JP6489774B2 - Rubber composition for transmission belt - Google Patents

Description

  The present invention relates to a rubber composition for a transmission belt comprising an ethylene / α-olefin / nonconjugated polyene copolymer, and a transmission belt comprising the rubber composition.

  Since ethylene-propylene-nonconjugated diene copolymer rubber (EPDM) has no unsaturated bond in the main chain, it is superior in heat resistance (including heat aging resistance) and weather resistance to general-purpose diene rubbers. It is used in many products such as automotive parts and industrial parts.

However, EPDM has been said to be inferior to the diene rubber in the points of dynamic fatigue resistance, abrasion resistance, adhesion to metals, fibers and the like.
In addition, when EPDM is used for applications such as a power transmission belt, it has been difficult to balance dynamic fatigue resistance and abrasion resistance. That is, in order to improve the wear resistance, the modulus may be increased. However, in order to increase the modulus, the amount of the crosslinking agent used is increased to increase the crosslink density, or the compounding amount of carbon black is increased. The tensile elongation (EB) is reduced and the dynamic fatigue resistance is reduced. On the contrary, when trying to improve the dynamic fatigue resistance, the wear resistance deteriorates.

  In Patent Document 1, as a composition capable of supplying a transmission belt satisfying all of heat resistance (including heat aging resistance), dynamic fatigue resistance and abrasion resistance, a reinforcing material, a cross-linking aid and the like are compounded to prevent abrasion. A rubber composition is disclosed in which heat resistance is improved by adopting radical (peroxide) crosslinking as a crosslinking method for enhancing the crosslinking density of the rubber while enhancing the properties.

  Further, Patent Document 2 discloses a transmission belt made of a radically crosslinked rubber mixture containing a specific carboxylic acid and a metal salt.

JP 2000-080224 A JP 2009-534486 gazette

  An object of the present invention is to provide a rubber composition capable of producing a transmission belt whose wear resistance is improved more than that of a conventional transmission belt.

  As a result of intensive studies to solve the above problems, the present inventors have improved the abrasion resistance by crosslinking a rubber composition containing a specific ethylene / α-olefin / nonconjugated polyene copolymer. It has been found that a power transmission belt can be obtained, and the present invention has been completed. That is, the present invention relates to, for example, the following [1] to [6].

  [1] Ethylene (a1), α-olefin having 3 to 20 carbon atoms (a2), and partial structures selected from the group consisting of the following general formulas (I) and (II) in total in a molecule: 2 It has an ethylene-α-olefin-nonconjugated polyene copolymer (A) which has a constituent unit derived from the non-conjugated polyene (a3) contained above and which satisfies the following requirements (i) to (v) A rubber composition for a transmission belt characterized in that.

（ｉ）エチレン（ａ１）／α−オレフィン（ａ２）のモル比が４０／６０〜９９．９／０．１である。
（ii）非共役ポリエン（ａ３）に由来する構成単位の重量分率が、エチレン・α−オレフィン・非共役ポリエン共重合体１００重量％中、０．０７重量％〜１０重量％である。
（iii）エチレン・α−オレフィン・非共役ポリエン共重合体（Ａ）の重量平均分子量（Ｍｗ）と、非共役ポリエン（ａ３）に由来する構成単位の重量分率（（ａ３）の重量分率（重量％））と、非共役ポリエン（ａ３）の分子量（（ａ３）の分子量）とが、下記式（１）を満たす。
４．５≦Ｍｗ×（ａ３）の重量分率／１００／（ａ３）の分子量≦４０ …（１）
（iv）レオメーターを用いた線形粘弾性測定（１９０℃）により得られた、周波数ω＝０．１ｒａｄ／ｓでの複素粘度η^* ₍ω_=0.1)（Ｐａ・ｓｅｃ）と周波数ω＝１００ｒａｄ／ｓでの複素粘度η^* ₍ω₌₁₀₀₎（Ｐａ・ｓｅｃ）との比Ｐ（η^* ₍ω_=0.1)／η^* ₍ω₌₁₀₀₎）と、極限粘度［η］と、前記非共役ポリエン（ａ３）に由来する構成単位の重量分率（（ａ３）の重量分率）とが、下記式（２）を満たす。
Ｐ／（[η]^2.9）≦（ａ３）の重量分率×６ …（２）
（ｖ）３Ｄ−ＧＰＣを用いて得られた、１０００炭素原子あたりの長鎖分岐数（ＬＣＢ_1000C）と、重量平均分子量（Ｍｗ)の自然対数[Ｌｎ（Ｍｗ）］とが下記式（３）を満たす。
ＬＣＢ_1000C≦１−０．０７×Ｌｎ（Ｍｗ） …（３）

(I) The molar ratio of ethylene (a1) / α-olefin (a2) is 40/60 to 99.9 / 0.1.
(Ii) The weight fraction of the structural unit derived from the nonconjugated polyene (a3) is 0.07% by weight to 10% by weight in 100% by weight of the ethylene / α-olefin / nonconjugated polyene copolymer.
(Iii) Weight fraction of weight average molecular weight (Mw) of ethylene / α-olefin / nonconjugated polyene copolymer (A) and weight fraction of constituent unit derived from nonconjugated polyene (a3) ((a3) (Wt%) and the molecular weight of the non-conjugated polyene (a3) (molecular weight of (a3)) satisfy the following formula (1).
4.5 ≦ Mw × (a3) weight fraction / 100 / (a3) molecular weight ≦ 40 (1)
(Iv) Complex viscosity ^** ₍ ω _{= 0.1)} (Pa · sec) at a frequency ω = _0.1 rad / s and frequency ω = 100 rad obtained by linear viscoelasticity measurement (190 ° C.) using a rheometer The ratio P (η ^* ₍ ω _{= 0.1)} / ^{* *} ₍ ω _{= 100)} ) to the complex viscosity ^{* *} ₍ ω _{= 100)} (Pa · sec) at / s, the limiting viscosity [η], The weight fraction of the structural unit derived from the conjugated polyene (a3) (the weight fraction of (a3)) satisfies the following formula (2).
Weight fraction of P / ([η] ^2.9 ) ≦ (a 3) × 6 (2)
(V) The number of long chain branches per 1000 carbon atoms (LCB _1000C ) obtained using 3D-GPC, and the natural logarithm [Ln (Mw)] of the weight average molecular weight (Mw) is represented by the following formula (3) Meet.
LCB _{1000 C} ≦ 1-0.07 × Ln (Mw) (3)

  [2] 1 to 10 parts by weight of an organic peroxide (B), 5 to 30 parts by weight of a metal salt of an α, β-unsaturated organic acid (C) and 100 parts by weight of the copolymer (A), The rubber composition for a transmission belt according to Item [1], containing 10 to 100 parts by weight of carbon black (D).

[3] The rubber composition for a transmission belt as described in [1] or [2], wherein the α-olefin (a2) is propylene.
[4] The rubber composition for a transmission belt according to any one of [1] to [3], wherein the nonconjugated polyene (a3) contains 5-vinyl-2-norbornene (VNB). .
[5] A method for producing a transmission belt comprising the step of crosslinking the rubber composition for a transmission belt according to any one of [1] to [4].
[6] A transmission belt obtained by crosslinking the rubber composition for a transmission belt according to any one of [1] to [4].

  According to the present invention, it is possible to obtain a transmission belt having significantly improved wear resistance despite the fact that the crosslink density is equivalent as compared with the case of using the conventional EPDM as disclosed in Patent Document 1 and the like. It is presumed that this is because the crosslinked network chain structure becomes uniform and the abrasion resistance is improved because the crosslinking points are uniformly contained.

Hereinafter, the present invention will be described in detail.
[Rubber composition for transmission belt]
The rubber composition for a transmission belt according to the present invention contains a specific ethylene / α-olefin / nonconjugated polyene copolymer (A) (hereinafter, also simply referred to as “copolymer (A)”) described later. It is characterized by The rubber composition for a transmission belt of the present invention preferably contains an organic peroxide (B), a metal salt of an α, β-unsaturated organic acid (C) and carbon black (D), and further, It may contain other ingredients.

<Ethylene · α-olefin · nonconjugated polyene copolymer (A)>
The copolymer (A) used in the present invention is selected from the group consisting of ethylene (a1), an α-olefin having 3 to 20 carbon atoms (a2), and the following general formulas (I) and (II) It has a structural unit derived from a nonconjugated polyene (a3) containing two or more partial structures in total in the molecule.

上記共重合体（Ａ）は、上記（ａ１）、（ａ２）、（ａ３）に由来する構造単位に加えて、さらに上記般式（Ｉ）および（II）からなる群から選ばれる部分構造を分子中に１つのみ含む非共役ポリエン（ａ４）に由来する構成単位を有していてもよい。

In addition to the structural units derived from the above (a1), (a2) and (a3), the above copolymer (A) further has a partial structure selected from the group consisting of the above general formulas (I) and (II) You may have the structural unit derived from nonconjugated polyene (a4) which contains only one in a molecule.

  Examples of the α-olefin (a2) include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene etc. are mentioned. Among these, α-olefins having 3 to 8 carbon atoms such as propylene, 1-butene, 1-hexene and 1-octene are preferable, and propylene is particularly preferable. Such an α-olefin is preferable because the cost of the raw material is relatively low, the obtained copolymer (A) exhibits excellent mechanical properties, and a molded article having rubber elasticity can be obtained.

  The above α-olefins (a2) may be used alone or in combination of two or more. That is, the copolymer (A) contains a structural unit derived from at least one α-olefin having 3 to 20 carbon atoms (a2), and 2 or more α having 3 to 20 carbon atoms -The structural unit derived from an olefin (a2) may be included.

  Examples of the nonconjugated polyene (a3) include 5-vinyl-2-norbornene (VNB), norbornadiene, 1,4-hexadiene, dicyclopentadiene and the like. Among these, the non-conjugated polyene (a3) is a VNB because the availability is high, the reactivity with the peroxide is good at the time of crosslinking reaction after polymerization, and the heat resistance of the polymer composition is easily improved. It is preferable that the nonconjugated polyene (a3) is VNB. The nonconjugated polyene (a3) may be used alone or in combination of two or more.

  As the non-conjugated polyene (a4), 5-ethylidene-2-norbornene (ENB), 5-methylene-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2 -Norbornene, 5- (1-methyl-2-propenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene, 5- (1-methyl-3-butenyl) -2-norbornene, 5- ( 5-hexenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene, 5- (2,3-dimethyl-3-butenyl) -2-norbornene, 5- (2-ethyl-) 3-butenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene, 5- (3-methyl-5-hexenyl) -2-norbornene, 5- (3,4-dimethyl) 4-pentenyl) -2-norbornene, 5- (3-ethyl-4-pentenyl) -2-norbornene, 5- (7-octenyl) -2-norbornene, 5- (2-methyl-6-heptenyl) -2 -Norbornene, 5- (1,2-dimethyl-5-hexenyl) -2-norbornene, 5- (5-ethyl-5-hexenyl) -2-norbornene, 5- (1,2,3-trimethyl-4-) And pentenyl) -2-norbornene. Among these, ENB is preferable because of high availability, high reactivity with sulfur and vulcanization accelerator at the time of crosslinking reaction after polymerization, easy control of crosslinking rate, and easy to obtain good mechanical properties. . The nonconjugated polyene (a4) may be used alone or in combination of two or more.

  When the copolymer (A) contains a constitutional unit derived from the non-conjugated polyene (a4), the ratio is not particularly limited as long as the object of the present invention is not impaired. 20 wt%, preferably 0 to 8 wt%, more preferably 0.01 to 8 wt% or so (provided that the weight fraction of (a1), (a2), (a3), (a4)) The sum of the rates is 100% by weight).

