viewpoint of easy synthesis of the metallocene compound, production cost, and copolymerization ability of the non-conjugated polyene, an unsubstituted cyclopentadienyl group in which R ¹ to R ⁴ are hydrogen atoms is preferable.

Examples of the fluorenyl group having R ⁵ to R ¹² in the formula [A1] include an unsubstituted fluorenyl group in which R ⁵ to R ¹² are hydrogen atoms; 2-methylfluorenyl group, 2-t-butylfluorenyl Group, 2-position 1-substituted fluorenyl group such as 2-phenylfluorenyl group; 4-position 1-substituted fluorenyl group such as 4-methylfluorenyl group, 4-t-butylfluorenyl group, 4-phenylfluorenyl group Group: 2,7-di-t-butylfluorenyl group, 3,6-di-t-butylfluorenyl group, etc. 2,7-position or 3,6-position disubstituted fluorenyl group; 2,7-dimethyl 2,3,6,7-position 4-substituted fluorenyl groups such as 3,6-di-t-butylfluorenyl group and 2,7-diphenyl-3,6-di-t-butylfluorenyl group; Represented by the formula [V-I] or [V-II]. That such groups, attached R ⁶ and R ⁷ together form a ring, R ¹⁰ and R ¹¹ are bonded to each other include 2,3,6,7-position 4-substituted fluorenyl group which forms a ring It is done.

式［Ｖ−Ｉ］、［Ｖ−II］中、Ｒ⁵、Ｒ⁸、Ｒ⁹、Ｒ¹²は前記式［Ａ１］における定義と同様であり、好ましくは水素原子であり、Ｒ^a、Ｒ^b、Ｒ^c、Ｒ^d、Ｒ^e、Ｒ^f、Ｒ^gおよびＲ^hは、それぞれ独立に水素原子または炭素数１〜５のアルキル基であり、隣接した置換基と互いに結合して環を形成していてもよい。アルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｔ−ブチル基、アミル基、ｎ−ペンチル基が挙げられる。

In the formulas [V-I] and [V-II], R ⁵ , R ⁸ , R ⁹ and R ¹² are as defined in the formula [A1], preferably a hydrogen atom, and R ^a , R ^b , R ^c , R ^d , R ^e , R ^f , R ^g and R ^h are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and are bonded to adjacent substituents to form a ring. It may be. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an amyl group, and an n-pentyl group.

In the formula [V-I], R ^x and R ^y are each independently a hydrocarbon group optionally having an unsaturated bond having 1 to 3 carbon atoms, and R ^x is a carbon to which R ^a or R ^c is bonded. May form a double bond, or R ^y may form a double bond with the carbon to which R ^e or R ^g is bonded. R ^x and R ^y are both _{-CH 2 -, - CH 2 -CH} 2 - or -CH ₂ = CH ₂ - is preferably, or, R ^x and R ^y are both having 1 or 2 hydrocarbon atoms R ^x is combined with carbon bonded to R ^a or R ^c to form a double bond, and R ^y is combined with carbon bonded to R ^e or R ^g to form a double bond It is preferable.

  Examples of the group represented by the formula [V-I] or [V-II] include an octamethyloctahydrodibenzofluorenyl group represented by the formula [V-III] and a formula [V-IV]. Tetramethyldodecahydrodibenzofluorenyl group, octamethyltetrahydrodicyclopentafluorenyl group represented by the formula [V-V], hexamethyldihydrodicyclopentafluor represented by the formula [V-VI] Examples include an oleenyl group and a b, h-dibenzofluorenyl group represented by the formula [V-VII].

Any of the metallocene compounds represented by the formula [A1] containing these fluorenyl groups is excellent in the copolymerization ability of the nonconjugated polyene. When Y ¹ is a silicon atom, it is represented by the above formula [V-I], a 2,7-position 2-substituted fluorenyl group, a 3,6-position 2-substituted fluorenyl group, a 2,3,6,7-position 4-substituted fluorenyl group. In particular, metallocene compounds having a 2,3,6,7-position 4-substituted fluorenyl group are particularly excellent. When Y ¹ is a carbon atom, 3, 6-position 2-substituted fluorenyl group, 2, 3, 6, 7-position 4-substituted fluorenyl group, 2, 3, 6, 7-position represented by the above formula [V-I] A metallocene compound having a 4-substituted fluorenyl group is particularly excellent.

Specific examples of the metallocene compound represented by the formula [A1] include
When Y ¹ is a silicon atom,
Diphenylsilylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Diphenylsilylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Diphenylsilylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Diphenylsilylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Diphenylsilylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Diphenylsilylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Diphenylsilylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Diphenylsilylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Diphenylsilylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Is mentioned.

When Y ¹ is a carbon atom,
Diphenylmethylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Diphenylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Diphenylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Diphenylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Diphenylmethylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Diphenylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Diphenylmethylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Diphenylmethylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (pt-butylphenyl) methylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride,
Di (pt-butylphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-tert-butylfluorenyl) zirconium dichloride,
Di (pt-butylphenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-tert-butylfluorenyl) zirconium dichloride,
Di (pt-butylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (pt-butylphenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (pt-butylphenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (pt-butylphenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (pt-butylphenyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride is mentioned.

  Examples of structural formulas of metallocene compounds include di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride ((A1-1) below) and di (p-chlorophenyl) The structural formula of methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride (the following (A1-2)) is shown below. These compounds are particularly preferable in synthesizing an ethylene copolymer that satisfies the requirements (1) and (2).

メタロセン化合物は１種単独で用いてもよく、２種以上組み合わせてもよい。

A metallocene compound may be used individually by 1 type, and may be combined 2 or more types.

  The metallocene compound represented by the formula [A1] can be produced by any method without any particular limitation. For example, J. et al. Organomet. Chem. 63, 509 (1996), WO 2005/100410, WO 2006/123759, WO 01/27124, JP 2004-168744, JP 2004-175759, JP The said compound can be manufactured based on the method as described in 2000-212194 gazette.

