JP6949497B2 - Anti-vibration rubber compositions and anti-vibration rubber products - Google Patents

Description

The present invention relates to an anti-vibration rubber composition containing an ethylene / α-olefin / non-conjugated polyene copolymer and an anti-vibration rubber product obtained by vulcanizing the composition.

Since ethylene / propylene / non-conjugated diene copolymer rubber (EPDM) does not have an unsaturated bond in the main chain, it has excellent heat resistance (including heat aging resistance) and weather resistance as compared with general-purpose diene rubber. It is used as an anti-vibration rubber to prevent vibration and noise in the fields of automobile parts and industrial material parts.

In the field of automobile parts, anti-vibration rubber is used in, for example, engine mounts and muffler hangers in order to absorb vibration during engine driving and prevent noise. Conventionally, as such a material for anti-vibration rubber, a rubber composition in which a filler such as silica or carbon black is mixed with EPDM has been used (see, for example, Patent Documents 1 and 2).

However, in recent years, the demand for anti-vibration characteristics such as dynamic magnification and compression set has been increasing more and more, and further improvement is desired.

Japanese Unexamined Patent Publication No. 2004-161985 Japanese Unexamined Patent Publication No. 2006-348095

An object of the present invention is to provide a rubber composition capable of producing a vibration-proof rubber having an improved dynamic magnification and compression set as compared with a conventional EPDM-based vibration-proof rubber.

As a result of diligent research to solve the above problems, the present inventors have grafted an unsaturated carboxylic acid or a derivative thereof onto an ethylene / α-olefin / non-conjugated polyene copolymer. By blending the copolymer and silica, it has been found that an anti-vibration rubber having improved dynamic magnification and compression set can be obtained, and the present invention has been completed. That is, the present invention relates to, for example, the following [1] to [10].

[1] Ethylene / α-olefin / non-conjugated polyene copolymer (A) having 3 to 20 carbon atoms, 100 parts by weight, graft-modified ethylene / α-olefin copolymer grafted with unsaturated carboxylic acid or a derivative thereof A composition for anti-vibration rubber, which comprises 1 to 100 parts by weight of (B) and 1 to 100 parts by weight of silica (C).

[2] The anti-vibration rubber composition according to Item [1], wherein the copolymer (A) satisfies the following conditions (i) to (v).
(I) The molar ratio [(a1) / (a2)] of the structural unit derived from ethylene (a1) to the structural unit derived from α-olefin (a2) is 40/60 to 99.9 / 0. 1;
(Ii) The content of the structural unit derived from the non-conjugated polyene (a3) is 0.07 to 10% by weight, where the total of the structural units of (a1), (a2) and (a3) is 100% by weight. ;
(Iii) Weight average molecular weight (Mw) of ethylene / α-olefin / non-conjugated polyene copolymer (A) and weight fraction of structural unit derived from non-conjugated polyene (a3) (weight fraction of (a3)) (% By weight)) and the molecular weight of the non-conjugated polyene (a3) (the molecular weight of (a3)) satisfy the following formula (1);
4.5 ≤Mw x (a3) weight fraction / 100 / (a3) molecular weight ≤40 ... (1)
^{(Iv) Complex viscosity η *} ₍ ω _{= 0.1)} (Pa · sec) at frequency ω = 0.1 rad / s and frequency ω = 100 rad obtained by linear viscous elasticity measurement (190 ° C.) using a leometer. The ratio P (η ^* ₍ ω _{= 0.1)} / η ^* ₍ ω _{= 100)} ^{) to the complex viscosity η *} ₍ ω _{= 100)} (Pa · sec) at / s, the extreme viscosity [η], and the non- 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 ) ≤ (a3) x 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) are expressed by the following formula (3). Meet.
LCB _1000C ≦ 1-0.07 × Ln (Mw)… (3)

[3] Item [1] or [2], wherein the non-conjugated polyene contains two or more partial structures selected from the group consisting of the following general formulas (I) and (II) in the molecule in total. The anti-vibration rubber composition according to.

［４］ 前記非共役ポリエンが５−ビニル−２−ノルボルネン（ＶＮＢ）を含むことを特徴とする項［１］〜［３］のいずれか一項に記載の防振ゴム用組成物。
［５］ 前記共重合体（Ｂ）の密度が、８６０ｋｇ／ｍ³以上８８０ｋｇ／ｍ³未満であることを特徴とする項［１］〜［４］のいずれか一項に記載の防振ゴム用組成物。
［６］ 前記共重合体（Ｂ）は、示差走査熱量分析（ＤＳＣ）によって測定された融点が２０℃以上６０℃未満であるか、または示差走査熱量分析（ＤＳＣ）により融点を示すピークが観察されないことを特徴とする項［１］〜［５］のいずれか一項に記載の防振ゴム用組成物。
［７］ さらに酸化亜鉛（Ｃ）を含有することを特徴とする項［６］に記載の防振ゴム用組成物。
［８］ 項［１］〜［７］のいずれか一項に記載の防振ゴム用組成物の架橋体からなる防振ゴム。
［９］ 項［１］〜［７］のいずれか一項に記載の防振ゴム用組成物の架橋体を含む自動車部品用防振ゴム製品。
［１０］ 前記自動車部品用防振ゴム製品がマフラーハンガーであることを特徴とする項［９］に記載の自動車部品用防振ゴム製品。

[4] The anti-vibration rubber composition according to any one of Items [1] to [3], wherein the non-conjugated polyene contains 5-vinyl-2-norbornene (VNB).
[5] The density of the copolymer (B), anti-vibration rubber according to any one of claim [1] to [4], which is a less than 860 kg / m ³ or more 880 kg / m ³ Composition for.
[6] The copolymer (B) has a melting point measured by differential scanning calorimetry (DSC) of 20 ° C. or higher and lower than 60 ° C., or a peak indicating a melting point is observed by differential scanning calorimetry (DSC). The anti-vibration rubber composition according to any one of items [1] to [5], wherein the composition is not provided.
[7] The anti-vibration rubber composition according to Item [6], which further contains zinc oxide (C).
[8] An anti-vibration rubber comprising a crosslinked product of the anti-vibration rubber composition according to any one of items [1] to [7].
[9] An anti-vibration rubber product for automobile parts, which comprises a crosslinked body of the anti-vibration rubber composition according to any one of items [1] to [7].
[10] The vibration-proof rubber product for automobile parts according to item [9], wherein the vibration-proof rubber product for automobile parts is a muffler hanger.

According to the present invention, it is possible to obtain a vibration-proof rubber having improved dynamic magnification and compression set as compared with the case of using a conventional EPDM-based rubber composition.

Hereinafter, the present invention will be described in detail.
[Composition for anti-vibration rubber]
The anti-vibration rubber composition according to the present invention (hereinafter, may be simply referred to as "the composition of the present invention" or "the rubber composition of the present invention") has an ethylene / α-olefin / non-conjugated polyene co-weight. Combined (A) (hereinafter, may be simply referred to as "copolymer (A)") 100 parts by weight, graft-modified ethylene / α-olefin copolymer (B) grafted with saturated carboxylic acid or a derivative thereof. (Hereinafter, it may be simply referred to as "copolymer (B)".) It is characterized by containing 1 to 100 parts by weight and 1 to 100 parts by weight of silica (C). In addition, the composition of the present invention preferably contains zinc oxide (D), and may further contain other components.

<Ethylene / α-olefin / non-conjugated polyene copolymer (A)>
The copolymer (A) used in the present invention has a structural unit derived from ethylene (a1), an α-olefin (a2) having 3 to 20 carbon atoms, and a non-conjugated polyene (a3).