The copolymer (A) is, as described above, ethylene (a1), α-olefin having 3 to 20 carbon atoms (a2), the above-described non-conjugated polyene (a3), and the above-described non-conjugated as required. It is a copolymer which has a structural unit derived from polyene (a4), Comprising: The requirements (following, requirements (i)-(v) are also mentioned.) Of following (i)-(v) are satisfy | filled.
(I) The molar ratio of ethylene (a1) / α-olefin (a2) is 40/60 to 99.9 / 0.1.
(Ii) The weight fraction of the structural unit derived from the nonconjugated polyene (a3) is 0.07% by weight to 10% by weight in 100% by weight of the ethylene / α-olefin / nonconjugated polyene copolymer.
(Iii) weight-average molecular weight (Mw) of ethylene / α-olefin / nonconjugated polyene copolymer and weight fraction (% by weight of component unit derived from nonconjugated polyene (a3) (% by weight) And the molecular weight of the nonconjugated polyene (a3) (molecular weight of (a3)) satisfy the following formula (1).
4.5 ≦ Mw × (a3) weight fraction / 100 / (a3) molecular weight ≦ 40 (1)
(Iv) Complex viscosity ^** ₍ ω _{= 0.1)} (Pa · sec) at a frequency ω = _0.1 rad / s and frequency ω = 100 rad obtained by linear viscoelasticity measurement (190 ° C.) using a rheometer The ratio P (η ^* ₍ ω _{= 0.1)} / ^{* *} ₍ ω _{= 100)} ) to the complex viscosity ^{* *} ₍ ω _{= 100)} (Pa · sec) at / s, the limiting viscosity [η], The weight fraction of the structural unit derived from the conjugated polyene (a3) (the weight fraction of (a3)) satisfies the following formula (2).
Weight fraction of P / ([η] ^2.9 ) ≦ (a 3) × 6 (2)
(V) The number of long chain branches per 1000 carbon atoms (LCB _1000C ) obtained using 3D-GPC, and the natural logarithm [Ln (Mw)] of the weight average molecular weight (Mw) is represented by the following formula (3) Meet.
LCB _{1000 C} ≦ 1-0.07 × Ln (Mw) (3)

«Requirement (i)»
Requirement (i) specifies that the molar ratio of ethylene (a1) / α-olefin (a2) in the above-mentioned copolymer (A) satisfies 40/60 to 99.9 / 0.1. The molar ratio is preferably 50/50 to 90/10, more preferably 55/45 to 85/15, and still more preferably 55/45 to 78/22.

By using the copolymer (A) satisfying the requirement (i), it is possible to obtain a transmission belt excellent in rubber elasticity, mechanical strength and flexibility. The amount of ethylene in the copolymer (A) (content of constituent unit derived from ethylene (a1)) and the amount of α-olefin (content of constituent unit derived from α-olefin (a2)) are ¹³ C- It can be determined by NMR.

«Requirement (ii)»
The requirement (ii) is that in the above copolymer (A), the weight fraction of the structural unit derived from the non-conjugated polyene (a3) is 100% by weight of the copolymer (A) (that is, the weight of all structural units It is specified that it is in the range of 0.07% by weight to 10% by weight). The weight fraction of the structural unit derived from this non-conjugated polyene (a3) is preferably 0.1% by weight to 8.0% by weight, more preferably 0.5% by weight to 5.0% by weight.

The copolymer (A) satisfying the requirement (ii) has sufficient hardness and is excellent in mechanical properties, and when crosslinked with a peroxide, exhibits a rapid crosslinking rate. The amount of nonconjugated polyene (a3) in the copolymer (A) (the content of the constitutional unit derived from the nonconjugated polyene (a3)) can be determined by ¹³ C-NMR.

<< requirement (iii) >>
Requirement (iii) is that, in the copolymer (A), the weight average molecular weight (Mw) of the copolymer (A) and the constituent unit derived from the nonconjugated polyene (a3) in the copolymer (A) It is specified that the weight fraction (weight fraction of (a3): weight%) and the molecular weight of the non-conjugated polyene (a3) (molecular weight of (a3)) satisfy the above formula (1). It is preferable that the said Formula (1) of requirement (iii) is following formula (1 ').
4.5 ≦ Mw × (a3) weight fraction / 100 / (a3) molecular weight ≦ 35 (1 ′)

  When the copolymer (A) satisfies the requirement (iii), the content of the structural unit derived from the non-conjugated polyene (a3) is appropriate, exhibits sufficient crosslinking performance, and is excellent in crosslinking rate, Transmission belts can be produced which exhibit excellent mechanical properties. In addition, the weight average molecular weight (Mw) of a copolymer (A) can be calculated | required as a numerical value of polystyrene conversion measured by gel permeation chromatography (GPC).

  In the above-mentioned copolymer (A), when “molecular weight of Mw × (a3) / 100 / (a3)” satisfies the above formula (1) or (1 ′), the degree of crosslinking becomes appropriate, and the machine It is possible to manufacture an excellent power transmission belt with well-balanced physical properties and heat aging resistance. When the value of “weight fraction of Mw × (a3) / 100 / (a3) molecular weight” ”is too low, the crosslinkability may be insufficient and the crosslinking rate may be slow, and when the value is too high However, excessive crosslinking may occur to deteriorate mechanical properties.

«Requirements (iv)»
Requirement (iv) is the complex viscosity η ^* ₍ ω _{= 0.1} at frequency ω = 0.1 rad / s) obtained by linear viscoelasticity measurement (190 ° C.) of the above-mentioned copolymer (A) using a rheometer The ratio P (η ^* ₍ ω _{= 0.1)} / η ^* ₍ ω _{= 100) of} (Pa · sec) to the complex viscosity ^** ₍ ω _{= 100 )} (Pa · sec) at a frequency ω = 100 rad / s ), The intrinsic viscosity [η], and the weight fraction of the constituent unit derived from the nonconjugated polyene (a3) (weight fraction of (a3): wt%) satisfy the above formula (2) It is to identify. It is preferable that said Formula (2) of requirement (iv) is following formula (2 ').
P / ([η] ^2.9 ) ≦ (a3) weight fraction × 5.7 (2 ′)

Here, the ratio P (η ^* ₍ ω ₎ between the complex viscosity η ^* ₍ ω _{= 0.1)} at frequency ω = _0.1 rad / s and the complex viscosity ^** ₍ ω _{= 100)} at frequency ω = 100 rad / s _{= 0.1)} / η ^* ₍ ω _{= 100)} ) represents the frequency dependency of viscosity, and P / ([η] ^2.9 ) corresponding to the left side of equation (2) represents short chain branching, molecular weight, etc. Although there is an influence, it tends to show a high value when there are many long chain branches. Generally, in the ethylene / α-olefin / nonconjugated polyene copolymer, the longer the long-chain branching tends to be, the more the component unit derived from the nonconjugated polyene contains, but the copolymer (A) of the present invention It is believed that the above formula (2) can be satisfied by having less long chain branching than conventionally known ethylene / α-olefin / nonconjugated polyene copolymers.

In the present invention, the P value is a complex viscosity at 0.1 rad / s, which is obtained by measurement using a viscoelasticity measuring apparatus Ares (manufactured by Rheometric Scientific) under conditions of 190 ° C., strain 1.0% and frequency change. The ratio (η ^* ratio) is determined from the complex viscosity at 100 rad / s and the complex viscosity at 100 rad / s. The intrinsic viscosity [粘度] means a value measured in decalin at 135 ° C.

«Requirements (v)»
The requirement (v) is obtained by using 3D-GPC of the above-mentioned copolymer (A), the number of long chain branches per 1000 carbon atoms (LCB _1000C ) and the natural logarithm [Ln of weight average molecular weight (Mw) (Mw)] specifies that the above equation (3) is satisfied. It is preferable that the said Formula (3) of requirement (v) is following formula (3 ').
LCB _1000C ≦ 1-0.071 × Ln (Mw) (3 ′)

The upper limit value of the long chain branch content per unit carbon number of the copolymer (A) is specified by the above formula (3) or (3 ′).
When the copolymer (A) satisfies the requirement (v), the proportion of long chain branching contained is small, and while it is excellent in the curing characteristics when crosslinking is performed using a peroxide, the transmission having excellent heat aging resistance You can get a belt.

Here, Mw and the number of long chain branches per 1000 carbon atoms (LCB _1000C ) can be determined by structural analysis using 3D-GPC. In the present specification, specifically, it was determined as follows.
The absolute molecular weight distribution was determined using a 3D-high temperature GPC apparatus PL-GPC 220 (manufactured by Polymer Laboratories), and at the same time, the limiting viscosity was determined with a viscometer. The main measurement conditions are as follows.
Detector: Built-in differential refractometer / GPC device
Two-angle light scattering photometer PD2040 (manufactured by Precison Detectors)
Bridge-type viscometer PL-BV 400 (manufactured by Polymer Laboratories)
Column: TSKgel GMH _HR- H (S) HT x 2 + TSKgel GMH _HR- M (S) x 1
(Each one has an inner diameter of 7.8 mmφ × 300 mm in length)
Temperature: 140 ° C
Mobile phase: 1,2,4-Trichlorobenzene (containing 0.025% BHT)
Injection volume: 0.5mL
Sample concentration: ca 1.5 mg / mL
Sample filtration: filtration with a 1.0 μm pore size sintered filter

  In the above, the dn / dc value necessary for the determination of the absolute molecular weight was determined for each sample from the dn / dc value 0.053 of standard polystyrene (molecular weight 190000) and the response intensity of the differential refractometer per unit injection mass.

  The long chain branching parameter g'i for each eluted component was calculated from the following formula (v-1) from the relationship between the intrinsic viscosity obtained from the viscometer and the absolute molecular weight obtained from the light scattering photometer.

ここで、［η］=ＫＭ^v；ｖ＝0.725の関係式を適用した。
また、ｇ'として各平均値を下記式（ｖ−２）、（ｖ−３）、（ｖ−４）から算出した。なお、短鎖分岐のみを有すると仮定したTrendlineは試料ごとに決定した。

Here, the relation of [η] = KM ^v ; v = 0.725 was applied.
Moreover, each average value was computed from following formula (v-2), (v-3), (v-4) as g '. In addition, Trendline assumed to have only short chain branching was determined for each sample.

更にｇ'wを用いて、分子鎖あたりの分岐点数ＢrＮo、炭素１０００個あたりの長鎖分岐数ＬＣＢ_1000C、単位分子量あたりの分岐度λを算出した。ＢrＮo算出はZimm-Stockmayerの下記式（ｖ−５）、また、ＬＣＢ_1000Cとλの算出は下記式（ｖ−６）、（ｖ−７）を用いた。ｇは慣性半径Rgから求められる長鎖分岐パラメーターであり、極限粘度から求められるｇ'との間に次の単純な相関付けが行われている。式中のεは分子の形に応じて種々の値が提案されている。ここではε＝１（すなわちｇ'＝ｇ）と仮定して計算を行った。

Furthermore, using g'w, the branch number BrNo per molecular chain, the number of long-chain branches LCB _1000C per 1000 carbons, and the degree of branch λ per unit molecular weight were calculated. Calculation of BrNo used the following formula (v-5) of Zimm-Stockmayer, and calculation of LCB _1000C and (lambda) used following formula (v-6) and (v-7). g is a long chain branching parameter determined from the radius of inertia Rg, and the following simple correlation is made with g 'determined from the limiting viscosity. In the formula, various values have been proposed according to the form of the molecule. Here, the calculation was performed assuming that ε = 1 (that is, g ′ = g).

λ＝ＢｒＮｏ／Ｍ …（Ｖ−６）
ＬＣＢ_1000C＝λ×１４０００ …（Ｖ−７）
式（Ｖ−７）中、「１４０００」はメチレン（ＣＨ²）単位で１０００個分の分子量を表す。

λ = Br No / M (V-6)
LCB _{1000 C} = λ × 14000 (V-7)
Wherein (V-7), "14000" represents a molecular weight of 1000 pieces of methylene (CH ²⁾ units.

The intrinsic viscosity [η] of the above copolymer (A) is preferably 0.1 to 5 dL / g, more preferably 0.5 to 5.0 dL / g, still more preferably 0.9 to 4.0 dL / g It is.
The weight average molecular weight (Mw) of the above-mentioned copolymer (A) is preferably 10,000 to 600,000, more preferably 30,000 to 500,000, and still more preferably 50,000 to 400,000. is there.

It is preferable that the above-mentioned copolymer (A) be satisfied in combination with the above-mentioned intrinsic viscosity [η] and weight average molecular weight (Mw).
In the copolymer (A), as described above, the non-conjugated polyene (a3) preferably contains VNB, more preferably VNB. That is, in the formulas (1), (2) and the formula (4) described later, it is preferable that "weight fraction of (a3)" is "weight fraction of VNB" (% by weight).

  As described above, the copolymer (A) further includes, in addition to the structural units derived from the (a1), (a2) and (a3), structural units derived from the non-conjugated polyene (a4) It is also preferable to include a weight fraction of 0% by weight to 20% by weight (provided that the total of the weight fractions of (a1), (a2), (a3) and (a4) is 100% by weight). In this case, it is preferable to satisfy the following requirement (vi).

«Requirements (vi)»
Weight average molecular weight (Mw) of the above-mentioned copolymer (A), weight fraction of constituent units derived from non-conjugated polyene (a3) (weight fraction of (a3) (% by weight)), non-conjugated polyene (a) The weight fraction of the constituent unit derived from a4) (the weight fraction of (a4) (wt%)), the molecular weight of the nonconjugated polyene (a3) (molecular weight of (a3)), and the nonconjugated polyene (a4) The molecular weight (molecular weight of (a4)) satisfies the following formula (4).
4.5 ≦ Mw × {(weight fraction of (a3) / 100 / molecular weight of (a3) + (weight fraction of (a4) / 100 / molecular weight of (a4))} ≦ 45 (4)
In Formula (4), the content of the nonconjugated diene (sum of (a3) and (a4)) in one copolymer molecule is specified.