(Catalyst containing metallocene compound)
As a polymerization catalyst that can be suitably used for the production of the ethylene copolymer of the present invention,
(A) a metallocene compound represented by the formula [A1],
(B) (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) a compound that reacts with the metallocene compound (a) to form an ion pair. Seed compounds,
If necessary,
A catalyst containing (c) a support is preferred.

The polymerization catalyst, if necessary,
(D) An organic compound component can also be included.

Hereinafter, each component will be specifically described.
<Organic metal compound (b-1)>
Examples of the organometallic compound (b-1) include organometallic compounds of Groups 1, 2 and 12, 13 of the periodic table, such as compounds represented by the following formulas [bI] to [bIII]. It is done.

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

  Such compounds include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, tricycloalkylaluminum, isobutylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methyl. Examples thereof include aluminum dichloride, dimethylaluminum chloride, diisobutylaluminum hydride and the like.

(B-1b) Formula M ² AlR ^a ₄ ... [BII] (In formula [bII], M ² represents Li, Na or K, and R ^a is a hydrocarbon having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. A complex alkylated product of a group 1 metal of a periodic table and aluminum.
Examples of such compounds include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

(B-1c) Formula R ^a R ^b M ³ ... [BIII] (In the formula [bIII], R ^a and R ^b may be the same or different from each other, and have 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. A dialkyl compound having a group 2 or group 12 metal in the periodic table represented by: M ³ is Mg, Zn or Cd.

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

<Organic aluminum oxy compound (b-2)
The organoaluminum oxy compound (b-2) may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687.

A conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon solvent.
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the suspension of the hydrocarbon.

  (2) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.

  (3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted 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 organometallic 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 aluminoxane solvent.

  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). Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum and triisobutylaluminum are particularly preferable. An organoaluminum compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  The benzene-insoluble organoaluminum oxy compound which is one embodiment of the organoaluminum oxy compound (b-2) is such that the Al component dissolved in benzene at 60 ° C. is usually 10% by weight or less with respect to 100% by weight of benzene in terms of Al atoms. The content is preferably 5% by weight or less, particularly preferably 2% by weight or less, that is, the one that is insoluble or hardly soluble in benzene.

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

〔式［bIV］中、Ｒ¹は炭素数１〜１０の炭化水素基を示し、Ｒ²〜Ｒ⁵は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素数１〜１０の炭化水素基を示す。〕

[In the formula [bIV], 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 may be a hydrogen atom, a halogen atom, or a carbon atom having 1 to 10 carbon atoms. A hydrocarbon group is shown. ]

The organoaluminum oxy compound containing boron represented by the formula [bIV] includes an alkyl boronic acid represented by the following formula [bV],
R ¹ −B (OH) ₂ ... [BV]
(In formula [bV], R ¹ represents the same group as R ¹ in formula [bIV].)

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 formula [bV] include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, and n-hexyl boronic 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, methyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic 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).

  Of 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 organoaluminum oxy compound (b-2) as described above is used singly or in combination of two or more.

<Compound (b-3) which forms an ion pair by reacting with the metallocene compound (a)>
Examples of the compound (b-3) that reacts with the metallocene compound (a) to form an ion pair (hereinafter referred to as “ionized ionic compound”) include JP-A-1-501950 and JP-A-1-502020. Lewis acids, ionic compounds, and boranes described in JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321106, and the like. Examples thereof include compounds and carborane compounds. 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, as the Lewis acid, a compound represented by BR ₃ (R is a phenyl group or fluorine which may have a substituent such as fluorine, methyl group or trifluoromethyl group) can be mentioned. 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.
Examples of the ionic compound include a compound represented by the following formula [bVI].

（式［bVI］中、Ｒ¹⁺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。Ｒ²〜Ｒ⁵は、互いに同一でも異なっていてもよく、有機基、好ましくはアリール基または置換アリール基である。）

(In the formula [bVI], examples of R ¹⁺ include H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal. ^{2 to} R ⁵ may be the same as or different from each other, and are an organic group, preferably an aryl group or a substituted aryl group.

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

Specifically, as the ammonium cation,
Trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, 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;
Dialkylammonium cations such as di (isopropyl) ammonium cations, dicyclohexylammonium cations;
Etc.

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

R ¹⁺ is preferably a carbonium cation, an ammonium cation or the like, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation.

  Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

  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 and the like.

  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 [bVII] or [bVIII]. Here, in the formula, Et represents an ethyl group.

ボラン化合物として具体的には、例えば、
デカボラン；
ビス〔トリ（ｎ−ブチル）アンモニウム〕ノナボレート、ビス〔トリ（ｎ−ブチル）アンモニウム〕デカボレート、ビス〔トリ（ｎ−ブチル）アンモニウム〕ウンデカボレート、ビス〔トリ（ｎ−ブチル）アンモニウム〕ドデカボレート、ビス〔トリ（ｎ−ブチル）アンモニウム〕デカクロロデカボレート、ビス〔トリ（ｎ−ブチル）アンモニウム〕ドデカクロロドデカボレートなどのアニオンの塩；
トリ（ｎ−ブチル）アンモニウムビス（ドデカハイドライドドデカボレート）コバルト酸塩（III）、ビス〔トリ（ｎ−ブチル）アンモニウム〕ビス（ドデカハイドライドドデカボレート）ニッケル酸塩（III）などの金属ボランアニオンの塩
などが挙げられる。

Specifically as a borane compound, for example,
Decaborane;
Bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate Salts of anions such as bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate;
Of metal borane anions such as tri (n-butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III) and bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickate (III) Examples include salt.

Specific examples of the carborane compound include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecarborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride. -1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaunaborane, 2,7-dicarbaundecaborane , Undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane, 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 dicarbaound decaborate, 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) Ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cuprate (III), tri (n-butyl) Ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (III), tri (n-butyl) ammonium Bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicar (Boundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarboundeborate) 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) cobalt acid (III), such as bis [tri (n- butyl) ammonium] bis (carborane borate) salt of a metal carborane anions such as nickel salt (IV).