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, and the like. Examples thereof include 1-tetradecene, 1-hexadecene, and 1-eikosen. Of 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 α-olefins are preferable because the raw material cost is relatively low, the obtained copolymer (A) exhibits excellent mechanical properties, and a molded product having rubber elasticity can be obtained.

The α-olefin (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 type of α-olefin (a2) having 3 to 20 carbon atoms, and two or more types of α having 3 to 20 carbon atoms. -It may contain a structural unit derived from the olefin (a2).

The non-conjugated polyene (a3) is not particularly limited as long as it is a compound having two or more unconjugated unsaturated bonds, but for example, a total of partial structures selected from the group consisting of the following general formulas (I) and (II). Examples thereof include compounds containing two or more in the molecule.

Examples of the non-conjugated polyene (a3) include 5-vinyl-2-norbornene (VNB), norbornadiene, 1,4-hexadiene, dicyclopentadiene and the like. Among these, the non-conjugated polyene (a3) is VNB because it is highly available, has good reactivity with peroxide during the cross-linking reaction after polymerization, and easily improves the heat resistance of the polymer composition. , And more preferably the non-conjugated polyene (a3) is VNB. The non-conjugated polyene (a3) may be used alone or in combination of two or more.

The copolymer (A) has, in addition to the structural units derived from the above (a1), (a2), and (a3), a partial structure further selected from the group consisting of the above general formulas (I) and (II). It may have a structural unit derived from a non-conjugated polyene (a4) containing only one in the molecule.

Examples of the non-conjugated polyene (a4) include 5-ethylidene-2-norbornene (ENB), 5-methylene-2-norbornene, 5- (2-propenyl) -2-norbornene, and 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-pentenyl) -2 -Norbornene and the like. Of these, ENB is preferable because it is highly available, highly reactive with sulfur and vulcanization accelerators during the cross-linking reaction after polymerization, the cross-linking rate can be easily controlled, and good mechanical properties can be easily obtained. .. The non-conjugated polyene (a4) may be used alone or in combination of two or more.

When the copolymer (A) contains a structural unit derived from the non-conjugated polyene (a4), the proportion thereof is not particularly limited as long as the object of the present invention is not impaired, but is usually 0 to 0. Included in a weight fraction of about 20% by weight, preferably 0 to 8% by weight, more preferably 0.01 to 8% by weight (however, by weight of (a1), (a2), (a3), (a4). The total rate is 100% by weight).

It is preferable that the copolymer (A) satisfies the following requirements (i) to (v) (hereinafter, also referred to as requirements (i) to (v), respectively).
(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 non-conjugated polyene (a3) is 0.07% by weight to 10% by weight in 100% by weight of the ethylene / α-olefin / non-conjugated polyene copolymer.
(Iii) The weight average molecular weight (Mw) of the ethylene / α-olefin / non-conjugated polyene copolymer and the weight fraction (% by weight) of the structural unit derived from the non-conjugated polyene (a3). )) And the molecular weight of the non-conjugated polyene (a3) (the molecular weight of (a3)) satisfy the following formula (1).
4.5 ≤Mw x (a3) weight fraction / 100 / (a3) molecular weight ≤40 ... (1)
^{(Iv) Complex viscosity η *} ₍ ω _{= 0.1)} (Pa · sec) at frequency ω = 0.1 rad / s and frequency ω = 100 rad obtained by linear viscous elasticity measurement (190 ° C.) using a leometer. The ratio P (η ^* ₍ ω _{= 0.1)} / η ^* ₍ ω _{= 100)} ^{) to the complex viscosity η *} ₍ ω _{= 100)} (Pa · sec) at / s, the extreme viscosity [η], and the non- The weight fraction of the structural unit derived from the conjugated polyene (a3) (weight fraction of (a3)) satisfies the following formula (2).
Weight fraction of P / ([η] ^2.9 ) ≤ (a3) x 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) are expressed by the following formula (3). Meet.
LCB _1000C ≦ 1-0.07 × Ln (Mw)… (3)

≪Requirement (i) ≫
Requirement (i) specifies that the molar ratio of ethylene (a1) / α-olefin (a2) in the 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 even more preferably 55/45 to 78/22.

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

≪Requirements (ii) ≫
The requirement (ii) is that the weight fraction of the structural unit derived from the non-conjugated polyene (a3) in the copolymer (A) is 100% by weight of the copolymer (A) (that is, the weight of all the structural units). It is specified that the fraction is in the range of 0.07% by weight to 10% by weight (in 100% by weight in total). 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 excellent mechanical properties, and exhibits a high cross-linking rate when cross-linked using a peroxide. The amount of non-conjugated polyene (a3) in the copolymer (A) (content of the structural unit derived from non-conjugated polyene (a3)) can be determined by ^{13 C-NMR.}

≪Requirements (iii) ≫
The requirement (iii) is the weight average molecular weight (Mw) of the copolymer (A) and the structural unit derived from the non-conjugated polyene (a3) in the copolymer (A) in the copolymer (A). It specifies 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). The above formula (1) of the requirement (iii) is preferably the following formula (1').
4.5 ≤Mw x (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, the cross-linking performance is sufficient, the cross-linking rate is excellent, and the cross-linking rate is excellent. It is possible to produce anti-vibration rubber exhibiting excellent mechanical properties. The weight average molecular weight (Mw) of the copolymer (A) can be determined as a polystyrene-equivalent numerical value measured by gel permeation chromatography (GPC).

In the above copolymer (A), when "weight fraction of Mw × (a3) / molecular weight of 100 / (a3)" satisfies the above formula (1) or (1'), the degree of cross-linking becomes appropriate and the machine It is possible to produce an anti-vibration rubber having a good balance between physical characteristics and heat aging resistance. If the value of "Mw × (a3) weight fraction / 100 / (a3) molecular weight" is too low, the crosslinkability may be insufficient and the cross-linking rate may be slowed down, and if the value is too high. , Excessive cross-linking may occur and the mechanical properties may deteriorate.

≪Requirements (iv) ≫
^{Requirement (iv) is the complex viscosity η *} ₍ ω _{= 0.1} ) at a frequency ω = 0.1 rad / s obtained by linear viscous elasticity measurement (190 ° C.) of the above copolymer (A) using a leometer. ₎ (Pa · sec) and complex viscosity η ^* ₍ ω _{= 100)} (Pa · sec) at ^{frequency ω = 100 rad / s ratio P (η *} ₍ ω _{= 0.1)} / η ^* ₍ ω _{= 100)} ), The ultimate viscosity [η], and the weight fraction of the structural unit derived from the non-conjugated polyene (a3) (weight fraction of (a3): weight%) satisfy the above formula (2). It is something to identify. The above equation (2) of the requirement (iv) is preferably the following equation (2').
Weight fraction of P / ([η] ^2.9 ) ≤ (a3) x 5.7 ... (2')

Here, the ratio P (η ^* ₍ ω)) of the complex viscosity η ^* ₍ ω _{= 0.1)} ^{at the frequency ω = 0.1 rad / s to the complex viscosity η *} ₍ ω _{= 100)} at the frequency ω = 100 rad / s. _{= 0.1)} / η ^* ₍ ω _{= 100)} ) represents the frequency dependence of viscosity, and P / ([η] ^2.9 ), which corresponds to the left side of equation (2), is short-chain branching, molecular weight, etc. Although there is an effect, it tends to show a high value when there are many long-chain branches. Generally, in an ethylene / α-olefin / non-conjugated polyene copolymer, the more structural units derived from the non-conjugated polyene, the more long-chain branches tend to be contained. It is considered that the above formula (2) can be satisfied because the number of long-chain branches is smaller than that of the conventionally known ethylene / α-olefin / non-conjugated polyene copolymer.