When the copolymer (A) containing the structural unit derived from the above (a4) satisfies the formula (4), it is possible to obtain a transmission belt excellent in mechanical properties and heat aging resistance.
Not satisfying the requirement (vi), “Mw × {((weight fraction of (a3)) / 100 / molecular weight of (a3) + (weight fraction of (a4) / 100 / (a4) in the formula (4) If the value of “molecular weight)} is too low, ie, the content of non-conjugated diene is too low, sufficient crosslinking may not be achieved and appropriate mechanical properties may not be obtained, and when the value is too high, ie When the content of conjugated diene is too large, crosslinking may be excessive to deteriorate mechanical properties, and heat aging resistance may be further deteriorated.

<< Requirement (vii) >>
The copolymer (A) is not particularly limited, but the complex viscosity η ^* at a frequency ω = 0.01 rad / s obtained by linear viscoelasticity measurement (190 ° C.) using a rheometer ^. ₍ ω _{= 0.01)} (Pa · sec), complex viscosity ^{* *} ₍ ω _{= 10)} at frequency ω = 10 rad / s (Pa · sec), and apparent iodine value derived from non-conjugated polyene (a3) However, it is preferable that the following formula (5) be satisfied.

Log {η ^* ₍ ω _{= 0.01)} } / Log {η ^* ₍ ω _{= 10)} } ≦ 0.0753 × {apparent iodine value derived from nonconjugated polyene (a3)} + 1.42 (5)
Here, the complex viscosity ^** ₍ ω _{= 0.01)} and the complex viscosity ^{* *} ₍ ω _{= 10)} are measured with the complex viscosity ^{* *} ₍ ω _{= 0.1)} and the complex viscosity ^{* *} ₍ ω _{= 100)} in requirement (iv) Other than the frequency can be obtained in the same manner. The apparent iodine value derived from the nonconjugated polyene (a3) can be determined by the following equation.
Apparent iodine number derived from (a3) = weight fraction of (a3) × 253.81 / (A3) molecular weight

  In the above formula (5), the left side represents the shear rate dependence which is an index of the amount of long chain branching, and the right side represents the index of the content of the nonconjugated polyene (a3) not consumed as the long chain branch during polymerization. When the said copolymer (A) satisfy | fills the said Formula (5), since the grade of a long chain branch is not too high, it is preferable. On the other hand, when the above formula (5) is not satisfied, it can be seen that the proportion of the copolymerized non-conjugated polyene (a3) consumed for the formation of long chain branching is high.

Furthermore, the copolymer (A) preferably contains a sufficient amount of a constituent unit derived from the non-conjugated polyene (a3), and the constituent unit derived from the non-conjugated polyene (a3) in the copolymer It is more preferable that the weight fraction (the weight fraction of (a3) (% by weight)) and the weight average molecular weight (Mw) of the copolymer satisfy the following formula (6).
6−0.45 × Ln (Mw) ≦ (a3) weight fraction ≦ 10 (6)

The copolymer (A) preferably has a number (n _C ) of structural units derived from the non-conjugated polyene (a3) per weight average molecular weight (Mw) of preferably 6 or more, more preferably 6 The number is 40 or more, more preferably 7 or more and 39 or less, and particularly preferably 10 or more and 38 or less.

  Such a copolymer (A) contains a sufficient amount of a structural unit derived from a nonconjugated polyene (a3) such as VNB, and has a long chain branch content and is crosslinked using a peroxide. As well as being excellent in the curing characteristics in the case of performing the above, the formability is good, the balance of physical properties such as mechanical characteristics is excellent, and in particular, the heat aging resistance is excellent.

The copolymer (A) preferably has a number (n _D ) of structural units derived from the non-conjugated polyene (a4) per weight average molecular weight (Mw) of preferably 29 or less, more preferably 10 The following is more preferably less than one.

  In such a copolymer (A), the content of structural units derived from non-conjugated polyenes (a4) such as ENB is suppressed within a range that does not impair the object of the present invention, and post-crosslinking hardly occurs. Heat aging resistance.

Here, the number of structural units derived from the nonconjugated polyene (a3) per weight average molecular weight (Mw) of the copolymer (A) ( _na3 ) or the number of structural units derived from the nonconjugated polyene (a4) ( _Na4 ) is the molecular weight of the nonconjugated polyene (a3) or (a4), and the weight fraction of the structural unit derived from the nonconjugated polyene (a3) or (a4) in the copolymer ((a3) or (a3) From the weight fraction (weight%) of a4) and the weight average molecular weight (Mw) of the copolymer (A), it can be determined by the following formula.
( _Na3 ) = (Mw) × {(a3) weight fraction / 100} / molecular weight of non-conjugated polyene (a3) ( _na4 ) = (Mw) × {(a4) weight fraction / 100} / Molecular weight of nonconjugated polyene (a4)

The copolymer (A), the per weight average molecular weight (Mw), and number of each constituent unit derived from a nonconjugated polyene (a3) and _{(a4) (n a3) (} n a4) are both When the above range is satisfied, the copolymer (A) has a small content of long-chain branching, and is excellent in the curing characteristics when crosslinking is performed using a peroxide, the formability is good, the mechanical characteristics, etc. It is preferable because it is excellent in the balance of physical properties of the above, hardly causes post-crosslinking, and in particular, is excellent in heat aging resistance.

<Preparation of Copolymer (A)>
The copolymer (A) is obtained by copolymerizing monomers consisting of ethylene (a1), α-olefin (a2), non-conjugated polyene (a3) and, if necessary, non-conjugated polyene (a4) Copolymer.

  The above copolymer (A) may be prepared by any method as long as the above requirements (i) to (v) are satisfied, but it is obtained by copolymerizing monomers in the presence of a metallocene compound It is preferable that it is a thing obtained by copolymerizing a monomer in the presence of the catalyst system containing a metallocene compound.

«Metallocene compounds»
The above copolymer (A) is preferably a monomer in the presence of at least one metallocene compound selected from a compound represented by the following general formula [A1] and a compound represented by the following general formula [A2] Preferably, it is obtained by copolymerizing When copolymerization of monomers is carried out using a catalyst system containing such a metallocene compound, the long chain branching contained in the resulting copolymer is suppressed, and the copolymer (A) satisfying the above requirements is easily obtained. It can be prepared.

式［Ａ１］および［Ａ２］中、Ｍは周期表第４族の原子を示し、Ｑはハロゲン原子、炭化水素基、ハロゲン化炭化水素基、中性の共役もしくは非共役ジエン、アニオン配位子または孤立電子対で配位可能な中性配位子を示し、ｊは１〜４の整数を示し、ｊが２以上の整数の場合、複数あるＱはそれぞれ同一でも異なっていてもよい。Ｃｐ¹およびＣｐ²は、互いに同一でも異なっていてもよく、Ｍと共にサンドイッチ構造を形成することができるシクロペンタジエニル基または置換シクロペンタジエニル基を示す。

In Formulas [A1] and [A2], M represents an atom of Group 4 of the periodic table, Q is a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or nonconjugated diene, an anionic ligand Alternatively, it represents a neutral ligand that can be coordinated with a lone electron pair, j represents an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Qs may be the same or different. Cp ¹ and Cp ² may be the same or different from each other, and denote a cyclopentadienyl group or a substituted cyclopentadienyl group which can form a sandwich structure with M.

In formula [A2], Y is a divalent hydrocarbon group having 1 to 30 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, and a divalent germanium-containing group group, a divalent tin-containing group, -O -, - CO -, - S -, - SO -, - SO 2 -, - Ge -, - Sn -, - NR a -, - P (R a) - ^{, -P (O) (R a} ) -, - BR a - or -AlR ^a - in indicating (wherein, R ^a is a hydrocarbon group having 1 to 20 carbon atoms, halogenated having 1 to 20 carbon atoms It is a nitrogen compound residue in which one or two hydrocarbon groups each having 1 to 20 carbon atoms are bonded to a hydrocarbon group, a hydrogen atom, a halogen atom or a nitrogen atom.

  In the above formulas [A1] and [A2], M represents an atom of Group 4 of the periodic table, preferably a titanium atom, a zirconium atom or a hafnium atom, more preferably a zirconium atom or a hafnium atom. When it is desired to obtain a copolymer (A) having a smaller amount of long chain branching, a zirconium atom is more preferable.

  Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or nonconjugated diene, an anionic ligand or a neutral ligand which can be coordinated with a lone electron pair, preferably, Q is A halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a neutral, conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, and a neutral ligand which can be coordinated with a lone electron pair To be elected. The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom.

  Specific examples of the hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a 2-methylpropyl group, a 1,1-dimethylpropyl group and a 2,2-dimethylpropyl group. 1,1-diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, sec-butyl group, t-butyl group, 1,1-dimethylbutyl group, Examples thereof include 1,1,3-trimethylbutyl group, neopentyl group, cyclohexylmethyl group, cyclohexyl group, 1-methyl-1-cyclohexyl group, benzyl group and the like, with preference given to methyl group, ethyl group and benzyl group.

Neutral having 10 or less carbon atoms, and specific examples of the conjugated or non-conjugated dienes, s- cis - or s- trans eta ^{4-1,3-butadiene,} s- cis - or s- trans eta ⁴ - 1,4-Diphenyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -3-methyl-1,3-pentadiene, s-cis- or s-trans ^{4 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-eta 4-1, ⁴ -ditolyl-1,3-butadiene, s-cis- or s-trans- eta 4-1, ⁴ -bis (trimethylsilyl) -1, ³ -butadiene and the like.

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

  Specific examples of the neutral ligand which can be coordinated by a lone electron pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine, or tetrahydrofuran, diethyl ether, dioxane, 1,2- 1,2- Ethers such as dimethoxyethane are mentioned.

  The copolymer (A) is more preferably one obtained by copolymerizing a monomer in the presence of a compound represented by the following general formula [A3]. The compound represented by the following general formula [A3] is a preferable embodiment of the compound represented by the above general formula [A2].

式［Ａ３］中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁸、Ｒ⁹およびＲ¹²はそれぞれ独立に水素原子、炭化水素基、ケイ素含有基またはケイ素含有基以外のヘテロ原子含有基を示し、Ｒ¹〜Ｒ⁴のうち隣接する二つの基同士は互いに結合して環を形成していてもよい。

In formula [A3], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a hetero group other than a silicon-containing group An atom-containing group is shown, and two adjacent groups among R ^{1 to} R ⁴ may be bonded to each other to form a ring.

  As a hydrocarbon group, a C1-C20 hydrocarbon group is preferable, For example, a C1-C20 alkyl group, a C7-C20 arylalkyl group, a C6-C20 aryl (aryl) And substituted aryl (aryl) groups. More specifically, methyl group, ethyl group, n-propyl group, isopropyl group, allyl (allyl) group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, amyl group, n-pentyl group 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, Examples include propylphenyl, t-butylphenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl, benzyl and cumyl groups, and oxygen-containing groups such as methoxy, ethoxy and phenoxy groups -Containing group such as nitro group, cyano group, N-methylamino group, N, N-dimethylamino group, N-phenylamino group, boron-containing group such as borane triyl group, diboranyl group, sulfonyl group, sulfenyl group And other sulfur-containing groups are also mentioned as hydrocarbon groups.

  In the above-mentioned hydrocarbon group, a hydrogen atom may be substituted by a halogen atom, and examples thereof include trifluoromethyl group, trifluoromethylphenyl group, pentafluorophenyl group, chlorophenyl group and the like.

  Examples of silicon-containing groups include silyl groups, siloxy groups, hydrocarbon-substituted silyl groups, and hydrocarbon-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) Silyl group etc. can be mentioned.

R ⁶ and R ¹¹ are the same atom or the same group selected from hydrogen atom, hydrocarbon group, silicon-containing group and hetero atom-containing group other than silicon-containing group, and R ⁷ and R ¹⁰ are hydrogen atom, hydrocarbon R ⁶ and R ⁷ may be combined with each other to form a ring, R ¹⁰ and R ¹⁰ and R ⁷ may be bonded to each other to form a ring. R ¹¹ may be bonded to each other to form a ring. However, R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.

R ¹³ and R ¹⁴ each independently represent an aryl group.
M ¹ represents a zirconium atom or a hafnium atom. The zirconium atom and the hafnium atom are both suitable as M ¹ of the metallocene compound of the above formula [A3], but from the viewpoint that a compound having a zirconium atom produces a copolymer (A) with a small amount of long-chain branching. More preferable.