  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 Groups 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium Etc. Salts, and organic salts such as triphenylethyl salts can be used, not limited thereto.

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

An ionized ionic compound (b-3) is used individually by 1 type or in combination of 2 or more types.
As a polymerization catalyst, the metallocene compound (a) represented by the above formula [A1], an organometallic compound (b-1) such as triisobutylaluminum, an organoaluminum oxy compound (b-2) such as methylaluminoxane, and tri Production of ethylene / α-olefin / non-conjugated polyene copolymer using a metallocene catalyst containing at least one selected from ionized ionic compounds (b-3) such as phenylcarbenium tetrakis (pentafluorophenyl) borate In this case, a very high polymerization activity can be exhibited.

<Carrier (c)>
The carrier (c) (particulate carrier) is an inorganic compound or an organic compound, and is a granular or particulate solid. Examples of inorganic compounds include porous oxides containing SiO ₂ and / or Al ₂ O ₃ as main components, inorganic halides such as MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ , clay, clay mineral, or ion exchange A layered compound. Examples of the organic compound include a polymer formed from a monomer containing a C 2-14 α-olefin as a main component, a polymer formed from a monomer containing styrene as a main component, and vinylcyclohexane as a main component. Examples include polymers formed from monomers.

<Organic compound component (d)>
The organic compound component (d) is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer as necessary. Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

<Production conditions for ethylene / α-olefin / non-conjugated polyene copolymer>
The ethylene-based copolymer of the present invention can be obtained by copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene. When such a monomer is copolymerized, the usage and order of addition of the components constituting the polymerization catalyst described above are arbitrarily selected. For example, (1) the metallocene compound (a) is added alone to the polymerization vessel. A method, (2) a method in which the metallocene compound (a) and the compound (b) are added to the polymerization vessel in an arbitrary order, (3) a catalyst component in which the metallocene compound (a) is supported on the carrier (c), and the compound (b ) In any order, (4) a catalyst component having the compound (b) supported on the carrier (c), and a method in which the metallocene compound (a) is added to the polymerizer in any order. (5) A method in which a catalyst component in which a metallocene compound (a) and a compound (b) are supported on a carrier (c) is added to a polymerization vessel.

In each of the above methods (2) to (5), at least two of the metallocene 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 metallocene compound (a) is supported on the carrier (c) and the solid catalyst component in which the metallocene compound (a) and the compound (b) are supported on the carrier (c) are prepolymerized with olefin. Alternatively, a catalyst component may be further supported on the prepolymerized solid catalyst component.

In the present invention, the ethylene / α-olefin / non-conjugated polyene copolymer can be suitably obtained by copolymerizing a monomer in the presence of the polymerization catalyst as described above.
When the olefin is polymerized using the polymerization catalyst as described above, the metallocene compound (a) is usually 10 ⁻¹² to 10 ⁻² mol, preferably 10 ⁻¹⁰ to 10 ⁻⁸ mol, per liter of reaction volume. Used in such an amount.

  In the compound (b-1), the molar ratio [(b-1) / M] of the compound (b-1) and all transition metal atoms (M) in the metallocene compound (a) is usually 0.01 to The amount used is 50000, preferably 0.05 to 15000. In the compound (b-2), the molar ratio [(b-2) / M] of the aluminum atom in the compound (b-2) and all the transition metal atoms (M) in the metallocene compound (a) is usually The amount used is 10 to 50000, preferably 20 to 10000. In the compound (b-3), the molar ratio [(b-3) / M] of the compound (b-3) and all transition metal atoms (M) in the metallocene compound (a) is usually 1 to 20, Preferably it is used in such an amount as to be 1-15.

  In the present invention, the method for producing an ethylene / α-olefin / non-conjugated polyene copolymer can be carried out by any of liquid phase polymerization methods such as solution (dissolution) polymerization and suspension polymerization, or gas phase polymerization methods. Although not particularly limited, it is preferable to have a step of obtaining the following polymerization reaction solution.

  The step of obtaining a polymerization reaction liquid is a method in which a monomer containing ethylene, an α-olefin, and a non-conjugated polyene is copolymerized in the presence of a polymerization catalyst using a polymerization solvent, thereby producing an ethylene / α-olefin / non-conjugated. This is a step of obtaining a polymerization reaction solution of a polyene copolymer.

  Examples of the polymerization solvent include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, benzene, toluene, xylene And aromatic hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. These may be used alone or in combination of two or more. Moreover, olefin itself can also be used as a solvent. Of these, hexane is preferable from the viewpoint of separation and purification from the obtained ethylene / α-olefin / non-conjugated polyene copolymer.

  The polymerization temperature is usually −50 to + 200 ° C., preferably 0 to + 200 ° C., more preferably +80 to + 200 ° C. Depending on the polymerization activity of the polymerization catalyst used, it may be higher (+ 80 ° C. or higher). From the viewpoint of catalytic activity, copolymerizability and productivity.

  The polymerization pressure is usually under normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out by any of batch, semi-continuous and continuous methods. . Furthermore, the polymerization can be performed in two or more stages having different reaction conditions. In the present invention, among these, it is preferable to employ a method in which a monomer is continuously supplied to a reactor to carry out copolymerization.

  The reaction time (average residence time when copolymerization is carried out in a continuous process) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 5 minutes to 3 hours. It is.

  The molecular weight of the resulting ethylene / α-olefin / non-conjugated polyene copolymer can be adjusted by allowing hydrogen to be present in the polymerization system or changing the polymerization temperature. Furthermore, it can also adjust with the quantity of the compound (b) to be used. Specific examples include triisobutylaluminum, methylaluminoxane, diethylzinc and the like. When hydrogen is added, the amount is suitably about 0.001 to 100 NL per kg of monomer.

  The molar ratio of ethylene to α-olefin having 3 to 20 carbon atoms (ethylene / α-olefin) is usually 40/60 to 99.9 / 0.1, preferably 50/50 to 90/10. Preferably it is 55 / 45-80 / 20.