In the present invention, the P value is a complex viscosity at 0.1 rad / s obtained by measuring the viscoelasticity measuring device Ares (manufactured by Rheometric Scientific) at 190 ° C., strain 1.0%, and changing the frequency. And the complex viscosity at 100 rad / s, the ratio (η ^* ratio) was calculated. The ultimate viscosity [η] means a value measured in decalin at 135 ° C.

≪Requirements (v) ≫
_{The requirement (v) is the number of long chain branches (LCB 1000C} ) per 1000 carbon atoms obtained by using 3D-GPC of the above copolymer (A) and the natural logarithm [Ln] of the weight average molecular weight (Mw). (Mw)] specifies that the above equation (3) is satisfied. The above formula (3) of the requirement (v) is preferably the following formula (3').
LCB _1000C ≤ 1-0.071 × Ln (Mw)… (3')

The upper limit of the long chain branching 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 branches contained is small, the curing characteristics are excellent when cross-linking is performed using a peroxide, and the heat aging resistance is excellent. A rubber shaker can be obtained.

Here, Mw and the number of long-chain branches per 1000 carbon atoms (LCB _1000C ) can be obtained by a structural analysis method using 3D-GPC. Specifically, in the present specification, it is obtained as follows.
Using a 3D-high temperature GPC device PL-GPC220 (manufactured by Polymer Laboratories), the absolute molecular weight distribution was determined, and at the same time, the ultimate viscosity was determined with a viscometer. The main measurement conditions are as follows.
Detector: Built-in differential refractometer / GPC device
2-angle light scattering photometer PD2040 type (manufactured by Precison Detectors)
Bridge type viscometer PL-BV400 type (manufactured by Polymer Laboratories)
Column: TSKgel GMH _HR -H (S) HT x 2 + TSKgel GMH _HR -M (S) x 1
(In each case, inner diameter 7.8 mmφ x length 300 mm)
Temperature: 140 ℃
Mobile phase: 1,2,4-trichlorobenzene (containing 0.025% BHT)
Injection volume: 0.5 mL
Sample concentration: ca 1.5 mg / mL
Sample filtration: Filtration with a 1.0 μm sintered filter

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

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

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 relational expression of [η] = KM ^v ; v = 0.725 was applied.
Further, each average value was calculated as g'from the following formulas (v-2), (v-3), and (v-4). The Trendline, which was assumed to have only short-chain branches, was determined for each sample.

Further, using g'w, the number of branch points BrNo per molecular chain, the number of long chain branching LCB _1000C per 1000 carbons, and the degree of branching λ per unit molecular weight were calculated. The following formulas (v-5) of Zimm-Stockmayer were used for BrNo calculation, and the following formulas (v-6) and (v-7) were used for the calculation of _{LCB 1000C and λ.} g is a long-chain branching parameter obtained from the radius of inertia Rg, and the following simple correlation is made with g'determined from the ultimate viscosity. Various values of ε in the formula have been proposed depending on the shape of the molecule. Here, the calculation was performed on the assumption 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 = BrNo / M ... (V-6)
LCB _1000C = λ × 14000… (V-7)
In the formula (V-7), "14000" represents the molecular weight of 1000 pieces in _{methylene (CH 2) units.}

The ultimate viscosity [η] of the 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. Is.
The weight average molecular weight (Mw) of the copolymer (A) is preferably 10,000 to 600,000, more preferably 30,000 to 500,000, still more preferably 50,000 to 400,000. be.

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

As described above, the copolymer (A) further contains structural units derived from the non-conjugated polyene (a4) in addition to the structural units derived from the above (a1), (a2) and (a3). , 0% by weight to 20% by weight (however, the total weight fraction of (a1), (a2), (a3), and (a4) is 100% by weight). In this case, it is preferable to satisfy the requirement (vi) below.

≪Requirements (vi) ≫
The weight average molecular weight (Mw) of the copolymer (A), the weight fraction of the constituent unit derived from the non-conjugated polyene (a3) (weight fraction (% by weight) of (a3)), and the non-conjugated polyene (a3). The weight fraction of the structural unit derived from a4) (the weight fraction (% by weight) of (a4)), the molecular weight of the non-conjugated polyene (a3) (the molecular weight of (a3)), and the non-conjugated polyene (a4). The molecular weight (molecular weight of (a4)) satisfies the following formula (4).
4.5 ≤ Mw x {(weight fraction of (a3) / 100 / molecular weight of (a3)) + (weight fraction of (a4) / 100 / molecular weight of (a4))} ≤ 45 ... (4)
In the formula (4), the content of the unconjugated diene (the sum of (a3) and (a4)) in one molecule of the copolymer is specified.

When the copolymer (A) containing the structural unit derived from the above (a4) satisfies the formula (4), a vibration-proof rubber having excellent mechanical properties and heat-resistant aging properties can be obtained.
The requirement (vi) is not satisfied, and “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, that is, if the content of non-conjugated diene is too small, sufficient cross-linking may not be performed and appropriate mechanical properties may not be obtained, and if the value is too high, that is, non-conjugated diene. If the content of the conjugated diene is too large, the cross-linking may be excessive and the mechanical properties may be deteriorated, and the heat aging property may be further deteriorated.

≪Requirements (vii) ≫
^{The copolymer (A) is not particularly limited, but is a 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 η ^* ₍ ω _{= 10)} (Pa · sec) at frequency ω = 10 rad / s, and apparent iodine value derived from unconjugated polyene (a3) However, it is preferable that the following formula (5) is satisfied.
Log {η ^* ₍ ω _{= 0.01)} } / Log {η ^* ₍ ω _{= 10)} } ≤0.0753 × {apparent iodine value derived from non-conjugated polyene (a3)} +1.42… (5)

Here, the complex viscosity η ^* ₍ ω _{= 0.01)} and the complex viscosity η ^* ₍ ω _{= 10)} are measured as the ^{complex viscosity η *} ₍ ω _{= 0.1)} and the complex viscosity η ^* ₍ ω _{= 100)} in the requirement (iv). Other than the frequency, it is obtained in the same way. The apparent iodine value derived from the non-conjugated polyene (a3) is calculated by the following formula.
Apparent iodine value derived from (a3) = weight fraction of (a3) x 253.81 / molecular weight of (A3)

In the above formula (5), the left side represents the shear rate dependence which is an index of the long chain branching amount, and the right side represents the index of the content of the non-conjugated polyene (a3) which is not consumed as a long chain branching at the time of polymerization. When the copolymer (A) satisfies the above formula (5), the degree of long chain branching is not too high, which 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 the long-chain branch is large.

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

Further, the copolymer (A) has a weight average molecular weight per (Mw), the number of structural units derived from nonconjugated polyene _(a3) (n a3) is preferably 6 or more, more preferably 6 or 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 non-conjugated polyene (a3) such as VNB, has a small long-chain branching content, and is crosslinked using a peroxide. Excellent curing characteristics, good moldability, excellent balance of physical properties such as mechanical properties, and particularly excellent heat aging resistance.

Further, the copolymer (A), per weight average molecular weight (Mw), the number of structural units derived from nonconjugated polyene _(a4) (n a4) is preferably 29 or less, more preferably 10 Hereinafter, the number is more preferably less than one.