Y ¹ represents a carbon atom or a silicon atom.
Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or nonconjugated diene having 4 to 20 carbon atoms, an anionic ligand or a neutral ligand capable of coordinating with a lone electron pair J represents an integer of 1 to 4 and when j is an integer of 2 or more, a plurality of Qs may be the same or different.

In the above formula [A3], examples of Q include the same as Q in the above formulas [A1] and [A2].
That is, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Preferably it is a chlorine atom.

  As a hydrocarbon group, a C1-C10 hydrocarbon group is preferable, and, specifically, a methyl group, an 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, t-butyl group, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl, benzyl and the like, with preference given to methyl, ethyl And benzyl.

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. Specific examples of the conjugated or nonconjugated diene neutral, s- cis - or s- trans eta ^{4-1,3-butadiene,} s- cis - or s- trans eta ^{4-1,4-diphenyl} - 1,3-butadiene, s- cis - or s- trans eta ^{4-3-methyl-1,3-pentadiene,} s- cis - or s- trans eta ^{4-1,4-dibenzyl-1,3} butadiene, s- cis - or s- trans eta ^{4-2,4-hexadiene,} s- cis - or s- trans eta ^{4-1,3-pentadiene,} s- cis - or s- trans eta ⁴ - 1,4-ditolyl-1,3-butadiene, s-cis- or s-trans-− ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene and the like can be mentioned.

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

  Specific examples of the neutral ligand which can be coordinated by a lone electron pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine, or tetrahydrofuran, diethyl ether, dioxane, 1,2- 1,2- Ethers such as dimethoxyethane are mentioned.

The cyclopentadienyl group having a substituent R ¹ to R ⁴ in the above formula [A3] is an unsubstituted cyclopentadienyl group in which R ¹ to R ⁴ is a hydrogen atom, 3-t-butylcyclopentadienyl group Group, 3-methylcyclopentadienyl group, 3-trimethylsilylcyclopentadienyl group, 3-phenylcyclopentadienyl group, 3-adamantylcyclopentadienyl group, 3-amyl cyclopentadienyl group, 3-cyclohexyl 3-substituted monosubstituted cyclopentadienyl group such as cyclopentadienyl 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-dimethylcyclopentadi group And 3,5-disubstituted cyclopentadienyl groups such as 3-phenyl-5-methylcyclopentadienyl group, 3-trimethylsilyl-5-methylcyclopentadienyl group, etc. is not. The cyclopentadienyl group which is unsubstituted (R < ¹ > -R < ⁴ > is a hydrogen atom) is preferable from the viewpoint of the easiness of the synthesis | combination of a metallocene compound, manufacturing cost, and the copolymerization ability of nonconjugated polyene.

As a fluorenyl group having a substituent R ⁵ to R ¹² in the formula [A3],
An unsubstituted fluorenyl group in which R ⁵ to R ¹² are a hydrogen atom,
2-position monosubstituted fluorenyl group such as 2-methylfluorenyl group, 2-t-butylfluorenyl group, 2-phenylfluorenyl group, etc.
4-substituted monosubstituted fluorenyl group such as 4-methylfluorenyl group, 4-t-butylfluorenyl group, 4-phenylfluorenyl group, etc.
Or 2,7- or 3,6-disubstituted fluorenyl group such as 2,7-di-t-butylfluorenyl group, 3,6-di-t-butylfluorenyl group, etc.
2,3,6,7 position 4 such as 2,7-dimethyl-3,6-di-t-butylfluorenyl group and 2,7-diphenyl-3,6-di-t-butylfluorenyl group Substituted fluorenyl group,
Alternatively, R ⁶ and R ⁷ are bonded to each other to form a ring, and R ¹⁰ and R ¹¹ are bonded to each other to form a ring, as represented by the following general formulas [V-I] and [V-II] Although 2, 3, 6 and 7 4-substituted fluorenyl group etc. are mentioned, it is not this limitation.

式[V−I]、[V−II]中、Ｒ⁵、Ｒ⁸、Ｒ⁹、Ｒ¹²は前記一般式［Ａ３］における定義と同様であり、
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。前記アルキル基としては、具体的にはメチル基、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−ペンチル基を例示できる。また、式[V−I]中、Ｒ^xおよびＲ^yはそれぞれ独立に炭素数１〜３の不飽和結合を有してもよい炭化水素基であり、Ｒ^xがＲ^aまたはＲ^cが結合した炭素と共同して二重結合を形成していてもよく、Ｒ^yがＲ^eまたはＲ^gが結合した炭素と共同して二重結合を形成していてもよく、Ｒ^xおよびＲ^yがともに炭素数１または２の飽和あるいは不飽和の炭化水素基であることが好ましい。

In the formulas [V-I] and [V-II], R ⁵ , R ⁸ , R ⁹ and R ¹² are the same as the definition in the general formula [A3],
R ^a , R ^b , R ^c , R ^d , R ^e , R ^f , R ^g and R ^h each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and they are mutually bonded to adjacent substituents And may form a ring. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, amyl group and n-pentyl group. Further, in the formula [V-I], R ^x and R ^y each independently represent a hydrocarbon group which may have a ^C 1 to ^C 3 unsaturated bond, and R ^x is R ^a or R ^c is a bond And R ^y may form a double bond in combination with carbon to which R ^e or R ^g is bonded, and R ^x and R ^y may form a double bond. It is preferable that both are a C1 or C2 saturated or unsaturated hydrocarbon group.

  Specifically, as a compound represented by the above general formula [V-I] or [V-II], an octamethyloctahydrodibenzofluorenyl group represented by the formula [V-III], a compound of the formula [V- A tetramethyldodecahydrodibenzofluorenyl group represented by formula IV, an octamethyltetrahydrodicyclopentafluorenyl group represented by formula [V-V], and a hexamethyl dihydrochloride represented by formula [V-VI] Examples thereof include a dicyclopentafluorenyl group and a b, h-dibenzofluorenyl group represented by the formula [V-VII].

The metallocene compounds represented by the above general formula [A3] containing any of these fluorenyl groups are all excellent in the copolymerization ability of non-conjugated polyenes, but when Y ¹ is a silicon atom, 2,7-position disubstituted fluorenyl group, Transition metals having a 3,6-position 2-substituted fluorenyl group, a 2,3,6,7-position 4-substituted fluorenyl group, and a 2,3,6,7-position 4-substituted fluorenyl group represented by the above general formula [V-I] The compounds are particularly good. When Y is a carbon atom, R ⁵ to R ^{12 each} represents a hydrogen atom, a unsubstituted fluorenyl group, a 3,6-disubstituted fluorenyl group, a 2,3,6,7-position 4-substituted fluorenyl group, the above general formula [V A metallocene compound having a 2,3,6,7-position 4-substituted fluorenyl group represented by -I] is particularly excellent.

In the present invention, in the metallocene compound represented by the above general formula [A3], when Y ¹ is a silicon atom and all of R ⁵ to R ¹² are hydrogen atoms, R ¹³ and R ¹⁴ are methyl. A group other than butyl, phenyl, silicon-substituted phenyl, cyclohexyl and benzyl;
When Y ¹ is a silicon atom, R ⁶ and R ¹¹ are both t-butyl, and R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹² are not t-butyl, R ¹³ And R ¹⁴ is selected from a group other than benzyl group and silicon-substituted phenyl group;
When Y ¹ is a carbon atom and all of R ⁵ to R ¹² are hydrogen atoms, R ¹³ and R ^{14 each} represent a methyl group, an isopropyl group, a t-butyl group, an isobutyl group, a phenyl group or p-t-butylphenyl A group other than a group, pn-butylphenyl group, silicon-substituted phenyl group, 4-biphenyl group, p-tolyl group, naphthyl group, benzyl group, cyclopentyl group, cyclohexyl group and xylyl group;
Y ¹ is a carbon atom, and R ⁶ and R ¹¹ are common groups selected from a t-butyl group, a methyl group or a phenyl group, and R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹² When they are different groups or atoms, R ¹³ and R ¹⁴ are selected from groups other than methyl group, phenyl group, p-t-butylphenyl group, p-n-butylphenyl group, silicon-substituted phenyl group, and benzyl group ;
A group in which Y ¹ is a carbon atom, R ⁶ is a dimethylamino group, a methoxy group or a methyl group, and R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are different from R ⁶ or When it is an atom, R ¹³ and R ¹⁴ are selected from a group other than methyl and phenyl;
When Y ¹ is a carbon atom and the site composed of a fluorenyl group and R ^{5 to} R ¹² is b, h-dibenzofluorenyl or a, i-dibenzofluorenyl, R ¹³ and R ¹⁴ are It is preferable to select from groups other than a methyl group and a phenyl group.

Specific examples of the metallocene compound represented by the above general formula [A3] will be shown below, but the scope of the present invention is not particularly limited thereby.
As specific examples of the metallocene compound represented by the above general formula [A3],
In the case where Y 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) (hexamethyl dihydro dicyclopentafluorenyl) 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,
Examples include di (m-tolyl) silylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride and the like.

In the case where Y 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) (tetramethyl dodecahydrodibenzofluorenyl) 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 (p-t-butylphenyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-t-butylphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-t-butylphenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-t-butylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (p-t-butylphenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (p-t-butylphenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (p-t-butylphenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (p-t-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 and the like can be mentioned.

  Examples of structural formulas of these metallocene compounds include di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride (the following (A)), and di (p-chlorophenyl): The structural formula of the (methylene) (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride (the following (B)) is shown below.

式［Ａ３］で表されるメタロセン化合物としては、上記例示の化合物のほか、上記例示の化合物のジルコニウム原子をハフニウム原子に置き換えた化合物、あるいは上記化合物のシクロペンタジエニル基を３−メチルシクロペンタジエニル基、３−フェニルシクロペンタジエニル基、３−ｔ−ブチルシクロペンタジエニル基、３−ｔ−ブチル−５−メチルシクロペンタジエニル基、３−ｔ−ブチル−５−エチルシクロペンタジエニル基、３，５−ジメチルシクロペンタジエニル基に置き換えた化合物、あるいは上記化合物の塩素原子をメチル基、ベンジル基に置き換えた化合物、あるいはこれらの組み合わせ等が挙げられるがこれらに限定されるものでもない。

As the metallocene compound represented by the formula [A3], in addition to the above-exemplified compounds, compounds in which the zirconium atom of the above-exemplified compounds is substituted with a hafnium atom, or a cyclopentadienyl group of the above-mentioned compound is 3-methylcyclopenta Dienyl group, 3-phenylcyclopentadienyl group, 3-t-butylcyclopentadienyl group, 3-t-butyl-5-methylcyclopentadienyl group, 3-t-butyl-5-ethylcyclopentan Compounds substituted with a dienyl group or 3,5-dimethylcyclopentadienyl group, or compounds substituted with a methyl group or a benzyl group for the chlorine atom of the above compound, or a combination of these and the like, but are limited thereto It is not a thing.

The above compounds may be used alone or in combination of two or more.
When the copolymer (A) is produced using the transition metal compound represented by the above formula [A1], [A2] or [A3], the hafnium atom is compared with the case where the central metal is a titanium atom or a zirconium atom The molecular weight of copolymer (A) tends to be higher in the case of. This is because (1) The Lewis acidity of the hafnium atom is smaller than that of the zirconium atom or titanium atom and the reactivity is lower. (2) The bonding energy between the hafnium atom and the carbon atom than that of the zirconium atom or titanium atom Is due to suppression of chain transfer reaction (including .beta.-hydrogen elimination reaction) of polymerization active species bound to the produced polymer chain which is one of the molecular weight determinants. it is conceivable that.

  The metallocene compound represented by the above formula [A1], [A2] or [A3] which can be suitably used for the preparation of the above-mentioned copolymer (A) is produced by any method without particular limitation. be able to. For example, J. Organomet. Chem. , 63, 509 (1996), WO 2005/100410, WO 2006123759, WO 01/27124, JP 2004-168744, JP 2004-175759, which is a publication related to an application filed by the present applicant. It can manufacture based on the method as described in the Unexamined-Japanese-Patent No. 2000-212194 grade | etc.,.

«Catalysts containing metallocene compounds»
As a polymerization catalyst which can be suitably used for the production of the above-mentioned copolymer (A), one which contains the metallocene compound of any of the above-mentioned [A1], [A2] or [A3] and which can copolymerize monomers It can be mentioned.

Preferably,
(A) A metallocene compound represented by the general formula [A1], [A2] or [A3],
(B) (b-1) at least one selected from organic metal compounds, (b-2) organic aluminum oxy compounds, and (b-3) compounds which react with the metallocene compound (a) to form an ion pair Compounds of the formula (hereinafter also referred to as "ionized ionic compounds"),
If necessary,
(C) A catalyst composed of a particulate carrier (hereinafter also referred to as "metallocene catalyst") can be mentioned. The components (b) and (C) will be specifically described below.