  The amount of the nonconjugated polyene used is usually 0.1 to 20% by mass, preferably 0 to 100% by mass of the total of ethylene, the α-olefin having 3 to 20 carbon atoms and the nonconjugated polyene (total monomer used amount). 0.1 to 10% by mass, more preferably 0.1 to 8.0% by mass, and particularly preferably 0.5 to 5.0% by mass.

[Composition]
The composition of the present invention contains an ethylene / α-olefin / non-conjugated polyene copolymer (hereinafter, also referred to as “ethylene copolymer (A)”) that satisfies the requirements (1) and (2) described above. The composition of the present invention may contain two or more ethylene copolymers (A).

  In the composition of the present invention, the content of the ethylene copolymer (A) is usually 12% by mass or more, preferably 15 to 90% by mass, more preferably 20 to 60% by mass, and particularly preferably 25 to 55%. % By mass. When the content ratio of the ethylene copolymer (A) is within the above range, it is preferable in that a crosslinked product having excellent fatigue resistance is formed.

《Other ingredients》
The composition of the present invention may further contain another polymer other than the ethylene-based copolymer (A) depending on the purpose. In addition, the composition of the present invention may contain a crosslinking agent, a crosslinking aid, a vulcanization accelerator, a vulcanization aid, a softening agent, an inorganic filler, a reinforcing agent, an antiaging agent, a processing aid, an activity depending on the purpose. It may contain at least one additive selected from agents, hygroscopic agents, heat stabilizers, weathering stabilizers, antistatic agents, colorants, lubricants, thickeners and foaming agents. Each additive may be used individually by 1 type, and may use 2 or more types together.

<Other polymers>
The composition of the present invention may contain other polymers in addition to the ethylene copolymer (A). Examples of other polymers that need to be crosslinked include crosslinkable rubbers such as natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, acrylic rubber, silicone rubber, fluorine rubber, and urethane rubber. Is mentioned. Other polymers that do not require crosslinking include, for example, a block copolymer of styrene and butadiene (SBS), polystyrene-poly (ethylene-butylene) -polystyrene (SEBS), polystyrene-poly (ethylene-propylene) -polystyrene ( SEPS) styrene thermoplastic elastomer (TPS), olefin thermoplastic elastomer (TPO), vinyl chloride elastomer (TPVC), ester thermoplastic elastomer (TPC), amide thermoplastic elastomer (TPA), urethane heat Examples include elastomers such as a plastic elastomer (TPU) and other thermoplastic elastomers (TPZ). The content of the other polymer is usually 50 parts by mass or less, preferably 20 parts by mass or less with respect to 100 parts by mass of the ethylene-based copolymer (A).

<Crosslinking agent, crosslinking aid, vulcanization accelerator and vulcanization aid>
The composition of the present invention preferably further contains a crosslinking agent.
Examples of the cross-linking agent include cross-linking agents generally used for cross-linking rubbers, and specifically include peroxides, sulfur compounds, phenol resins, amino resins, quinones or their derivatives, amines. Compounds, azo compounds, epoxy compounds, isocyanate compounds, and hydrosilicone compounds. Among these, a peroxide is preferable from the viewpoint that the crosslinked body is not affected by the structure of the crosslinking agent itself.

Examples of the peroxide include an organic peroxide.
Examples of organic peroxides include dialkyl peroxides, diacyl peroxides, peroxyketals, peroxyesters, peroxycarbonates, peroxydicarbonates, ketone peroxides, and hydroperoxides. Dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, 2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert- Butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, benzoyl peroxide, p- Chlorobenzoyl peroxide, 2,4- Chlorobenzoyl peroxide, lauroyl peroxide, diacetyl peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) ) Valerate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate.

When a peroxide is used as the crosslinking agent, the amount of peroxide in the composition is selected from the ethylene copolymer (A) and other polymers that need to be crosslinked (crosslinkable rubber, etc.). ) Is usually 0.1 to 20 parts by mass, preferably 0.15 to 15 parts by mass, and more preferably 0.15 to 10 parts by mass. When the amount of the peroxide is within the above range, there is no bloom on the surface of the obtained crosslinked product, and the composition exhibits excellent crosslinking properties.
When using a peroxide as a crosslinking agent, it is preferable to use a crosslinking aid in combination.

  Examples of the crosslinking aid include sulfur; quinone dioxime crosslinking aids such as p-quinonedioxime; acrylic crosslinking aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; diallyl phthalate and triallyl isocyanurate Allyl-based crosslinking aids such as: maleimide-based crosslinking aids; divinylbenzene; zinc oxide (for example, ZnO # 1 and two types of zinc oxide, manufactured by Hux Itec Corp.), magnesium oxide, zinc white (for example, “META-Z102”) (Zinc oxide such as “trade name; manufactured by Inoue Lime Industry Co., Ltd.”).

  When a crosslinking aid is used, the blending amount of the crosslinking aid in the composition is the sum of the ethylene-based copolymer (A) and other polymers that need to be blended (crosslinkable rubber, etc.) blended as necessary. It is 0-15 mass parts normally with respect to 100 mass parts, Preferably it is 0.1-10 mass parts.

  Examples of the sulfur compound (vulcanizing agent) include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dithiocarbamate.

  When a sulfur compound is used as a crosslinking agent, the compounding amount of the sulfur compound in the composition is such that the ethylene copolymer (A) and other polymers (crosslinkable rubber, etc.) that are blended as necessary. ) Is generally 0.3 to 10 parts by mass, preferably 0.5 to 7.0 parts by mass, and more preferably 0.7 to 5.0 parts by mass. When the compounding amount of the sulfur compound is within the above range, there is no bloom on the surface of the obtained crosslinked product, and the composition exhibits excellent crosslinking characteristics.

When a sulfur compound is used as the crosslinking agent, it is preferable to use a vulcanization accelerator in combination.
Examples of the vulcanization accelerator include a thiazole vulcanization accelerator, a guanidine vulcanization accelerator, an aldehyde amine vulcanization accelerator, an imidazoline vulcanization accelerator, a thiuram vulcanization accelerator, and a dithioate vulcanization accelerator. Examples thereof include a sulfur accelerator, a thiourea vulcanization accelerator, and a xanthate vulcanization accelerator.