In such a copolymer (A), the content of the structural unit derived from the non-conjugated polyene (a4) such as ENB is suppressed within a range that does not impair the object of the present invention, and post-crosslinking is unlikely to occur, which is sufficient. Has excellent heat resistance and aging properties.

_{Here, the number of structural units derived from the non-conjugated polyene (a3} ) or the number of structural units derived from the non-conjugated polyene (a4) per weight average molecular weight (Mw) of the copolymer (A). (N _a4 ) is the molecular weight of the non-conjugated polyene (a3) or (a4) and the weight fraction of the structural unit derived from the non-conjugated polyene (a3) or (a4) in the copolymer ((a3) or (a4). It can be calculated by the following formula from the weight fraction (% by weight) of a4) and the weight average molecular weight (Mw) of the copolymer (A).
(N _a3 ) = (Mw) × {Molecular weight fraction of (a3) / 100} / Molecular weight of non-conjugated polyene (a3) (n _a4 ) = (Mw) × {Weight fraction of (a4) / 100} / Molecular weight of non-conjugated 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 long-chain branching content, excellent curing characteristics when cross-linking is performed using a peroxide, good moldability, mechanical characteristics, etc. It is preferable because it has an excellent balance of physical properties, is less likely to cause post-crosslinking, and is particularly excellent in heat aging resistance.

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

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

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

In the 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 non-conjugated diene, and an anionic ligand. Alternatively, it indicates a neutral ligand that can be coordinated with a lone electron pair, j indicates 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 represent a cyclopentadienyl group or a substituted cyclopentadienyl group capable of forming a sandwich structure with M.

In the 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, 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 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, and more preferably a zirconium atom or a hafnium atom. When it is desired to obtain the copolymer (A) having a smaller amount of long-chain branching, a zirconium atom is more preferable.

Q indicates a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or unconjugated diene, an anionic ligand or a neutral ligand capable of coordinating with a lone electron pair, preferably Q , Halogen atoms, hydrocarbon groups with 1 to 10 carbon atoms, neutral, conjugated or unconjugated dienes with 10 or less carbon atoms, anionic ligands, and neutral ligands that can be coordinated with lone electron pairs. To be elected. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable.

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 and benzyl group, and methyl group, ethyl group and benzyl group are preferable.

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 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 eta ^4-1,4-bis (trimethylsilyl) -1,3-butadiene and the like.

Specific examples of the anion ligand include an alkoxy group such as methoxy, t-butoxy and phenoxy, a carboxylate group such as acetate and benzoate, and a sulfonate group such as mesylate and tosylate.

Specific examples of neutral ligands that can be coordinated with lone electron pairs include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, or tetrahydrofuran, diethyl ether, dioxane, 1,2-. Examples include ethers such as dimethoxyethane.

The copolymer (A) is more preferably 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].

In the formula [A3], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² are independently heteroatoms other than hydrogen atom, hydrocarbon group, silicon-containing group or silicon-containing group, respectively. It indicates an atom-containing group, and ^{two adjacent groups of R 1 to} R ⁴ may be bonded to each other to form a ring.

The hydrocarbon group is preferably a hydrocarbon group having 1 to 20 carbon atoms, for example, an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. ) Group or a substituted aryl group and the like. More specifically, methyl group, ethyl group, n-propyl group, isopropyl group, allyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, amyl group, n-pentyl Group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl Group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group, cyclopentyl group, cyclohexyl Group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xsilyl group, isopropylphenyl group, t-butylphenyl group, naphthyl group, Examples thereof include biphenyl group, terphenyl group, phenanthryl group, anthracenyl group, benzyl group and cumyl group, which include oxygen-containing groups such as methoxy group, ethoxy group and phenoxy group, nitro group, cyano group and N-methylamino group. Propyl groups containing nitrogen-containing groups such as N, N-dimethylamino group and N-phenylamino group, boron-containing groups such as bolantriyl group and diboranyl group, and sulfur-containing groups such as sulfonyl group and sulphenyl group are also listed as hydrocarbon groups. Be done.

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

Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, and a hydrocarbon-substituted siloxy group. 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). ) Cyril group and the like can be mentioned.

R ⁶ and R ¹¹ are the same atom or the same group selected from heteroatom-containing groups other than hydrogen atom, hydrocarbon group, silicon-containing group and silicon-containing group, and R ⁷ and R ¹⁰ are hydrogen atom and hydrocarbon. The same atom or the same group selected from a group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group, and R ⁶ and R ⁷ may be bonded to each other to form a ring, and R ¹⁰ and R ¹¹ may be coupled 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. ^{Both the zirconium atom and the hafnium atom are suitable as M 1} of the metallocene compound of the above formula [A3], but from the viewpoint that the compound having the zirconium atom produces the copolymer (A) having a small amount of long-chain branching. More preferred.

Y ¹ represents a carbon atom or a silicon atom.
Q is a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or unconjugated diene having 4 to 20 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair. Shown, j indicates 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, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.

As the hydrocarbon group, a hydrocarbon group having 1 to 10 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a 2-methylpropyl group, and a 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, Examples thereof include 1,1-dimethylbutyl group, 1,1,3-trimethylbutyl group, neopentyl group, cyclohexylmethyl group, cyclohexyl group, 1-methyl-1-cyclohexyl group, benzyl group, and the like, preferably methyl group and ethyl. Group, benzyl group.

As the neutral conjugated or unconjugated diene having 4 to 20 carbon atoms, a neutral conjugated or unconjugated diene having 4 to 10 carbon atoms is preferable. 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 eta ^4-1,4-bis (trimethylsilyl) -1,3-butadiene and the like.

Specific examples of the anion ligand include an alkoxy group such as methoxy, t-butoxy and phenoxy, a carboxylate group such as acetate and benzoate, and a sulfonate group such as mesylate and tosylate.

Specific examples of neutral ligands that can be coordinated with lone electron pairs include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, or tetrahydrofuran, diethyl ether, dioxane, 1,2-. Examples include ethers such as dimethoxyethane.

^{Examples of the cyclopentadienyl group having substituents R 1} to R ⁴ in the above formula [A3] include an unsubstituted cyclopentadienyl group in which R ¹ to R ⁴ are hydrogen atoms, and 3-t-butylcyclopentadienyl. Group, 3-methylcyclopentadienyl group, 3-trimethylsilylcyclopentadienyl group, 3-phenylcyclopentadienyl group, 3-adamantylcyclopentadienyl group, 3-amylcyclopentadienyl group, 3-cyclohexyl 3-T-unisubstituted 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-dimethylcyclopentadienyl group, 3-phenyl-5-methylcyclopentadienyl group, 3 Examples thereof include, but are not limited to, a 3,5-position disubstituted cyclopentadienyl group such as a −trimethylsilyl-5-methylcyclopentadienyl group. From the viewpoint of ease of synthesis of the metallocene compound, production cost, and copolymerization ability of the non-conjugated polyene, a ^{cyclopentadienyl group which is unsubstituted (R 1 to} R ⁴ are hydrogen atoms) is preferable.