(B-1) Organometallic Compound The organometallic compound (b-1) includes, for example, the groups 1, 2 and 13, and 13 of the periodic table represented by the following general formulas [VII] to [IX]. And organic metal compounds of

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

As such an organoaluminum compound, for example, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri n-octylaluminum, tricycloalkylaluminum, isobutylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, ethyl Aluminum sesquichloride, methylaluminum dichloride, dimethylaluminum chloride, diisobutylaluminum hydride and the like can be mentioned.
M ² Al R ^a ₄ ... [VIII]
In formula [VIII], M ² represents Li, Na or K, and R ^a is a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms.

Examples of such complex alkylates of periodic table group 1 metal and aluminum include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .
-R ^a R ^b M ³ ... [IX]
In the formula [IX], R ^a and R ^{b, which} may be the same or different, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ³ is Mg, Zn or Cd It is.

  Examples of such a compound having a metal of Group 2 or Group 12 of the periodic table and two hydrocarbon groups include dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium, dimethyl zinc, diethyl zinc, diphenyl zinc, and the like. Di-n-propylzinc, diisopropylzinc, di-n-butylzinc, diisobutylzinc, bis (pentafluorophenyl) zinc, dimethylgodium and diethylcadmium and the like.

  Among the above organic metal compounds (b-1), organic aluminum compounds such as triethylaluminum, triisobutylaluminum and tri n-octylaluminum are preferable. Moreover, such an organometallic compound (b-1) may be used individually by 1 type, and may be used combining 2 or more types.

(B-2) Organic Aluminum Oxy Compound The organic aluminum oxy compound (b-2) may be a conventionally known aluminoxane, or a benzene insoluble organic compound as exemplified in JP-A-2-78687. It may be an aluminum oxy compound.

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

  The aluminoxane may contain a small amount of an organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be distilled off from the recovered solution of the aluminoxane, and then redissolved in a solvent or suspended in a poor solvent of the aluminoxane.

  Examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as exemplified as the organoaluminum compound represented by the above-mentioned formula [VII], and among them, trialkylaluminums and tricycloalkyls. Aluminum is preferred, and trimethylaluminum and triisobutylaluminum are particularly preferred. The organoaluminum compounds as described above can be used singly or in combination of two or more.

  Further, in the benzene-insoluble organoaluminum oxy compound which is one aspect of the above organoaluminum oxy compound (b-2), an Al component dissolved in benzene at 60 ° C. is usually 10 weight relative to 100 wt% benzene in terms of Al atom % Or less, preferably 5% by weight or less, particularly preferably 2% by weight or less, that is, those insoluble or poorly soluble in benzene are preferred.

  As said organoaluminum oxy compound (b-2), the organoaluminum oxy compound containing boron represented by following General formula [X] can also be mentioned.

式[X]中、Ｒ¹は炭素原子数が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、炭素原子数が１〜１０の炭化水素基を示す。

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

The organoaluminum oxy compound containing boron represented by the above general formula [X] is obtained by converting an alkylboronic acid represented by the following general formula [XI] and an organoaluminum compound into an inert solvent under an inert gas atmosphere. Can be produced by reacting at a temperature of -80.degree. C. to room temperature for 1 minute to 24 hours.
R ¹ -B (OH) ₂ ... [XI]
In formula [XI], R ¹ represents the same group as R ¹ in the general formula [X].

  Examples of the alkylboronic acid represented by the above general formula [XI] include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexyl Boronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid and the like can be mentioned. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid and pentafluorophenylboronic acid are preferable. These can be used singly or in combination of two or more.

As the organoaluminum compound to be reacted with such alkylboronic acid, the same organoaluminum compounds as those exemplified as the organoaluminum compound represented by the above-mentioned formula [VII] can be mentioned, and among them, trialkylaluminum and tricyclo Alkyl aluminum is preferred, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferred. These can be used singly or in combination of two or more.
The organoaluminum oxy compounds (b-2) as described above are used singly or in combination of two or more.

(B-3) Ionizing ionic compound The above ionizing ionic compound (b-3) includes, for example, JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, and JP-A-3-23. Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in, for example, 179006, JP-A-3-207703, JP-A-3-207704, and US Pat. No. 5,321,106. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned. Such an ionizing ionic compound (b-3) can be used individually by 1 type or in combination of 2 or more types.

Examples of the Lewis acid include compounds represented by BR ₃ (R is a phenyl group which may have a substituent such as fluorine, a methyl group or a trifluoromethyl group, or fluorine), for example, trifluoro Boron, 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 can be mentioned.

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

式[XII]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 [XII], as R ¹⁺ , H ⁺ , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptitrilienyl cation, a ferrocenium cation having a transition metal, and the like can be mentioned. R ^{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.

  Examples of the carbonium cation include trisubstituted carbonium cations such as triphenyl carbonium cation, tri (methylphenyl) carbonium cation, tri (dimethylphenyl) carbonium cation and the like.

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

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

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

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

  Examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammoniumtetra (phenyl) boron, trimethylammoniumtetra (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-ditrifluoromethylphenyl) Boron, tri (n- butyl) ammonium tetra (o-tolyl) and boron and the like.

  Examples of the N, N-dialkylanilinium salts include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N, 2,4,6-penta Methylanilinium tetra (phenyl) boron and the like can be mentioned.

  Examples of the dialkyl ammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

  Furthermore, as the above-mentioned ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium Mention may also be made of pentaphenyl cyclopentadienyl complex, N, N-diethylanilinium pentaphenyl cyclopentadienyl complex, boron compounds represented by the following formula [XIII] or [XIV], and the like. Here, in the formula, Et represents an ethyl group.

上記ボラン化合物としては、たとえば
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。

Examples of the borane compound include decaborane;
Bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate And salts of anions such as bis [tri (n-butyl) ammonium] decachlorodecaborate and bis [tri (n-butyl) ammonium] dodecachlorododecaborate;
Of metal borane anions such as tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydrate dodecaborate) nickelate (III) Salt etc. are mentioned.

Examples of the above carborane compounds include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1 -Methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane, une Decahydride-7,8-dimethyl-7,8-dicarbaundecaborane, dodecahydride-11-methyl-2,7-dicarbaundecaborane, tri (n-butyl) ammonium 1-carbadecaborate, tri (n -Butyl) ammonium-1-carbundecaborate, tri (n-butyl) ammonium-1-carbado Carbolate, 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-dicarbaundecaborate, tri (n-butyl) ammonium-2,9-dicarbaundecaborate, tri (n-butyl) ammonium 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-dical Anion salts such as boundecadecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate;
Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobalt acid salt (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) Ferrite (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-dicarbaundecaborate) cuprate (III), tri (n-butyl) Ammonium bis (undecahydride-7,8-dicarbaundecaborate) aborate (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-dical) Boundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III), tris [tri (n-butyl) ammonium ] Bis (undecahydride-7-carbundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbundecaborate) manganate (IV) Bis (tri (n-butyl) ammonium) bis (undecahydride-7-carbundecaborate) 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 an atom selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphorus vanadic acid, germano vanadic acid, arsenic vanadic acid, phosphoniobic acid, germano niobic acid, silicono molybdic acid, phosphomolybdic acid, titanium molybdic acid, germano molybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, linmolybdovanadic acid, lintungstovanadic acid, germanotungstovanadic acid, linmolybd tangstovanadic acid, germano molybd tungstovanadic acid, linmolybd tungstic acid , Linmolybdo niobic acid, and salts of these acids, such as metals of group 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium Etc Salts, and organic salts such as triphenylethyl salts can be used, not limited thereto.

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

  In the present invention, as the catalyst, the metallocene compound (a), an organic metal compound (b-1) such as triisobutylaluminum, an organic aluminum oxy compound (b-2) such as methylaluminoxane, and triphenylcarbenium tetrakis ( When a metallocene catalyst containing an ionizing ionic compound (b-3) such as pentafluorophenyl) borate is used, very high polymerization activity can be exhibited in the production of the copolymer (A).

(C) Carrier In the present invention, the carrier (c) optionally used is an inorganic compound or an organic compound, and is a granular or particulate solid.

As said inorganic compound, a porous oxide, an inorganic halide, clay, a clay mineral, or an ion exchange layered compound is preferable.
Examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _{2 and the} like, or composites or mixtures thereof, such as natural or the use synthetic zeolite, SiO ₂ -MgO, etc. _{SiO 2 -Al 2 O 3, SiO} 2 -TiO 2, SiO 2 -V 2 O 5, SiO 2 -Cr 2 O 3, SiO 2 -TiO 2 -MgO Can. Among these, those based on SiO ₂ and / or Al ₂ O ₃ are preferable. Such porous oxide differs in its properties depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of 50 to 1000 m. ^The pore volume is desirably in the range of ² / g, preferably 100 to 700 m ² / g, and in the range of 0.3 to 3.0 cm ³ / g. Such porous oxides are used after calcination at 100 to 1000 ° C., preferably 150 to 700 ° C., as necessary.

MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ or the like is used as the inorganic halide. The inorganic halide may be used as it is or after being crushed by a ball mill or a vibration mill. Moreover, after dissolving an inorganic halide in solvent, such as alcohol, what was made to precipitate in fine particle shape with a precipitation agent can also be used.

  The clay is usually composed mainly of clay minerals. The ion exchangeable layered compound is a compound having a crystal structure in which planes constituted by ionic bonds etc. are stacked in parallel with each other with weak bonding force, and the contained ions can be exchanged. Most clay minerals are ion exchange layered compounds. Moreover, as these clays, clay minerals, and ion exchangeable layered compounds, not only naturally occurring ones but also artificially synthesized ones can be used.

In addition, clay, clay mineral, and ion crystalline compounds having a layered crystal structure such as hexagonal close packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. as clay, clay mineral or ion exchange layered compound It can be illustrated. Such clays, clay minerals such as kaolin, bentonite, cypress clay, gilome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite And ion exchangeable layered compounds such as α-Zr (HAsO ₄ ) ₂ · H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ · 3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ · H ₂ O, α-Sn (HPO ₄ ) ₂ · H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO _{4 2} ), crystalline acid salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O, and the like.

  Such clay, clay mineral or ion exchangeable layered compound preferably has a pore volume of at least 0.1 cc / g and a radius of at least 20 Å as measured by mercury porosimetry, preferably 0.3 to 5 cc / g. Particularly preferred. Here, the pore volume is measured in the range of a pore radius of 20 to 30,000 Å by mercury porosimetry using a mercury porosimeter.

When a pore volume of a radius of 20 Å or more and a pore volume smaller than 0.1 cc / g is used as a carrier, it tends to be difficult to obtain high polymerization activity.
Chemical treatment is also preferably applied to the clay and clay mineral used in the present invention. As the chemical treatment, any of surface treatment for removing impurities adhering to the surface, treatment for affecting the crystal structure of clay, and the like can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, organic matter treatment and the like. The acid treatment not only removes surface impurities but also increases the surface area by eluting cations such as Al, Fe and Mg in the crystal structure. The alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic substance treatment, an ion complex, a molecular complex, an organic derivative or the like can be formed to change the surface area and the interlayer distance.

The ion exchangeable layered compound used in the present invention may be a layered compound in which the interlayer is expanded by utilizing ion exchangeability and exchanging exchange ions between layers with another large bulky ion. . Such bulky ions play the role of a pillar supporting a layered structure, and are usually called pillars. Also, introducing another substance between the layers of the layered compound in this way is called intercalation. The guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl _4, and metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ and B (OR) ₃ R represents a metal hydroxide ion such as a hydrocarbon group, [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ^+, etc. Etc. These compounds can be used alone or in combination of two or more. Also, when intercalating these compounds, polymerization obtained by hydrolyzing metal alkoxides (R is a hydrocarbon group etc.) such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ etc. And colloidal inorganic compounds such as SiO ₂ can be coexistent. Moreover, as a pillar, the oxide etc. which are produced | generated by heat-dehydrating are said after intercalating the said metal hydroxide ion between layers.

  The clay, clay mineral, and ion exchange layered compound used in the present invention may be used as it is, or may be used after processing such as ball milling and sieving. In addition, water may be newly added and adsorbed, or may be used after being subjected to heat dehydration treatment. Furthermore, they may be used alone or in combination of two or more.

Among these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, hectorite, teniolite and synthetic mica.
As said organic compound, the granular form thru | or the particulate-form solid which have a particle size in the range of 10-300 micrometers can be mentioned. Specifically, (co) polymers produced from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene as a main component, or vinylcyclohexane, styrene The (co) polymers produced by using as a main component and their modified products can be exemplified.