  When a vulcanization accelerator is used, the blending amount of the vulcanization accelerator in the composition is such that the ethylene-based copolymer (A) and other polymers that need to be cross-linked are included as necessary (cross-linkable rubber, etc.) The total amount is generally 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass. When the blending amount of the vulcanization accelerator is within the above range, there is no bloom on the surface of the obtained crosslinked product, and the composition exhibits excellent crosslinking properties.

When a sulfur compound is used as the crosslinking agent, a vulcanization aid can be used in combination.
Examples of the vulcanization aid include zinc oxide, magnesium oxide, and zinc white.
When a vulcanization aid is used, the blending amount of the vulcanization aid in the composition is determined based on the ethylene copolymer (A) and other polymers that need to be cross-linked (crosslinkable rubber, etc.). The total amount is usually 1 to 20 parts by mass.

<Softener>
Examples of the softener include petroleum oil softeners such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and petroleum jelly; coal tar softener such as coal tar; castor oil, linseed oil, rapeseed oil, large Fat oil-based softeners such as bean oil and coconut oil; waxes such as beeswax and carnauba wax; naphthenic acid, pine oil, rosin or derivatives thereof; synthetic polymer substances such as terpene resin, petroleum resin and coumarone indene resin; dioctyl Ester softeners such as phthalate and dioctyl adipate; other examples include microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon synthetic lubricating oil, tall oil, and sub (factis). Among them, petroleum softener And process oil is particularly preferred.

  When the composition contains a softener, the blending amount of the softener is a total of 100 masses of the ethylene copolymer (A) and other polymers (elastomer, crosslinkable rubber, etc.) blended as necessary. The amount is usually 2 to 100 parts by mass, preferably 10 to 100 parts by mass with respect to parts.

<Inorganic filler>
Examples of the inorganic filler include light calcium carbonate, heavy calcium carbonate, talc, and clay.

  When the composition contains an inorganic filler, the blending amount of the inorganic filler is the total of the ethylene copolymer (A) and other polymers (elastomer, crosslinkable rubber, etc.) blended as necessary. It is 2-100 mass parts normally with respect to 100 mass parts, Preferably it is 5-100 mass parts. When the blending amount of the inorganic filler is within the above range, the composition is excellent in kneadability and a crosslinked product excellent in mechanical properties can be obtained.

<Reinforcing agent>
Examples of the reinforcing agent include carbon black, carbon black surface-treated with a silane coupling agent, silica, calcium carbonate, activated calcium carbonate, fine powder talc, and differential silicic acid.

  When the composition contains a reinforcing agent, the amount of the reinforcing agent is 100 mass in total of the ethylene copolymer (A) and other polymers (elastomer, crosslinkable rubber, etc.) compounded as necessary. The amount is usually 5 to 300 parts by mass, preferably 10 to 100 parts by mass with respect to parts.

<Anti-aging agent (stabilizer)>
By blending an anti-aging agent (stabilizer) with the composition of the present invention, the lifetime of the crosslinked product formed therefrom can be extended. Such anti-aging agents include conventionally known anti-aging agents such as amine-based anti-aging agents, phenol-based anti-aging agents, and sulfur-based anti-aging agents.

  When the composition contains an antioxidant, the blending amount of the antioxidant is the sum of the ethylene copolymer (A) and other polymers (elastomer, crosslinkable rubber, etc.) blended as necessary. It is 0.3-10 mass parts normally with respect to 100 mass parts, Preferably it is 0.5-7.0 mass parts. When the blending amount of the anti-aging agent is within the above range, there is no bloom on the surface of the obtained crosslinked product, and generation of vulcanization inhibition can be further suppressed.

<Processing aid>
As processing aids, those generally blended into rubber as processing aids can be widely used. As processing aids, for example, fatty acids such as ricinoleic acid, stearic acid, palmitic acid, lauric acid, fatty acid salts such as barium stearate, zinc stearate, calcium stearate, ricinoleic acid ester, stearic acid ester, palmitic acid ester, Examples include fatty acid esters such as lauric acid esters, and fatty acid derivatives such as N-substituted fatty acid amides. Of these, stearic acid is preferred.

  When the composition contains a processing aid, the blending amount of the processing aid is the total of the ethylene copolymer (A) and other polymers (elastomer, crosslinkable rubber, etc.) blended as necessary. The amount is usually 10 parts by mass or less, preferably 8.0 parts by mass or less with respect to 100 parts by mass.

<Activator>
Examples of the activator include amines such as di-n-butylamine, dicyclohexylamine, and monoelaanolamine; diethylene glycol, polyethylene glycol, lecithin, triarylate melilate, aliphatic carboxylic acid, and aromatic carboxylic acid zinc compound. Activators; zinc peroxide preparations; octadecyltrimethylammonium bromide, synthetic hydrotalcite, special quaternary ammonium compounds.

  When the composition contains an active agent, the amount of the active agent is 100 mass in total of the ethylene-based copolymer (A) and other polymers (elastomer, crosslinkable rubber, etc.) to be blended as necessary. The amount is usually 0.2 to 10 parts by mass, preferably 0.3 to 5 parts by mass with respect to parts.

<Hygroscopic agent>
Examples of the hygroscopic agent include calcium oxide, silica gel, sodium sulfate, molecular sieve, zeolite, and white carbon.

  When the composition contains a hygroscopic agent, the amount of the hygroscopic agent is 100 mass in total of the ethylene copolymer (A) and other polymers (elastomer, crosslinkable rubber, etc.) blended as necessary. The amount is usually 0.5 to 15 parts by mass, preferably 1.0 to 12 parts by mass with respect to parts.