As a fluorenyl group having ^{substituents R 5} to R ¹² in the formula [A3],
An unsubstituted fluorenyl group in which R ⁵ to R ^{12 are hydrogen atoms,}
2-position, 1-substituted fluorenyl groups such as 2-methylfluorenyl group, 2-t-butylfluorenyl group, 2-phenylfluorenyl group,
4-Methylfluorenyl group, 4-t-butylfluorenyl group, 4-phenylfluorenyl group, etc., 4-position, 1-substituted fluorenyl group,
Alternatively, a 2,7-position or 3,6-position 2-substituted fluorenyl group such as a 2,7-di-t-butylfluorenyl group or a 3,6-di-t-butylfluorenyl group,
2,7-Diphenyl-3,6-di-t-butylfluorenyl group, 2,7-diphenyl-3,6-di-t-butylfluorenyl group, etc. 2,3,6,7-position 4 Substituted fluorenyl group,
^{Alternatively, R 6} and R ⁷ as represented by the following general formulas [V-I] and [V-II] are bonded to each other to form a ring, and R ¹⁰ and R ¹¹ are bonded to each other to form a ring. Examples thereof include, but are not limited to, a 4-substituted fluorenyl group at the 2,3,6,7 position.

In the formulas [V-I] and [V-II], R ⁵ , R ⁸ , R ⁹ , and R ¹² are the same as the definitions in the general formula [A3].
R ^a , R ^b , R ^c , R ^d , R ^e , R ^f , R ^g and R ^h are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and are bonded to each other with adjacent substituents. May form a ring. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an amyl group, and an n-pentyl group. Further, in the formula [V−I], R ^x and R ^y are hydrocarbon groups that may independently have unsaturated bonds having 1 to 3 carbon atoms, respectively, and R ^x is R ^a or R ^c is bonded. The carbon may form a double bond in cooperation with the carbon, and R ^y may form a double bond in cooperation with the carbon to which R ^e or R ^g is bonded, and R ^x and R ^y may form a double bond. Both are preferably saturated or unsaturated hydrocarbon groups having 1 or 2 carbon atoms.

Specific examples of the compound represented by the above general formula [V-I] or [V-II] include an octamethyloctahydrodibenzofluorenyl group represented by the formula [V-III] and a formula [V-]. Tetramethyldodecahydrodibenzofluorenyl group represented by IV], octamethyltetrahydrodicyclopentafluorenyl group represented by formula [V-V], hexamethyldihydro represented by formula [V-VI] Examples thereof include a dicyclopentafluorenyl group and a b, h-dibenzofluorenyl group represented by the formula [V-VII].

All of the metallocene compounds represented by the above general formula [A3] containing these fluorenyl groups are excellent in the copolymerization ability of non-conjugated polyenes, but when Y ¹ is a silicon atom, the 2,7-position 2-substituted fluorenyl group, A transition metal having a 2,3,6-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 [VI]. The compounds are particularly good. When Y is a carbon atom, ^{an unsubstituted fluorenyl group in which R 5} to R ¹² are hydrogen atoms, a 2, 3, 6-position 2-substituted fluorenyl group, a 2, 3, 6, 7-position 4-substituted fluorenyl group, the above general formula [V A metallocene compound having a 4-substituted fluorenyl group at the 2,3,6,7-position 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 R ⁵ to R ¹² are all hydrogen atoms, R ¹³ and R ¹⁴ are methyl. Selected from groups other than groups, butyl groups, phenyl groups, silicon-substituted phenyl groups, cyclohexyl groups, and benzyl groups;
If Y ¹ is a silicon atom, R ⁶ and R ¹¹ are both t-butyl groups, and R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹² are not t-butyl groups, then R ¹³ And R ¹⁴ are selected from groups other than benzyl and silicon-substituted phenyl groups;
When Y ¹ is a carbon atom and R ⁵ to R ¹² are all hydrogen atoms, R ¹³ and R ¹⁴ are methyl group, isopropyl group, t-butyl group, isobutyl group, phenyl group, pt-butylphenyl. Selected from groups other than groups, pn-butylphenyl groups, silicon-substituted phenyl groups, 4-biphenyl groups, p-tolyl groups, naphthyl groups, benzyl groups, cyclopentyl groups, cyclohexyl groups, and xsilyl groups;
Y ¹ is a carbon atom and R ⁶ and R ¹¹ are common groups selected from t-butyl, methyl or phenyl groups, with R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹² . If a different group or atom, R ^13, R ¹⁴ is selected from methyl, phenyl, p-t-butylphenyl group, p-n-butylphenyl group, silicon-substituted phenyl group, a group other than a benzyl group ;
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 groups from ^{R 6 or} When it is an atom, R ¹³ and R ¹⁴ are selected from groups other than methyl and phenyl groups;
If 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, then R ¹³ and R ¹⁴ are It is preferably selected from groups other than the methyl group and the 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 by this.
As a specific example of the metallocene compound represented by the above general formula [A3],
If Y is a silicon atom
Diphenylcilylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Diphenylcilylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Diphenylcilylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Diphenylcilylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Diphenylcilylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Diphenylcilylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Diphenylcilylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Diphenylcilylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Diphenylcilylene (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 thereof include di (m-tolyl) silylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride and the like.

If 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) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Diphenylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Diphenylmethylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Diphenylmethylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (pt-butylphenyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (pt-butylphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (pt-butylphenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (pt-butylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (pt-butylphenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (pt-butylphenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (pt-butylphenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (pt-butylphenyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,

Di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Examples thereof include di (2-naphthyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride.

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

Examples of the metallocene compound represented by the formula [A3] include, in addition to the above-exemplified compound, a compound in which the zirconium atom of the above-exemplified compound is replaced 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-ethylcyclopenta Examples thereof include, but are limited to, a compound in which a dienyl group or a 3,5-dimethylcyclopentadienyl group is replaced, a compound in which the chlorine atom of the above compound is replaced with a methyl group or a benzyl group, or a combination thereof. It's 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 polymer (A) tends to have a higher molecular weight. This is because (1) the Lewis acidity of the hafnium atom is smaller and the reactivity is lower than that of the zirconium atom and the titanium atom, and (2) the bond energy between the hafnium atom and the carbon atom is lower than that of the zirconium atom and the titanium atom. Is due to the fact that it suppresses the chain transfer reaction (including the β-hydrogen elimination reaction) of the 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 copolymer (A), is produced by any method without particular limitation. be able to. For example, J. Organomet. Chem. , 63,509 (1996), WO2005 / 100410, WO2006 / 123759, WO01 / 27124, JP2004-168744, JP2004-175759, which are publications related to the application by the present applicant. It can be manufactured in accordance with the methods described in Japanese Patent Application Laid-Open No. 2000-212194 and the like.

≪Catalyst containing metallocene compound≫
Examples of the polymerization catalyst that can be suitably used for the production of the above-mentioned copolymer (A) include those containing any of the above-mentioned [A1], [A2] or [A3] metallocene compounds and capable of copolymerizing a monomer. Can be mentioned.

Preferably,
(A) The metallocene compound represented by the general formula [A1], [A2] or [A3], and
(B) At least one selected from (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) a compound that reacts with the metallocene compound (a) to form an ion pair. (Hereinafter, also referred to as "ionized ionic compound") and
Further if necessary
(C) A catalyst composed of a particulate carrier (hereinafter, also referred to as “metallocene catalyst”) can be mentioned. Hereinafter, the components (b) and (c) will be specifically described.

(B-1) Organometallic compound Examples of the organometallic compound (b-1) include groups 1 and 2 and groups 12 and 13 of the periodic table represented by the following general formulas [VII] to [IX]. Organometallic compounds of.
_{^{· R a m Al (OR b}} ) n H p X q ... [VII]
In formula [VII], ^Ra and R ^b may be the same or different from each other and represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, where X represents a halogen atom and m. Is 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.