  The metallocene catalyst used in the present invention is at least selected from a metallocene compound (a), (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) an ionizing ionic compound. A specific organic compound component (d) as described later may optionally be included together with one type of compound (b) and optionally a carrier (c).

(D) Organic Compound Component In the present invention, the organic compound component (d) is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer as required. Examples of such organic compounds include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds and sulfonates, but not limited thereto.

«Method for producing copolymer (A)»
The above-mentioned copolymer (A) comprises ethylene (a1), α-olefin having 3 to 20 carbon atoms (a2), non-conjugated polyene (a3) and, if necessary, non-conjugated polyene (a4) Can be produced by copolymerizing the following monomers.

When such a monomer is copolymerized, the usage method and addition order of each component which comprise the polymerization catalyst mentioned above are chosen arbitrarily, but methods like following (1)-(5) are illustrated.
(1) A method of independently adding a metallocene compound (a) to a polymerization vessel.
(2) A method in which the metallocene compound (a) and the compound (b) are added to the polymerizer in any order.
(3) A method of adding a catalyst component having a metallocene compound (a) supported on a carrier (c) and a compound (b) in any order to a polymerizer.
(4) A method in which the catalyst component supporting the compound (b) on the carrier (c) and the metallocene compound (a) are added to the polymerization vessel in an arbitrary order.
(5) A method of adding a catalyst component having a metallocene compound (a) and a compound (b) supported on a carrier (c) to a polymerizer.

In each of the methods (2) to (5), at least two of the compound (A), the compound (B) and the carrier (C) may be contacted in advance.
In each of the methods (4) and (5) in which the compound (b) is supported, the compound (b) not supported may be added in an arbitrary order, as necessary. In this case, the compound (b) may be the same as or different from the compound (b) carried on the carrier (c).

  The solid catalyst component having the metallocene compound (a) supported on the carrier (c) and the solid catalyst component having the metallocene compound (a) and the compound (b) supported on the carrier (c) is olefin prepolymerization The catalyst component may further be supported on the prepolymerized solid catalyst component.

The copolymer (A) can be suitably obtained by copolymerizing monomers in the presence of a metallocene 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 the reaction volume when the polymerization of olefin is carried out using the metallocene catalyst as described above. It is used in such an amount that

  In the compound (b-1), the molar ratio [(b-1) / M] of the compound (b-1) to all transition metal atoms (M) in the metallocene compound (a) is usually 0.01 to 0.01. It is used in an amount of 50,000, preferably 0.05 to 10,000. In the compound (b-2), the molar ratio [(b-2) / M] of the aluminum atom in the compound (b-2) to the total transition metal (M) in the metallocene compound (a) is usually 10 It is used in an amount of about 50000, preferably 20 to 10,000. In the compound (b-3), the molar ratio [(b-3) / M] of the compound (b-3) to the transition metal atom (M) in the metallocene compound (a) is usually 1 to 20, preferably Is used in an amount of 1 to 15.

  In the present invention, the method for producing the copolymer (A) can be carried out in any of liquid phase polymerization methods such as solution (solution) polymerization and suspension polymerization, or gas phase polymerization methods, and is not particularly limited. It is preferable to have the process of obtaining the following polymerization reaction liquid.

In the step of obtaining a polymerization reaction solution, an aliphatic hydrocarbon is used as a polymerization solvent, and the above metallocene catalyst, preferably, R ¹³ and R ¹⁴ bonded to Y ¹ in the general formula [A3] is a phenyl group or , A phenyl group substituted by an alkyl group or a halogen group, and R ⁷ and R ^{10 each} have an alkyl substituent, and in the presence of a metallocene catalyst containing a transition metal compound, ethylene (a1) and 3 to 20 carbon atoms The step of obtaining a polymerization reaction liquid of the copolymer (A) by copolymerizing a monomer consisting of the α-olefin (a2) of the above, a nonconjugated polyene (a3) and optionally a nonconjugated polyene (a4) .

When the concentration of the copolymer (A) with respect to the polymerization solvent exceeds the above range, the viscosity of the polymerization solution is too high, the solution may not be uniformly stirred, and the polymerization reaction may be difficult.
Examples of the polymerization solvent include aliphatic hydrocarbons and aromatic hydrocarbons. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane, benzene, toluene and xylene And aromatic hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, and the like, and they can be used singly or in combination of two or more. Also, olefin itself can be used as a solvent. Among these, hexane is preferable from the viewpoint of separation with the copolymer (A) to be obtained and purification.

  The polymerization temperature is usually -50 to + 200 ° C, preferably in the range of 0 to + 200 ° C, more preferably in the range of +80 to + 200 ° C, although depending on the ultimate molecular weight of the metallocene catalyst system used and the polymerization activity, higher temperature It is desirable from the viewpoint of catalyst activity, copolymerizability and productivity that it is (+ 80 ° C. or higher).

  The polymerization pressure is usually under the conditions of normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch system, semi-continuous system and continuous system. Furthermore, it is also possible to divide the polymerization into two or more stages under different reaction conditions. In the present invention, among these, it is preferable to adopt a method of continuously supplying monomers to the reactor to carry out copolymerization.

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

  The molecular weight of the resulting copolymer (A) can also be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can also be adjusted by the amount of compound (b) used. Specifically, triisobutylaluminum, methylaluminoxane, diethyl zinc and the like can be mentioned. When hydrogen is added, its amount is suitably about 0.001 to 100 NL per kg of olefin.

  Further, the molar ratio ((a1) / (a2)) of the preparation of ethylene (a1) and the above α-olefin (a2) is preferably 40/60 to 99.9 / 0.1, more preferably 50 / 50 to 90/10, more preferably 55/45 to 85/15, and most preferably 55/45 to 78/22.

  The preparation amount of the non-conjugated polyene (a3) is usually 0. 1% with respect to 100% by weight of the total (total monomer preparation amount) of ethylene (a1), α-olefin (a2) and non-conjugated polyene (a3). It is 07 to 10% by weight, preferably 0.1 to 8.0% by weight, and more preferably 0.5 to 5.0% by weight.

<Organic peroxide (B)>
When the rubber composition of the present invention contains an organic peroxide (B) as a crosslinking agent, as the organic peroxide (B), conventionally known organic peroxides generally used in crosslinking of rubber Can be used.

In particular,
Dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide, di-t-amyl peroxide, 2,5-dimethyl-2,5 -Di (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, α , Alkyl peroxides such as α'-bis (t-butylperoxy-m-isopropyl) benzene and t-butyl hydroperoxide;
t-Butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxypivalate, t-butylperoxymaleic acid, t-butylperoxyneodecanoate, t-butylperoxybenzoate, di-t-butylperoxyphthalate Peroxyesters such as;
And ketone peroxides such as dicyclohexanone peroxide. These can be used alone or in combination of two or more. Among these, organic peroxides having a one-minute half-life temperature of 130 to 200 ° C. are preferable. For example, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethyl Preferred are cyclohexane, t-butylcumyl peroxide, di-t-amyl peroxide and t-butyl hydroperoxide.

  The organic peroxide (B) can obtain the desired physical properties by sufficient crosslinking, and in the composition of the present invention, the above copolymer (A) in terms of prevention of adverse effects due to excessive decomposition products and cost. Preferably, 1 to 10 parts by weight, more preferably 2 to 8 parts by weight, is used per 100 parts by weight.

<Metal salt of α, β-unsaturated organic acid (C)>
When the rubber composition of the present invention contains the metal salt (C) of the α, β-unsaturated organic acid, it is possible to improve the dynamic fatigue resistance and the wear resistance of the rubber composition in a well-balanced manner.

  Examples of the metal salt (C) of the α, β-unsaturated organic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, ethacrylic acid, vinyl-acrylic acid, itaconic acid, methylitaconic acid, aconitic acid, methyl Metal salts of acids such as aponitic acid, crotonic acid, alpha-methyl crotonic acid, cinnamic acid and 2,4-dihydroxycinnamic acid. These salts can be zinc, cadmium, calcium, magnesium, sodium or aluminum salts, but in particular zinc salts. Preferred metal salts (C) of α, β-unsaturated organic acids are zinc diacrylate and zinc dimethacrylate, and particularly preferred is zinc dimethacrylate. The metal salt (C) of the α, β-unsaturated organic acid can be used alone or in combination of two or more.

  The metal salt (C) of the α, β-unsaturated organic acid is preferably 5 to 30 parts by weight, more preferably 5 to 25 parts by weight, particularly preferably 100 parts by weight of the copolymer rubber (A). Is used in the range of 7 to 20 parts by weight.

<Carbon black (D)>
By containing a specific amount of carbon black (D), the rubber composition of the present invention improves the processability of the rubber composition and further improves the mechanical properties such as tensile strength, tear strength and abrasion resistance. A rubber composition for a transmission belt can be obtained.

  As carbon black (D), for example, Asahi # 55 G, Asahi # 60 G (all, manufactured by Asahi Carbon Co., Ltd.), Siest (SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, MT, etc.) Above, known materials such as Tokai Carbon Co., Ltd. can be used. These can be used alone or in combination. Moreover, what was surface-treated by the silane coupling agent etc. can also be used.

  The carbon black (D) is preferably in the range of 10 to 100 parts by weight, more preferably 10 to 90 parts by weight, particularly preferably 20 to 80 parts by weight with respect to 100 parts by weight of the copolymer rubber (A). Used. When the compounding amount of carbon black (D) is in the above range, a rubber composition excellent in dynamic magnification (dynamic modulus / static modulus), processability, mechanical properties and the like can be obtained.

<Other ingredients>
The rubber composition for a transmission belt according to the present invention is not limited to the components (A) to (D) described above, and unless the purpose of the present invention is impaired, rubber compounding agents known per se, such as softeners and antiaging agents. An agent, a crosslinking aid, a crosslinking accelerator, a filler, a processing aid, an activator, an antioxidant, a foaming agent, a plasticizer, a tackifier and the like can be appropriately blended.

«Softeners»
As the softener, softeners conventionally used for rubber can be used. Specifically, petroleum-based softeners such as process oil, lubricating oil, liquid paraffin, petroleum asphalt, vaseline; coal tar-based softeners such as coal tar and coal tar pitch; castor oil, linseed oil, rapeseed oil, soybean oil Fatty oil-based softeners such as coconut oil; tall oil; sub (factice); waxes such as beeswax, carnauba wax, lanolin, etc .: ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate, zinc laurate, etc. Fatty acids and fatty acid salts; and synthetic polymers such as petroleum resins, atactic polypropylene and coumarone indene resins. Among them, petroleum-based softeners are preferable, process oils are more preferable, paraffin-based process oils, naphthene-based process oils, aroma-based process oils and the like are more preferable, and paraffin-based process oils are particularly preferable. These softeners can be used alone or in combination of two or more.

«Anti-aging agent»
When an antiaging agent is used, at least one selected from a sulfur antiaging agent, a phenolic antiaging agent, and an amine antiaging agent can be used.

  As a sulfur-based antioxidant, a sulfur-based antioxidant generally used for rubber is used. Specifically, imidazole-based aging such as 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, zinc salt of 2-mercaptomethylbenzimidazole, zinc salt of 2-mercaptomethylimidazole, etc. Aliphatic thioether such as dimyristyl thiodipropionate, dilaurylthiodipropionate, distearylthiodipropionate, ditridecylthiodipropionate, pentaerythritol-tetrakis (β-lauryl-thiopropionate) Examples include anti-aging agents and the like. Among these, 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, zinc salt of 2-mercaptomethylbenzimidazole, pentaerythritol-tetrakis (β-lauryl-thiopropionate). Is preferred.