<Foaming agent>
The crosslinked body formed from the composition of the present invention may be a non-foamed body or a foamed body. A foaming agent can be used in forming the foam. For example, inorganic foaming agents such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite; N, N′-dinitroterephthalamide, N, N Nitroso compounds such as'-dinitrosopentamethylenetetramine; azo compounds such as azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate; benzenesulfonylhydrazide, toluenesulfonylhydrazide, p , P′-oxybis (benzenesulfonylhydrazide) diphenylsulfone-3,3′-disulfenylhydrazide and other sulfonylhydrazide compounds; calcium azide, 4,4′-diphenylsulfonylazide, Azide compounds such as La toluenesulfonyl azide and the like.

  When the composition contains a foaming agent, the blending amount of the foaming agent is appropriately selected so that the specific gravity of the foamed product after crosslinking foaming is usually 0.01 to 0.9. The blending amount of the blowing agent is usually 0.5 to 30 with respect to 100 parts by mass in total of the ethylene copolymer (A) and other polymers (elastomer, crosslinkable rubber, etc.) blended as necessary. Part by mass, preferably 1 to 20 parts by mass.

<< Method for Preparing Composition >>
By using the composition of the present invention, a crosslinked product having excellent fatigue resistance can be formed. The composition of the present invention is prepared by mixing the ethylene copolymer (A) and other components (eg, other polymers and additives) blended as necessary, for example, a mixer, a kneader, a roll, etc. It can be prepared by kneading at a desired temperature using a machine.

  Specifically, using a conventionally known kneader such as a mixer or a kneader, the ethylene copolymer (A) and, if necessary, the other component 1 are added at a predetermined temperature and time, for example, 80 to 200 ° C. After kneading for ˜30 minutes, other components 2 such as a cross-linking agent are added to the obtained kneaded material as necessary, and a predetermined temperature and time using a roll, for example, a roll temperature of 30 to 80 ° C. The composition of the present invention can be prepared by kneading for ˜30 minutes.

  Examples of other components 1 include other polymers, crosslinking aids, vulcanization accelerators, vulcanization aids, softeners, inorganic fillers, reinforcing agents, anti-aging agents, processing aids, activators, and hygroscopic agents. And at least one selected from a heat stabilizer, a weather stabilizer, an antistatic agent, a colorant, a lubricant, and a thickener. Examples of the other component 2 include a crosslinking agent (vulcanizing agent) and, if necessary, a crosslinking aid, a vulcanization accelerator, a vulcanization aid, a softening agent, an inorganic filler, a reinforcing agent, and an antiaging agent. , Processing aids, activators, hygroscopic agents, heat stabilizers, weathering stabilizers, antistatic agents, colorants, lubricants, thickeners and foaming agents.

[Crosslinked product]
As a method for producing a crosslinked product from the composition of the present invention, for example, the composition (uncrosslinked composition) is molded into a desired shape, and the composition is subjected to a crosslinking treatment simultaneously with or after the molding. The method of doing is mentioned.

  For example, (I) a method of forming a desired shape using the composition of the present invention containing an ethylene copolymer (A) and a crosslinking agent, and crosslinking by heat treatment; (II) the composition of the present invention. Can be formed into a desired shape and crosslinked by irradiation with an electron beam.

  In the above molding, the composition of the present invention is molded into a desired shape using an extrusion molding machine, a calender roll, a press molding machine, an injection molding machine, a transfer molding machine or the like. Examples of the shape of the molded body include a sheet shape. For example, although the thickness of a sheet-like molded object is not specifically limited, Preferably it is 0.5-5 mm, More preferably, it is 0.8-3 mm.

  In the method (I), the molded body is heated at, for example, 50 to 200 ° C. for 1 to 120 minutes simultaneously with or after the molding. By this heating, a crosslinking process is performed, or a foaming process is performed together with the crosslinking process.

In the above method (II), an electron beam having an energy of 0.1 to 10 MeV is applied to the molded article simultaneously with or after molding, and the absorbed dose is usually 0.5 to 35 Mrad, preferably 0.8. Irradiate to 5-20 Mrad.
A crosslinked product can be obtained as described above.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to the said Example. In the following description of Examples and the like, “parts” means “parts by mass” unless otherwise specified.

[Production Example 1]
An ethylene / propylene / ENB copolymer formed from ethylene, propylene and 5-ethylidene-2-norbornene (ENB) by synthesizing a copolymer according to Example 1 of International Publication No. 2013/054882 (Hereinafter also referred to as “EPDM1”).

[Production Example 2]
An ethylene / propylene / VNB copolymer formed from ethylene, propylene and 5-vinyl-2-norbornene (VNB) by synthesizing a copolymer according to Example 1 of JP-A-11-005818 (Hereinafter also referred to as “EPDM2”).

[Production Example 3]
A polymerization reaction of ethylene, propylene and 5-vinyl-2-norbornene (VNB) was continuously carried out at 87 ° C. using a 300 L polymerization vessel equipped with a stirring blade.

  As a polymerization solvent, hexane (feed amount: 32.6 L / h) is used continuously, ethylene feed amount is 3.6 kg / h, propylene feed amount is 6.1 kg / h, and VNB feed amount is 290 g / h. The hydrogenation amount was continuously supplied to the polymerization reactor so that the hydrogen feed amount was 6.3 NL / h.

Feeding amount using di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride as the main catalyst while maintaining the polymerization pressure at 1.6 MPaG and the polymerization temperature at 87 ° C. Was continuously supplied to the polymerization vessel so that the amount of the water was 0.0015 mmol / h. As a cocatalyst, (C ₆ H ₅ ) ₃ CB (C ₆ F ₅ ) ₄ was fed at a feed rate of 0.0075 mmol / h, and an organoaluminum compound was fed triisobutylaluminum (TIBA) at a feed rate of 20 mmol / h. Thus, each was continuously fed to the polymerization vessel.

  Thus, a solution containing 15.2% by mass of an ethylene / propylene / VNB copolymer formed from ethylene, propylene and VNB was obtained. A small amount of methanol is added to the polymerization reaction liquid extracted from the lower part of the polymerization vessel to stop the polymerization reaction, and the ethylene / propylene / VNB copolymer is separated from the solvent by a steam stripping treatment, and then reduced in pressure at 80 ° C. overnight. Dried.