Examples of such organic aluminum compounds include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and trin-octylaluminum, tricycloalkylaluminum, isobutylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, and ethyl. Examples thereof include aluminum sesquichloride, methylaluminum dichloride, dimethylaluminum chloride, and diisobutylaluminum hydride.
・ M ² AlR ^a ₄ … [VIII]
In formula [VIII], M ² represents Li, Na or K, and ^Ra is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.

Examples of the complex alkylated product of such a Group 1 metal of the periodic table 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 may be the same or different from each other, and represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ³ is Mg, Zn or Cd. Is.

Examples of the compound having such a group 2 or 12 metal of the periodic table and two hydrocarbon groups include dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium, dimethyl zinc, diethyl zinc, and diphenyl zinc. Examples thereof include di-n-propyl zinc, diisopropyl zinc, di-n-butyl zinc, diisobutyl zinc, bis (pentafluorophenyl) zinc, dimethyl gadomium and diethyl cadmium.

Among the above-mentioned organometallic compounds (b-1), organoaluminum compounds such as triethylaluminum, triisobutylaluminum, and trin-octylaluminum are preferable. Further, such an organometallic compound (b-1) may be used alone or in combination of two or more.

(B-2) Organoaluminium oxy compound The organoaluminum 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.

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 water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method in which an organic aluminum compound such as trialkylaluminum is added to the hydrocarbon medium suspension of the above, and adsorbed water or water of crystallization is reacted with the organic aluminum compound.
(2) A method in which water, ice or water vapor is allowed to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

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

Examples of the organoaluminum compound used when preparing alminoxane include organoaluminum compounds similar to those exemplified as the organoaluminum compound represented by the above formula [VII], and among them, trialkylaluminum and tricycloalkyl. Aluminum is preferable, and trimethylaluminum and triisobutylaluminum are particularly preferable. The above-mentioned organoaluminum compounds can be used alone or in combination of two or more.

Further, in the benzene-insoluble organic aluminum oxy compound which is one aspect of the organic aluminum oxy compound (b-2), the Al component dissolved in benzene at 60 ° C. is usually 10 weight by weight based on 100% by weight of benzene in terms of Al atom. % Or less, preferably 5% by weight or less, particularly preferably 2% by weight or less, that is, those that are insoluble or sparingly soluble in benzene are preferable.

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

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

The organoaluminum oxy compound containing boron represented by the general formula [X] comprises an alkylboronic acid represented by the following general formula [XI] and an organoaluminum compound in an inert solvent under an inert gas atmosphere. It can be produced by reacting at a temperature of −80 ° 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 general formula [XI] include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, and cyclohexyl. Examples thereof include boronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, and 3,5-bis (trifluoromethyl) phenylboronic acid. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferable. These can be used alone or in combination of two or more.

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

(B-3) Ionic Ionic Compound Examples of the ionized ionic compound (b-3) include JP-A-1-501950, JP-A-1-502306, JP-A-3-179005, and JP-A-3- Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-179006, JP-A-3-207703, JP-A-3-207704, USP-5321106 and the like. Further, heteropoly compounds and isopoly compounds can also be mentioned. Such an ionized ionic compound (b-3) can be used alone or in combination of two or more.

Examples of the Lewis acid include compounds represented by BR ₃ (R is a phenyl group or fluorine which may have a substituent such as a fluorine, a methyl group or a trifluoromethyl group), and examples thereof include trifluoro. Boron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) Examples thereof include boron, tris (o-tolyl) boron, and tris (3,5-dimethylphenyl) boron.
Examples of the ionic compound include compounds represented by the following general formula [XII].

In the formula [XII], ^examples of R 1+ include H ⁺ , carbonium cations, oxonium cations, ammonium cations, phosphonium cations, cycloheptilylienyl cations, and ferrosenium cations having transition metals. R ^{2 to} R ⁵ may be the same or different from each other and are organic groups, preferably aryl groups or substituted aryl groups.

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

Examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium 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;
Examples thereof include dialkylammonium cations such as di (isopropyl) ammonium cations and dicyclohexylammonium cations.

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

As R ¹⁺ , carbonium cations, ammonium cations and the like are preferable, and triphenylcarbonium cations, N, N-dimethylanilinium cations and N, N-diethylanilinium cations are particularly preferable.

Moreover, as the ionic compound, a trialkyl-substituted ammonium salt, an N, N-dialkylanilinium salt, a dialkylammonium salt, a triarylphosphonium salt and the like can also be mentioned.

Examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, and the like. 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) boron and the like.

Examples of the N, N-dialkylanilinium salt include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N, 2,4,6-penta. Examples thereof include methylanilinium tetra (phenyl) boron.

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

Further, as the above-mentioned ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrosenium tetra (pentafluorophenyl) borate, triphenylcarbenium Examples thereof include a pentaphenylcyclopentadienyl complex, an N, N-diethylanilinium pentaphenylcyclopentadienyl complex, and a boron compound represented by the following formula [XIII] or [XIV]. Here, in the formula, Et represents an ethyl group.

Examples of the borane compound include decaborane;
Bis [tri (n-butyl) ammonium] nonabolate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate , Anionic salts such as bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachloro dodecaborate;
Metal borane anions such as tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III) Examples include salt.

Examples of the carborane compound include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, and dodecahydride-1. -Methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane, un 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-carbadodecaborate, tri (n-butyl) ammonium-1-trimethylsilyl-1-carbadecaboleate, tri (n-butyl) Ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium-6-carbadecaboleate, tri (n-butyl) ammonium-7-carbundecaborate, tri (n-butyl) ammonium-7,8- Dicarbundecaborate, tri (n-butyl) ammonium-2,9-dicarbundecaborate, tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarbundecaborate, tri (n-butyl) ) Ammonium undecahydride-8-ethyl-7,9-dicarbundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbundecaborate, tri (n-butyl) ammonium Undeca Hydlide-8-allyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecaborate Anion salts such as hydride-4,6-dibromo-7-carbundecaborate;
Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonabolate) cobalt salt (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) Iron salt (III), tri (n-butyl) ammonium bis (Undecahydride-7,8-dicarbaundecaborate) Cobalate (III), tri (n-butyl) ammonium bis (Undecahydride-7) , 8-Dicarbaundecabolate) Nikrate (III), Tri (n-butyl) ammonium bis (Undecahydrate-7,8-dicarbaundecaborate) Copper salt (III), Tri (n-butyl) Ammonium bis (Undecahydride-7,8-dicarbundecaborate) Hydrochloride (III), Tri (n-butyl) ammonium bis (Nonahydrate-7,8-dimethyl-7,8-dicarbaundecaborate) Iron salt (III), tri (n-butyl) ammonium bis (nonahydrate-7,8-dimethyl-7,8-dicarbundecaborate) chromate (III), tri (n-butyl) ammonium bis (nonahydrate) Tribromooctahydride-7,8-dicarbaundecabolate) cobaltate (III), tris [tri (n-butyl) ammonium] bis (undecahydrate-7-carbaundecaborate) chromate (III) , Bis [tri (n-butyl) ammonium] bis (Undecahydride-7-carbaundecarbolate) manganate (IV), bis [tri (n-butyl) ammonium] bis (Undecahydride-7-cal) Bound decaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbundecaborate) nickate (IV) and other salts of metal carborane anions. Be done.