  As a phenolic anti-aging agent, a phenolic anti-aging agent usually used for rubber is used. Specifically, styrenated phenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2 4,6-tri-t-butylphenol, butylhydroxyanisole, 1-hydroxy-3-methyl-4-isopropylbenzene, mono-t-butyl-p-cresol, mono-t-butyl-m-cresol, 2, 4-dimethyl-6-t-butylphenol, butylated bisphenol A, 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2,2'-methylene-bis (4-ethyl-6-) t-Butylphenol), 2,2'-methylene-bis (4-methyl-6-t-nonylphenol), 2,2'-isobutylidene-bis (4,6-dimethylpheno) ), 4,4'-Butylidene-bis (3-methyl-6-t-butylphenol), 4,4'-methylene-bis (2,6-di-t-butylphenol), 2,2'-thio -Bis (4-methyl-6-t-butylphenol), 4,4'-thio-bis (3-methyl-6-t-butylphenol), 4,4'-thio-bis (2-methyl-6-butylphenol) ), 4,4′-thio-bis (6-t-butyl-3-methylphenol), bis (3-methyl-4-hydroxy-5-t-butylbenzene) sulfide, 2,2′-thio [diethyl] -Bis 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], bis [3,3-bis (4-hydroxy-3-t-butylphenyl) butyric acid] glycol ester, bis [2 -(2-hydroxy-5-methyl -3-tert-Butylbenzene) -4-methyl-6-tert-butylphenyl] terephthalate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, N , N'-hexamethylene-bis (3,5-di-t-butyl-4-hydroxyhydrocinnamide), n-octadecyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, pentaerythritol-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate], 1,1′-bis (4-hydroxyphenyl) cyclohexane, mono (α-methylbenzene) phenol, di (α-methylbenzyl) ) Phenol, tri (α-methylbenzyl) phenol, 2,6-bis (2-hydroxy-3-t-butyl-5-methylbenzyl) -4-methylphenol, 3,9-bis [2- {3- (3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,5- Di-t-amyl hydroquinone, 2,6-di-t-butyl-α-dimethylamino-p-cresol, 2,5-di-t-butylhydroquinone, 3,5-di-t-butyl-4-hydroxy Diethyl ester of benzyl phosphate, catechol, hydroquinone and the like can be mentioned. Examples of particularly preferred phenolic antioxidants include 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), 4,4'-methylene-bis (2,6-di-t-butylphenol ), 2,2′-thio-bis (4-methyl-6-t-butylphenol), 4,4′-thio-bis (3-methyl-6-t-butylphenol), 4,4′-thio-bis (2-methyl-6-butylphenol), 4,4′-thio-bis (6-t-butyl-3-methylphenol), tetrakis [methylene-3- (3,5-di-t-butyl-4-4) Hydroxyphenyl) propionate] methane, pentaerythritol-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,9-bis [2- {3- (3-t-butyl) -4- Dorokishi-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-spiro [5.5] and the like undecane.

  As an amine anti-aging agent, an amine anti-aging agent usually used for rubber is used. Specifically, amine-ketone based antioxidants such as 2,2,4-trimethyl-1,2-dihydroquinoline polymers; and naphthylamine based antioxidants such as phenyl-α-naphthylamine and phenyl-β-naphthylamine; p- (p-toluenesulfonylamido) diphenylamine, 4,4'-bis (α, α-dimethylbenzyl) diphenylamine, alkylated diphenylamine, octylated diphenylamine, dioctylated diphenylamine (eg, 4,4'-dioctyl diphenylamine), Diphenylamine based antioxidant such as high temperature reaction product of diphenylamine and acetone, low temperature reaction product of diphenylamine and acetone, low temperature reaction product of diphenylamine and aniline and acetone, reaction product of diphenylamine and diisobutylene; N , N'- Gife Le-p-phenylenediamine, n-isopropyl-N'-phenyl-p-phenylenediamine, N, N'-di-2-naphthyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine N-phenyl-N '-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-bis ( 1,4-dimethylpentyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl- p-phenylenediamide such as p-phenylenediamine, phenylhexyl-p-phenylenediamine, phenyloctyl-p-phenylenediamine and the like System antioxidant, and the like. Among these, especially 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, N, N′-diphenyl-p-phenylenediamine, N , N′-di-2-naphthyl-p-phenylenediamine is preferred.

  In the present invention, sulfur based antioxidants, phenol based antioxidants and amine based antioxidants may be used alone, but two or more types are used in terms of maintaining heat aging resistance for a long time under high temperature. It is preferable to use in combination.

  In the present invention, the sulfur-based antioxidant is preferably 0.2 to 10 parts by weight, more preferably 0.2 to 8 parts by weight, particularly preferably 0.2 to 10 parts by weight, per 100 parts by weight of the copolymer (A). It can be used in the range of 2 to 6 parts by weight. It is preferable to use a sulfur-based anti-aging agent in the above range because the effect of improving the heat aging resistance is large, and furthermore, the crosslinking of the rubber composition of the present invention is not inhibited.

  The phenolic antioxidant is preferably 0.2 to 5 parts by weight, more preferably 0.5 to 4 parts by weight, particularly preferably 0.5 to 3 parts by weight, per 100 parts by weight of the copolymer (A). It can be used in the range of parts. It is preferable to use a phenolic anti-aging agent in the above-mentioned range because the effect of improving the heat aging resistance is large, and furthermore, the crosslinking of the rubber composition of the present invention is not inhibited.

  The amine-based antioxidant is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 4 parts by weight, particularly preferably 0.2 to 3 parts by weight per 100 parts by weight of the copolymer (A). Used in the range of parts. It is preferable to use an amine-based anti-aging agent in the above-mentioned range because the effect of improving the heat aging resistance is large, and furthermore, the crosslinking of the rubber composition of the present invention is not inhibited.

«Crosslinking aids»
Specific examples of the crosslinking assistant include: sulfur; quinone dioxime compounds such as p-quinone dioxime; methacrylate compounds such as polyethylene glycol dimethacrylate; allyl compounds such as diallyl phthalate and triallyl cyanurate; maleimide And divinylbenzene and the like. Such a coagent is used in an amount of 0.5 to 2 moles, preferably about equimole, to 1 mole of the organic peroxide (B) used.

«Fillers»
Examples of fillers include silica, finely divided silicic acid, activated calcium carbonate, light calcium carbonate, ground calcium carbonate, talc, clay and the like. These fillers may be used alone or in combination of two or more. Such a filler is used in an amount of usually 1 to 500 parts by mass, preferably 1 to 400 parts by mass, and more preferably 1 to 300 parts by mass with respect to 100 parts by mass of the copolymer rubber (A). When the blending amount of the filler is within the above range, mechanical properties such as tensile strength, tear strength and abrasion resistance of the transmission belt can be improved.

«Processing aids»
As a processing aid, those generally blended with rubber as a processing aid can be widely used. Specifically, ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, zinc laurate or esters, etc. may be mentioned. These processing aids may be used alone or in combination of two or more. The processing aid can be suitably blended in an amount of usually 30 parts by mass or less, preferably 25 parts by mass or less, more preferably 20 parts by mass or less, based on 100 parts by mass of the copolymer rubber (A). It is excellent in processability, such as kneading | mixing processability, extrusion processability, injection moldability, as the compounding quantity of a processing aid is in the said range.

«Activator»
Examples of the activator include glycols such as polyethylene glycol and diethylene glycol; and amines such as di-n-butylamine and triethanolamine. These active agents may be used alone or in combination of two or more. The activator is suitably used in an amount of 0.2 to 10 parts by mass, preferably 0.3 to 5 parts by mass, more preferably 0.5 to 4 parts by mass, per 100 parts by mass of the copolymer rubber (A). It can be blended.

<Preparation of rubber composition for transmission belt>
The rubber composition for a transmission belt of the present invention can be prepared by sequentially or simultaneously blending the above-described components by known methods.

  In order to produce a cross-linked product from the rubber composition for a transmission belt of the present invention, an uncrosslinked rubber composition is prepared once as in the case of crosslinking a known rubber composition, and then this rubber composition is intended. The cross-linking may be carried out after being formed into the following shape. Preparation, molding and crosslinking of the rubber composition may be carried out separately or continuously.

  The crosslinkable rubber composition of the present invention can be produced, for example, by internal mixers (closed mixers) such as Banbury mixers, kneaders and intermixes, the above component (A) and optionally the above (C). The component (D) and the other components are kneaded at a temperature of 80 to 190 ° C., preferably 80 to 170 ° C., for 2 to 20 minutes, preferably 3 to 10 minutes, and then the above (B Component), component (C) and other components are additionally mixed, and after kneading at a roll temperature of 40 to 80 ° C. for 3 to 30 minutes using rolls or a kneader such as an open roll, the kneaded material is extruded / minute It can be prepared by dispensing. When the kneading temperature in the internal mixers is low, a vulcanization accelerator or the like may be simultaneously kneaded.

[Power transmission belt and its manufacturing method]
The transmission belt of the present invention is obtained by crosslinking the rubber composition for transmission belt of the present invention. Moreover, the manufacturing method of the transmission belt of this invention includes the process of bridge | crosslinking the rubber composition for transmission belts of this invention.

  The cross-linking is formed into the intended shape by simultaneously molding the uncrosslinked rubber composition of the present invention by various forming methods using an extruder, calender roll, press, injection molding machine, transfer molding machine, etc. Alternatively, the molded product can be introduced into the crosslinking tank and heated at a temperature of 100 to 270 ° C. for 1 to 40 minutes, or irradiated with radiation such as light, γ-ray or electron beam. Moreover, it can also bridge | crosslink at normal temperature.

  Such crosslinking step may use a mold or may perform crosslinking without using a mold. When a mold is not used, the steps of molding and crosslinking are usually carried out continuously. As a heating method in the crosslinking tank, a method using a heating tank such as hot air, glass bead fluidized bed, UHF (ultrahigh frequency electromagnetic wave), steam, LCM (hot molten salt tank), etc. may be mentioned.

  Hereinafter, the present invention will be more specifically described based on examples, but the present invention is not limited to these examples. In addition, the evaluation method of each physical property in a following example and a comparative example is as follows.

<Composition of Ethylene / α-Olefin / Non-Conjugated Polyene Copolymer>
The weight fraction (% by weight) of each constituent unit of the ethylene / α-olefin / nonconjugated polyene copolymer was determined by the measurement value by ¹³ C-NMR. The measurement value is measured using an ECX400P nuclear magnetic resonance apparatus (manufactured by JEOL) at a measurement temperature of 120 ° C., a measurement solvent: ortho-dichlorobenzene / deuterated benzene = 4/1, and the number of integrations: 8,000. It was obtained by measuring the ¹³ C-NMR spectrum of the polymer.

<Intrinsic viscosity>
The intrinsic viscosity [η] was measured at a temperature of 135 ° C. and a measurement solvent of decalin using a fully automatic limiting viscometer manufactured by Rigosha Co., Ltd.

<Weight Average Molecular Weight (Mw), Number Average Molecular Weight (Mn), Molecular Weight Distribution (Mw / Mn)>
The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw / Mn) are polystyrene equivalent values measured by gel permeation chromatography (GPC). The measuring device and conditions are as follows. In addition, the molecular weight was calculated based on a conversion method by preparing a calibration curve using commercially available monodispersed polystyrene.
Equipment: Gel permeation chromatography Alliance GP 2000 (manufactured by Waters),
Analyzer: Empower 2 (manufactured by Waters),
Column: TSKgel GMH6-HTx2 + TSKgel GMH6-HTLx2 (7.5 mm ID x 30 cm, manufactured by Tosoh Corporation),
Column temperature: 140 ° C,
Mobile phase: o-dichlorobenzene (containing 0.025% BHT),
Detector: Differential refractometer (RI), flow rate: 1.0 mL / min,
Injection volume: 400 μL,
Sampling time interval: 1s,
Column calibration: monodispersed polystyrene (made by Tosoh Corporation),
Molecular weight conversion: Calibration method taking into consideration old method EPR conversion / viscosity.

<Complex viscosity ^{* *} >
As a rheometer, using a viscoelasticity measuring apparatus Ares (manufactured by Rheometric Scientific), complex viscosity ^** ₍ ω _{= 0.01)} at a frequency ω = 0.01 rad / s under conditions of 190 ° C. and strain 1.0%. Complex viscosity ^** ₍ ω _{= 0.1)} at frequency ω _{= 0.1} rad / s, complex viscosity ^** ₍ ω _{= 10) at} frequency ω = ₁₀ rad / s and complex viscosity η ^* at frequency ω = 100 rad / s ₍ ω _{= 100)} (in all units, Pa · sec) was measured. Also, from the results obtained, the P value (η ^* ₍ ω _{= 0.1)} / ^{* *} ₍ ω) which is the ratio (η ^* ratio) of the complex viscosity of η ^* ₍ ω _{= 0.1)} and η ^* ₍ ω _{= 100) = 100)} ) was calculated.

<Number of long chain branches per 1000 carbon atoms (LCB _1000c )>
It measured by the method mentioned above.
<Evaluation of physical properties of unvulcanized rubber>
(1) Mooney viscosity (ML (1 + 4) 100 ° C.)
The Mooney viscosity (ML (1 + 4) 100 ° C.) at 100 ° C. was measured under the condition of 100 ° C. using a Mooney viscometer (Model SMV 202 manufactured by Shimadzu Corporation) in accordance with JIS K6300.

(2) Vulcanization induction time Using the uncrosslinked rubber compound in the examples and comparative examples, a vulcanizing measuring apparatus: MDR 2000 (manufactured by ALPHA TECHNOLOGIES) under measurement conditions of a temperature of 160 ° C. and a time of 30 minutes. The induction time (TS1) was measured as follows.