By the above operation, an ethylene / propylene / VNB copolymer (hereinafter also referred to as “EPDM3”) formed from ethylene, propylene and VNB was obtained.
The physical properties of the obtained EPDM were measured by the methods described below. The results are shown in Table 1.

[Content of each structural unit]
The content (mass%) of each structural unit and the molar ratio between the ethylene unit and the α-olefin unit of the ethylene copolymer were determined from the measured values by ¹³ C-NMR. The measured values were measured using an ECX400P nuclear magnetic resonance apparatus (manufactured by JEOL) at a measurement temperature of 120 ° C., a measurement solvent: orthodichlorobenzene / deuterated benzene = 4/1, and the number of integrations: 8000 times. It was obtained by measuring the ¹³ C-NMR spectrum of the polymer.

[Intrinsic viscosity]
The intrinsic viscosity [η] (dl / g) of the ethylene-based copolymer was measured using a fully automatic intrinsic viscometer manufactured by Koiso Co., Ltd. at a temperature of 135 ° C. and a measurement solvent: decalin.

[Iodine number]
The iodine value of the ethylene copolymer was measured by a titration method.

[Reagents used in Examples 1A to 2A and Comparative Examples 1A to 4A]
DCP: Park Mill D, manufactured by NOF Corporation
[Examples 1A to 2A, Comparative Examples 1A to 4A: Preparation of Samples]
In accordance with the formulation shown in Table 2, an ethylene / α-olefin / non-conjugated polyene copolymer and a crosslinking agent (park mill D: dicumyl peroxide as an organic peroxide) were used, and a roll temperature was adjusted using a 6 inch roll. The front roll / rear roll = 50 ° C./50° C., the roll peripheral speed was the front roll / rear roll = 18 rpm / 15 rpm, the roll gap was 2.5 mm, and the kneading time was 8 minutes. Next, the kneaded material was press-molded at 180 ° C. for 10 minutes using a 50 t press molding machine (KMF50-1E, manufactured by Kotaki Seiki Co., Ltd.) to obtain a sheet-like sample having a thickness of about 1 mm.

The sheet-like sample was cut into a round shape with a diameter of 1.2 mm, and then placed in a round bottom flask together with a sufficient amount of xylene. Here, a sufficient amount of xylene means 100 mL of xylene per gram of sample. Then, reflux operation was performed at 140 degreeC for 3 hours. After completion of the reflux operation, the sample was taken out, left on a petri dish, and dried at room temperature for 1 day. Thereafter, the sample was transferred to a desiccator kept in a vacuum and dried at room temperature under vacuum for 43 hours. After completion of drying, the sample was transferred to a fluororesin container, and a sample which was immersed in deuterated xylene at room temperature for 3 days and swollen was used as a sample for small angle neutron scattering measurement. A sample swollen with deuterated xylene was fixed to a sample holder, and the sample was irradiated with a neutron beam under the following conditions, and small angle neutron scattering measurement was performed.
・ Measuring device: Industrial-use beamline iMATERIA installed at MLF, Materials and Life Science Research Facility, J-PARC (Ibaraki Prefecture)
-Incident neutron beam: Pulsed neutron beam-Detector: iMATERIA small angle detector bank-Measurement range: q = 0.2 nm ^-1 to q = 5 nm ^-1
・ Measurement temperature: Room temperature (25 ℃)

With respect to the obtained scattering intensity curve I (q), curve fitting was performed in the range of 0.2 to 4.2 nm ⁻¹ using the above formula (A), and fitting parameters were obtained. For curve fitting, Igor Pro manufactured by WaveMetrics, which is data analysis software, was used. The results are shown in Table 2 and FIG. FIG. 1 shows the results of the scattering intensity curve I (q) and curve fitting for Example 1A. The obtained parameters were substituted into the above formulas (2) and (3) to obtain a non-uniform structure size b and a non-uniform structure amount c of the crosslinked network structure.

  Further, after cutting the sheet-like sample into a size of 20 mm × 20 mm × 2 mmt, it was immersed in toluene at 37 ° C. for 72 hours and swollen according to JIS K6258 (1993), and according to the Flory-Rehner formula (B) Chain density was calculated.

式（Ｂ）中、ν（個／ｃｍ³）は有効網目鎖密度であり、純ゴム１ｃｍ³中の有効網目鎖の数であり、Ｖ_Rは膨潤した架橋ゴム中の純ゴムの容積分率であり、Ｖ₀は溶剤の分子容であり、μはゴム−溶剤間の相互作用定数＝０．４９であり、Ａはアボガドロ数である。
以上の結果を表２に示す。

Wherein (B), [nu (pieces / cm ³⁾ is the effective network chain density, the number of effective network chains of pure rubber 1cm in ^3, V _R is the volume fraction of the pure rubber crosslinked rubber swollen Where V ₀ is the molecular volume of the solvent, μ is the rubber-solvent interaction constant = 0.49, and A is the Avogadro number.
The results are shown in Table 2.

[Example 1B]
As a first stage, using a BB-2 type Banbury mixer (manufactured by Kobe Steel), 100 parts of the ethylene / propylene / VNB copolymer (EPDM3) obtained in Production Example 3 was masticated for 30 seconds, and then In addition, 10 parts of zinc oxide “META-Z102” (trade name; manufactured by Inoue Lime Industry Co., Ltd.) as a crosslinking aid, 1 part of stearic acid as a processing aid, and seast 116 (MAF) as a reinforcing agent (trade name) ; Tokai Carbon Co., Ltd.) 5 parts, hydrophilic fumed silica “AEROSIL200” (trade name; Nippon Aerosil Co., Ltd.) 30 parts, paraffinic process oil “Diana Process Oil PW-380” (product) Name: Idemitsu Kosan Co., Ltd.) was added in an amount of 50 parts and kneaded at 140 ° C. for 2 minutes. Thereafter, the ram was raised and cleaned, and further kneaded for 1 minute and discharged at about 150 ° C. to obtain a first-stage formulation.