The heteropoly compound comprises an atom selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, limvanadic acid, germanovanadic acid, arsenic vanadic acid, linniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdenum acid, germanomolybdic acid, arsenic molybdenum acid, tin molybdenum acid, phosphorus. Tungsonic acid, germanotungsic acid, tin tungsic acid, phosphoribdovanadic acid, lintangstovanadic acid, germanotangstovanadic acid, lysmolibdotangstovanadic acid, germanomoribdotangstovanadic acid, phosphoribdotungstate , Phosphoribdoniobic acids, and salts of these acids, such as Group 1 or Group 2 metals of the Periodic Table, specifically lithium, sodium, potassium, rubidium, cesium, berylium, magnesium, calcium, strontium, barium. , And organic salts such as triphenylethyl salt can be used, but this is not the case.

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

In the present invention, as the catalyst, the metallocene compound (a), an organometallic compound such as triisobutylaluminum (b-1), an organoaluminum oxy compound such as methylaluminoxane (b-2), and triphenylcarbenium tetrakis ( When a metallocene catalyst containing an ionized 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) used as required is an inorganic compound or an organic compound, which is a solid in the form of granules or fine particles.

As the 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 a composite or mixture containing these, for example, natural or natural. Use synthetic zeolite, SiO _2- MgO, 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, etc. Can be done. Of these, those _{containing SiO 2} and / or Al ₂ O ₃ as main components are preferable. Although the properties of such a porous oxide differ depending on the type and production method, 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. It is desirable that ^{the pore volume is in the range of 2} / g, preferably 100 to 700 m ² / g, and the pore volume is in ^{the range of 0.3 to 3.0 cm 3 / g.} Such a porous oxide is used by firing at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

As the inorganic halide, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr _{2 and the} like are used. The inorganic halide may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a product obtained by dissolving an inorganic halide in a solvent such as alcohol and then precipitating it in the form of fine particles with a precipitant.

The clay is usually composed mainly of clay minerals. Further, the ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other with a weak bonding force, and the contained ions can be exchanged. Most clay minerals are ion-exchange layered compounds. Further, as these clays, clay minerals, and ion-exchange layered compounds, not only naturally produced ones but also artificial synthetic compounds can be used.

Further, as clay, clay mineral or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as _{hexagonal fine packing type, antimony type, CdCl 2} type and CdI _{2 type can be used.} It can be exemplified. Such clays and clay minerals include kaolin, bentonite, knot clay, gailome clay, alophen, hisingel stone, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudei stone group, parigolskite, kaolinite, nacrite, and dicite. , and the like halloysite, the ion-exchange layered _{compounds, α-Zr (HAsO 4)} 2 · H 2 O, α-Zr (HPO 4) 2, α-Zr (KPO 4) 2 · 3H 2 O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ · H ₂ O, α-Sn (HPO ₄ ) ₂ · H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄₎ ) ₂ , γ-Ti (NH ₄ PO ₄ ) ₂ , H ₂ O and other polyvalent metals such as crystalline acid salts.

Such clays, clay minerals or ion-exchange layered compounds preferably have a pore volume of 0.1 cc / g or more with a radius of 20 Å or more measured by a mercury intrusion method, preferably 0.3 to 5 cc / g. Especially preferable. Here, the pore volume is measured in the range of a pore radius of 20 to 30,000 Å by a mercury intrusion method using a mercury porosimeter.

When a carrier having 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.
It is also preferable to chemically treat the clay and clay mineral used in the present invention. As the chemical treatment, any of a surface treatment for removing impurities adhering to the surface, a 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, and organic substance treatment. The acid treatment removes impurities on the surface and increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkaline treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. Further, in the salt treatment and the organic substance treatment, an ion complex, a molecular complex, an organic derivative and the like can be formed, and the surface area and the interlayer distance can be changed.

The ion-exchangeable layered compound used in the present invention may be a layered compound in a state in which the layers are expanded by utilizing the ion exchange property and exchanging the exchangeable ions between the layers with another large bulky ion. .. Such bulky ions play a supporting role in supporting the layered structure, and are usually called pillars. Further, the introduction of another substance between the layers of the layered compound in this way is called intercalation. Guest compounds to be intercalated include cationic inorganic compounds such as _{TiCl 4} , ZrCl _4, and metal alkoxides such as _{Ti (OR) 4} , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) _3. R is a hydrocarbon group, etc.), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ and other metal hydroxide ions And so on. These compounds can be used alone or in combination of two or more. Further, when these compounds are intercalated, a polymerization obtained by hydrolyzing a metal alkoxide (R is a hydrocarbon group or the like) such as _{Si (OR) 4} , Al (OR) ₃ , and Ge (OR) _{4 is obtained.} A colloidal inorganic compound such as a substance or SiO _{2 can coexist.} Examples of pillars include oxides produced by intercalating the metal hydroxide ions between layers and then heating and dehydrating them.

The clay, clay mineral, and ion-exchange layered compound used in the present invention may be used as they are, or may be used after being subjected to a treatment such as ball milling or sieving. Further, it may be used after newly adding and adsorbing water or heat dehydration treatment. Further, it may be used alone or in combination of two or more.

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

The metallocene catalyst used in the present invention is at least selected from the metallocene compound (a), (b-1) organometallic compound, (b-2) organoaluminum oxy compound, and (b-3) ionized ionic compound. It is also possible to include a specific organic compound component (d) as described later, if necessary, together with one kind of compound (b) and a carrier (c) used as needed.

(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, if necessary. Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, sulfonates and the like.

<< Production method of copolymer (A) >>
The copolymer (A) is composed of ethylene (a1), an α-olefin (a2) having 3 to 20 carbon atoms, a non-conjugated polyene (a3), and, if necessary, a non-conjugated polyene (a4). Can be produced by copolymerizing the monomers.

When copolymerizing such a monomer, the method of use and the order of addition of each component constituting the above-mentioned polymerization catalyst are arbitrarily selected, and the following methods (1) to (5) are exemplified.
(1) A method of adding the metallocene compound (a) alone to a polymerizer.
(2) A method of adding the metallocene compound (a) and the compound (b) to the polymerizer in an arbitrary order.
(3) A method of adding a catalyst component in which a metallocene compound (a) is supported on a carrier (c) and a compound (b) to a polymerizer in an arbitrary order.
(4) A method of adding a catalyst component in which compound (b) is supported on a carrier (c) and a metallocene compound (a) to a polymerizer in an arbitrary order.
(5) A method of adding a catalyst component in which a metallocene compound (a) and a compound (b) are supported on a carrier (c) to a polymerizer.

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

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

The above-mentioned copolymer (A) can be preferably obtained by copolymerizing a monomer in the presence of the above-mentioned metallocene catalyst.
When polymerizing an olefin using 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 reaction volume. It is used in such an amount.

Compound (b-1) usually has a molar ratio [(b-1) / M] of compound (b-1) to all transition metal atoms (M) in the metallocene compound (a) of 0.01 to. It is used in an amount such that it is 50,000, preferably 0.05 to 10000. 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 in the compound (b-2). It is used in an amount of up to 50,000, preferably 20 to 10000. 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 1 to 20. Is used in an amount such that 1 to 15.

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

In the step of obtaining the polymerization reaction solution, an aliphatic hydrocarbon is used as a polymerization solvent, and the metallocene catalyst, preferably ^{R 13} and R ¹⁴ bonded to ^{Y 1} in the general formula [A3] are phenyl groups, or , A phenyl group substituted with an alkyl group or a halogen group, and ethylene (a1) and 3 to 20 carbon atoms in the presence of a metallocene catalyst containing a transition metal compound in which ^{R 7} and R ^{10 have an alkyl substituent.} This is a step of copolymerizing a monomer composed of α-olefin (a2), non-conjugated polyene (a3) and, if necessary, non-conjugated polyene (a4) to obtain a polymerization reaction solution of the copolymer (A). ..