  The torque change obtained under conditions of constant temperature and constant shear rate was measured. The time taken for the torque to increase by 1 point (1 dNm) from the minimum torque value was taken as the vulcanization induction time (TS1; minutes).

(3) Vulcanization rate Using the uncrosslinked rubber composition in the Examples and Comparative Examples, the vulcanizing rate is measured by a measuring device MDR 2000 (manufactured by ALPHA TECHNOLOGIES) under the measurement conditions of a temperature of 160 ° C. and a time of 30 minutes. (TC90) was measured as follows.

  The torque change obtained under conditions of constant temperature and constant shear rate was measured. The time to reach 90% of the difference between the maximum value and the minimum value of the torque was taken as the vulcanization speed (TC 90; minutes).

Physical properties of vulcanized rubber
(1) Hardness test (Duro-A hardness)
According to JIS K 6253, measurement of sheet hardness (type A durometer, HA) was carried out by stacking flat portions to a thickness of about 12 mm using six 2 mm vulcanized rubber sheets having a smooth surface. However, test pieces containing foreign matter, bubbles, and flaws were not used. In addition, the dimensions of the measurement surface of the test piece were such that the tip of the needle could be measured at a position at least 12 mm away from the end of the test piece.

(2) Tensile Test The vulcanized rubber sheets obtained in Examples and Comparative Examples were punched out to prepare No. 3 dumbbell test pieces described in JIS K 6251 (2001). Using this test piece, a tensile test is carried out under the conditions of a measuring temperature of 25 ° C. and a tensile speed of 500 mm / min according to the method specified in the same JIS K 6251, 25% modulus (M ₂₅ ), 50% modulus (M ₅₀ ) 100% modulus (M ₁₀₀ ), 200% modulus (M ₂₀₀ ), 300% modulus (M ₃₀₀ ), tensile stress at break (T _B ) and tensile elongation at break (E _B ) were measured.

<Heat resistance aging test>
(1) The heat aging resistance test was done according to JIS K 6257. That is, the vulcanized rubber sheet was placed in an oven at 150 ° C. for 96 hours and heat treated, and then a tensile test was performed under conditions of a measuring temperature of 23 ° C. and a tensile speed of 500 mm / min. E _B ) and strength (T _B ) were measured, and tensile strength change rate A _C (T _B ) and elongation change rate A _C (E _B ) were calculated. In addition, the hardness (HA) of the sheet after heat treatment is measured in the same manner as the hardness test (Duro-A hardness) in the physical properties of vulcanized rubber, and the rate of change in hardness (AH) is calculated based on the following equation. did.
AH = H _1- H ₀
In the above equation, H ₀ indicates the hardness (HA) of the sheet before heat treatment, and H ₁ indicates the hardness (HA) of the sheet after heat treatment.
(2) Tests and measurements were carried out in the same manner as in (1) above, except that the vulcanized rubber sheet was put in an oven at 150 ° C. for 168 hours and heat treated in (1) above.

<Bending test>
The bending test was performed according to JIS K6260. Set a 120 mm long, 25 mm wide and 7 mm thick flawless strip test specimen on a Dematcher Flex Fatigue Tester with a distance between chucks of 75 mm, and perform bending deformation by moving the distance between chucks of 75 mm to 18 mm at a cycle of 5 Hz at room temperature. The number of times before giving and cutting was determined.

<Abrasion test>
The Taber abrasion test was performed according to JIS K6264. That is, using a rotary abrasion tester (Model TS manufactured by Toyo Seiki Seisaku-sho, Ltd.), the amount of wear after 1000 times was determined under the conditions of wear wheel H-18, load 1000 g, rotation speed 60 rpm.

<Crosslink density>
The crosslinking density ν was calculated from the Flory-Rehner equation (a) using the following equilibrium swelling. V _R in the formula (a) was determined by extracting the crosslinked 2 mm sheet with toluene under the condition of 37 ° C. × 72 h.

[Ethylene-propylene-nonconjugated polyene copolymer]
Production Example 1 Production of Ethylene / Propylene / VNB Copolymer (A-1) 1.5 L / h of hexane dehydrated and purified from a supply port of a continuous polymerizer made of SUS having a volume of 1 L, and a hexane solution of triisobutylaluminum 0.1 L / h (0.5 mmol / h) of (5 mmol / L), a solution of di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride in hexane (0. 01 mmol / L, 0.03 L / h (0.0003 mmol / h), triphenylcarbenium tetrakis (pentafluorophenyl) borate in toluene solution (0.025 mmol / L), 0.06 L / h (0.0015 mmol / L) h) supplied continuously. At the same time, 50 g / h of ethylene, 38 g / h of propylene, 6.1 g / h of 5-vinyl-2-norbornene (VNB) and 0.3 NL / h of hydrogen are continuously supplied from the other feed port of the continuous polymerization vessel. The polymerization vessel was filled with a liquid phase, and continuous solution polymerization was performed under the conditions of a polymerization temperature of 95 ° C., a total pressure of 3.6 MPaG, and a residence time of 30 minutes.

The polymerization solution containing the ethylene / propylene / VNB copolymer produced in the polymerization vessel is continuously discharged through the outlet provided at the bottom of the polymerization vessel, and the jacket portion is 10 kg / cm to maintain the temperature of the polymerization solution. ^{(2) A} steam-heated connecting pipe is introduced, and a feed port through which methanol, which is a catalyst deactivator, is injected is attached immediately before reaching the connecting pipe, and injected at a rate of about 0.15 L / h to join the polymerization solution. I did.

  The polymerization solution in the steam-heated connection pipe was continuously fed to the flash tank by adjusting the opening of the pressure control valve provided at the end of the connection pipe so as to maintain 3.6 MPaG. In addition, the pressure in the polymerization vessel was always controlled by the pressure control valve so as to be 3.6 MPaG. As a result, in the obtained ethylene-propylene-VNB copolymer (A-1), the weight fraction of constituent units derived from ethylene is 61.5% by weight, and the weight fraction of constituent units derived from VNB is 0 .8 wt%, intrinsic viscosity [.eta.]: 2.3 dl / g. Physical properties are shown in Table 1.

<Ethylene-propylene-nonconjugated polyene copolymer (A'-1) and (A'-2)>
Physical properties of the ethylene / propylene / non-conjugated polyene copolymers (A′-1) and (A′-2) used in Comparative Examples described later are shown in Table 1 below.

Example 1
As a first step, 100 parts by weight of the ethylene-propylene-VNB copolymer (A-1) obtained in Preparation Example 1 is masticated for 30 seconds using a BB-2 type Banbury mixer (manufactured by Kobe Steel). Next, 55 parts by weight of carbon black (Asahi # 60G, manufactured by Asahi Carbon Co., Ltd.) as component (D), and 15 parts by weight of paraffinic process oil (Diana Process PW-380, manufactured by Idemitsu Kosan Co., Ltd.) And 1 part by weight of an anti-aging agent (Nocrac 224, manufactured by Ouchi Shinko Chemical Co., Ltd.), and kneaded at 140 ° C. for 2 minutes. Thereafter, the ram was raised and cleaned, and kneading was further carried out for 1 minute, and the mixture was discharged at about 150 ° C. to obtain a first stage composition.

  Next, as a second step, the composition obtained in the first step was treated as an 8-inch roll (Nippon Roll Co., Ltd., front roll surface temperature 50 ° C., rear roll surface temperature 50 ° C. front roll) And the number of revolutions of the rear roll 18 rpm), and 6.8 parts by weight of dicumyl peroxide (Kayakumiru D-40C, Kayaku Akzo Co., Ltd.) as the component (B) and the component (C) Then, 10 parts by weight of zinc methacrylate (ZMA) (manufactured by Kawaguchi Chemical Co., Ltd.) was added and the mixture was kneaded for 10 minutes to obtain an uncrosslinked rubber compound. Unvulcanized rubber physical properties were evaluated using this rubber compound.

  The kneaded product was divided into sheets, and pressed at 160 ° C. for 20 minutes using a 100-ton press molding machine to prepare a 2 mm-thick vulcanized rubber sheet. Using this, evaluation of the physical properties of vulcanized rubber, heat aging test, abrasion test and measurement of crosslink density were performed. For the bending test, a sample having a length of 120 mm, a width of 25 mm, and a thickness of 7 mm obtained by pressing at 160 ° C. for 25 minutes was used. The results are shown in Table 2.

[Examples 2 to 3 and Comparative Examples 1 to 5]
A non-crosslinked rubber composition in the same manner as in Example 1 except that the types and amounts of each compounded in the first step and the second step were as shown in Table 2 in Example 1. An uncrosslinked rubber sheet and a vulcanized rubber sheet were prepared and evaluated. The results are shown in Table 2.

表２中の１）〜５）は以下のとおりである。
１）カーボンブラック（旭＃６０Ｇ、旭カーボン（株）社製）
２）パラフィン系プロセスオイル（ダイアナプロセスＰＷ−３８０、出光興産（株）製）
３）アミン系老化防止剤（ノクラック２２４、大内新興化学（株）製）
４）メタクリル酸亜鉛（川口化学社製）
５）ジクミルパーオキシド（カヤクミルD-40C、化薬アクゾ社製）

1) to 5) in Table 2 are as follows.
1) Carbon black (Asahi # 60G, manufactured by Asahi Carbon Co., Ltd.)
2) Paraffinic process oil (Diana Process PW-380, manufactured by Idemitsu Kosan Co., Ltd.)
3) Amine based anti-aging agent (Nocrac 224, made by Ouchi New Chemical Co., Ltd.)
4) Zinc methacrylate (manufactured by Kawaguchi Chemical Co., Ltd.)
5) Dicumyl peroxide (Kayakumiru D-40C, manufactured by Kayaku Akzo)

Claims (5)

A non-molecular containing two or more in total of partial structures selected from the group consisting of ethylene (a1), α-olefins of 3 to 20 carbon atoms (a2), and the following general formulas (I) and (II) Containing ethylene / α-olefin / non-conjugated polyene copolymer (A) having a constitutional unit derived from conjugated polyene (a3) and satisfying the following requirements (i) to (v) , and A rubber composition for a transmission belt , wherein the nonconjugated polyene (a3) contains 5-vinyl-2-norbornene (VNB) .

(I) The molar ratio of ethylene (a1) / α-olefin (a2) is 40/60 to 99.9 / 0.1.
(Ii) The weight fraction of the structural unit derived from the nonconjugated polyene (a3) is 0.07% by weight to 10% by weight in 100% by weight of the ethylene / α-olefin / nonconjugated polyene copolymer.
(Iii) Weight fraction of weight average molecular weight (Mw) of ethylene / α-olefin / nonconjugated polyene copolymer (A) and weight fraction of constituent unit derived from nonconjugated polyene (a3) ((a3) (Wt%) and the molecular weight of the non-conjugated polyene (a3) (molecular weight of (a3)) satisfy the following formula (1).
4.5 ≦ Mw × (a3) weight fraction / 100 / (a3) molecular weight ≦ 40 (1)
(Iv) Complex viscosity ^** ₍ ω _{= 0.1)} (Pa · sec) at a frequency ω = _0.1 rad / s and frequency ω = 100 rad obtained by linear viscoelasticity measurement (190 ° C.) using a rheometer The ratio P (η ^* ₍ ω _{= 0.1)} / ^{* *} ₍ ω _{= 100)} ) to the complex viscosity ^{* *} ₍ ω _{= 100)} (Pa · sec) at / s, the limiting viscosity [η], The weight fraction of the structural unit derived from the conjugated polyene (a3) (the weight fraction of (a3)) satisfies the following formula (2).
Weight fraction of P / ([η] ^2.9 ) ≦ (a 3) × 6 (2)
(V) The number of long chain branches per 1000 carbon atoms (LCB _1000C ) obtained using 3D-GPC, and the natural logarithm [Ln (Mw)] of the weight average molecular weight (Mw) is represented by the following formula (3) Meet.
LCB _{1000 C} ≦ 1-0.07 × Ln (Mw) (3)   1 to 10 parts by weight of an organic peroxide (B), 5 to 30 parts by weight of a metal salt of an α, β-unsaturated organic acid (C) and carbon black (100 parts by weight of the copolymer (A) The rubber composition for a transmission belt according to claim 1, which contains 10 to 100 parts by weight of D).   The rubber composition for a transmission belt according to claim 1 or 2, wherein the α-olefin (a2) is propylene. A method for producing a transmission belt comprising the step of crosslinking the rubber composition for a transmission belt according to any one of claims 1 to 3 . A transmission belt obtained by crosslinking the rubber composition for a transmission belt according to any one of claims 1 to 3 .