  Next, as the second stage, the composition obtained in the first stage is 8 inch roll (manufactured by Nippon Roll Co., Ltd., the surface temperature of the front roll is 50 ° C., the surface temperature of the rear roll is 50 ° C., Wrapped around a rotation speed of 16 rpm and a rear roll rotation speed of 18 rpm), 5.0 parts of dicumyl peroxide (Kayakmir D-40C, manufactured by Kayaku Akzo Co., Ltd.) as a crosslinking agent was added thereto, and kneaded for 10 minutes. An uncrosslinked rubber compound was obtained.

  This rubber compound was dispensed into a sheet and pressed at 170 ° C. for 15 minutes using a 100 t press molding machine to produce a crosslinked rubber sheet having a thickness of 2 mm. Using this, physical properties of the crosslinked rubber were evaluated.

[Example 2B, Comparative Examples 1B to 2B]
A crosslinked rubber sheet having a thickness of 2 mm was produced in the same manner as in Example 1B except that a rubber compound was prepared according to the compounding recipe shown in Table 3. Using this, physical properties of the crosslinked rubber were evaluated.

[Hardness test (Durometer-A)]
The flat part of the 2 mm-thick crosslinked rubber sheet obtained above was overlapped to form a 12 mm-thick sheet, and the hardness (JIS-A) was measured according to JIS K6253.

[Tensile test]
The crosslinked rubber sheet having a thickness of 2 mm obtained above was subjected to a tensile test under the conditions of a measurement temperature of 23 ° C. and a tensile speed of 500 mm / min in accordance with JIS K6251, and the tensile stress when the elongation was 25% (25% Modulus (M25)), tensile stress when elongation is 50% (50% modulus (M50)), tensile stress when elongation is 100% (100% modulus (M100)), elongation is 200 % Tensile stress (200% modulus (M200)), tensile stress when elongation is 300% (300% modulus (M300)), strength at break (TB) and elongation at break (EB) did.

(Bending fatigue test)
The 2 mm thick crosslinked rubber sheet obtained above was subjected to a bending fatigue test according to JIS K6260 (bending determination method), and cracks were evaluated according to the following criteria. The measurement was stopped when the grade 6 was reached.
1st grade: When a crack like a “needle hole” is seen with the naked eye,
When there are 10 or less “needle holes”.
2nd grade: When it corresponds to one of the following: 1) When there are 11 or more “needle holes”.
2) Even when there are 10 or less “needle holes”, there is one crack larger than “needle holes”.
Or when there is more than that and the crack length is less than 0.5 mm.
Third grade: When the number of “needle holes” is one and the crack length is 0.5 mm or more and less than 1.0 mm.
Fourth grade: When the crack length is 1.0 mm or more and less than 1.5 mm.
Grade 5: When the crack length is 1.5 mm or more and less than 3.0 mm.
Grade 6: When the crack length is 3.0 mm or more.

[Evaluation according to requirements (1) and (2)]
In the Flory-Rehner method, an effective network chain density can be obtained, but it is impossible to grasp the point of non-uniformity of the crosslinked network structure. On the other hand, in the small-angle neutron scattering method, the heterogeneous structure size and the heterogeneous structure amount of the crosslinked body can be obtained, and more detailed analysis is possible.

  The graph which plotted the heterogeneous structure amount c with respect to the compounding quantity (mass part) of the peroxide per 100 mass parts of EPDM about the peroxide crosslinked body obtained in Example 1A-2A and Comparative Example 1A-4A. FIG. 2 shows a graph in which the non-uniform structure size b is plotted.

From the results of the bending fatigue tests in Examples 1B to 2B and Comparative Examples 1B to 2B, the heterogeneous structure amount c and peroxide (PO) compounding amount determined by the small angle neutron scattering method are 0 ≦ c ≦ −30 × “ The amount of peroxide (PO) blended per 100 parts by weight of the copolymer (parts by weight) ”+ 30, and the heterogeneous structure size b and the amount of peroxide (PO) blended obtained by the small angle neutron scattering method are: When using EPDM satisfying 0 ≦ b [Å] ≦ −7.5 × “peroxide (PO) blending amount per 100 parts by mass of the copolymer (parts by mass)” + 25 (that is, using EPDM3) In the case of Examples 1B and 2B), it can be seen that a crosslinked product having excellent fatigue resistance can be obtained. On the other hand, when EPDM that does not satisfy these requirements is used (that is, in the case of Comparative Examples 1B to 2B using EPDM 1 or 2), the fatigue resistance is not a satisfactory result.
Therefore, it turns out that the crosslinked body excellent in fatigue resistance can be obtained by using the ethylene-type copolymer which satisfy | fills the requirements (1) and (2) mentioned above.

Claims (5)

An ethylene / C3-C20 α-olefin / nonconjugated polyene copolymer satisfying the following requirements (1) and (2):
When the copolymer is crosslinked with a peroxide and the heterogeneous structure amount c and the heterogeneous structure size b are determined by the small-angle neutron scattering method for the obtained crosslinked product, (1) the heterogeneous structure amount c And the peroxide blending amount satisfies the formula (1a), and (2) the heterogeneous structure size b and the peroxide blending amount satisfy the formula (2a).

The heterogeneous structure size b and the heterogeneous structure amount c are obtained by crosslinking the copolymer with a peroxide, and the scattering intensity curve I (q) obtained by the small-angle neutron scattering method for the obtained crosslinked product. Is a value obtained using equations (2) and (3) from parameters Ξ, I _ξ (0) and I _Ξ (0) obtained by curve fitting according to equation (A). 1. The ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer according to 1.

[In the formulas (A) and (1) to (3), θ is the scattering angle (rad), λ is the wavelength (nm) of the neutron beam, and I _ξ (0), I _Ξ (0), ξ , Ξ and I _inc are fitting parameters. ]   In the above requirements (1) and (2), the peroxide used when the copolymer is crosslinked is dicumyl peroxide. -Olefin / non-conjugated polyene copolymer.   A composition containing the ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer according to claim 1.   The crosslinked body obtained by bridge | crosslinking the composition of Claim 4.

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