If 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, so that the solution may not be agitated uniformly 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. Examples thereof include aromatic hydrocarbons such as, ethylene chloride, chlorobenzene, and halogenated hydrocarbons such as dichloromethane, and one type alone or two or more types can be used in combination. Moreover, the olefin itself can also be used as a solvent. Of these, hexane is preferable from the viewpoint of separation and purification from the obtained copolymer (A).

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

The polymerization pressure is usually under the condition of normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out by any of batch type, semi-continuous type and continuous type. Further, it is also possible to carry out the polymerization in two or more stages having different reaction conditions. Of these, in the present invention, it is preferable to adopt a method in which monomers are continuously supplied to a reactor to carry out copolymerization.

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

The molecular weight of the obtained copolymer (A) can also be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can be adjusted according to the amount of compound (b) used. Specific examples thereof include triisobutylaluminum, methylaluminoxane, and diethylzinc. When hydrogen is added, the amount thereof is appropriately about 0.001 to 100 NL per 1 kg of olefin.

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

The amount of the non-conjugated polyene (a3) charged is usually 0. It is 07 to 10% by weight, preferably 0.1% by weight to 8.0% by weight, and more preferably 0.5% by weight to 5.0% by weight.

<Graft-modified ethylene / α-olefin copolymer (B)>
The copolymer (B) used in the present invention is a copolymer obtained by graft-modifying an ethylene / α-olefin copolymer with an unsaturated carboxylic acid or a derivative thereof.

Density of the copolymer (B) is preferably 860 kg / m ³ or more 880 kg / m less than ^3, more preferably 860~875kg / m ^3, more preferably a 865~875kg / m ^3. When the density of the copolymer (B) is within the above range, the composition of the present invention has an excellent balance between flexibility and physical properties.

The copolymer (B) has a melting point of 20 ° C. or higher and lower than 60 ° C. measured by differential scanning calorimetry (DSC), or no peak indicating the melting point is observed by differential scanning calorimetry (DSC). preferable. When the copolymer (B) satisfies this condition, the dispersibility in rubber during kneading molding is excellent. When a peak indicating a melting point is observed by differential scanning calorimetry (DSC), the melting point is more preferably 30 ° C. or higher and lower than 60 ° C., and further preferably 40 ° C. or higher and lower than 60 ° C.

The graft ratio in the copolymer (B) is preferably 0.01 to 10 as the amount of the grafted unsaturated carboxylic acid or its derivative with respect to 100 parts by weight of the ethylene / α-olefin copolymer before graft modification. By weight, more preferably 0.1 to 5% by weight. When the graft ratio is within the above range, the composition of the present invention has good mechanical properties.

The ethylene / α-olefin copolymer used in the production of the copolymer (B) is a unit derived from ethylene and a unit derived from α-olefin having 3 or more carbon atoms, preferably 3 to 20 carbon atoms. It is a copolymer containing and, and may be a random copolymer or a block copolymer.

Specific examples of the α-olefin include propylene, 1-butene, 4-methylpentene-1, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-. Dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptene, 1-nonadecene, 1-eicosene, 9-methyldecene-1, 11-methyldodecene-1, 12-ethyltetradecene-1, etc. Can be mentioned. Of these, propylene, 1-butene, 4-methylpentene-1, 1-hexene and 1-octene are preferable, and propylene is particularly preferable. These α-olefins may be used alone or in combination of two or more.

The content of the structural unit derived from ethylene in the ethylene / α-olefin copolymer is usually 50.0 mol% or more and less than 100 mol% with respect to the total structural unit contained in the ethylene / α-olefin copolymer. It is preferably 80.0 to 99.5 mol%, more preferably 90.0 to 99.0 mol%.

The density of the ethylene / α-olefin copolymer is preferably such that the density of the graft-modified ethylene / α-olefin copolymer (B) obtained by graft-modifying it is within the above range. Specifically, it is 850 to 880 kg / m ³ , more preferably 855 to 875 kg / m ³ .

The melting point of the ethylene / α-olefin copolymer is preferably such that the melting point of the graft-modified ethylene / α-olefin copolymer (B) obtained by graft-modifying it satisfies the above conditions. Specifically, the melting point measured by differential scanning calorimetry (DSC) is 20 to 70 ° C., or no peak indicating the melting point is observed by differential scanning calorimetry (DSC), which is more preferable. The melting point measured by caloric analysis (DSC) is 30-60 ° C., or no peak indicating the melting point is observed by differential scanning calorimetry (DSC).

The melt flow rate (MFR; ASTM D 1238, 190 ° C., 2.16 kg load) of the ethylene / α-olefin copolymer is preferably 0.1 to 100 g / 10 minutes, more preferably 0.2 to 50 g / 10. Minutes, more preferably 0.3 to 20 g / 10 minutes.

When a copolymer (B) obtained by graft-modifying an ethylene / α-olefin copolymer having a density, an ethylene content and an MFR in the above ranges is used, the balance between the processability of the composition and the rubber elasticity is good. become.

Examples of the unsaturated carboxylic acid or its derivative used for graft modification of the ethylene / α-olefin copolymer include acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, and methyltetrahydrophthalic acid. Acids, citraconic acid, crotonic acid, isocrotonic acid, endocis-bicyclo [2.2.1] hept-2,3-dicarboxylic acid (nadic acid, trademark), methyl-endosis-bicyclo [2.2.1] hept- Unsaturated carboxylic acids such as 5-ene-2,3-dicarboxylic acid (methylnadic acid, trademark); anhydrides of these unsaturated carboxylic acids; unsaturated carboxylic acid halides, unsaturated carboxylic acid amides, unsaturated carboxylic acids Examples thereof include derivatives such as esters of imide and unsaturated carboxylic acids. More specifically, maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, methyl methacrylate and the like can be mentioned. Among these, acrylic acid, maleic acid, nadic acid, maleic anhydride, nadic acid anhydride, and methyl methacrylate are preferable. The unsaturated carboxylic acid or a derivative thereof may be used alone or in combination of two or more.

The copolymer (B) uses a conventionally known graft modification method for polyolefin, for example, an extruder, or the like to graft an ethylene / α-olefin copolymer to a graft monomer, that is, an unsaturated carboxylic acid or an unsaturated carboxylic acid thereof, without using a solvent. It can be produced by graft-modifying with a derivative. In any of the graft modification methods, it is preferable to carry out the graft reaction in the presence of a radical initiator in order to efficiently carry out the graft copolymerization of the graft monomer.

The radical initiator is preferably used in a proportion of 0.001 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the ethylene / α-olefin copolymer.

As the radical initiator, an organic peroxide, an organic peroxide, an azo compound and the like can be used. More specifically, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (peroxide benzoate) hexin-3,1,4-bis ( t-butylperoxyisopropyl) benzene, lauroyl peroxide, t-butylperacetate, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexin-3,2,5-dimethyl-2,5-di (T-butylperoxy) hexane; t-butylperbenzoate, t-butylperphenylacetate, t-butylperisobutyrate, t-butylper-sec-octate, t-butylperpivarate, cumylperpivarate and t-butylperdiethyl acetate; azobisisobutyronitrile, dimethylazoisobutyrate and the like can be mentioned. Of these, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3,2,5-dimethyl-2,5-di (t) Dialkyl peroxides such as -butylperoxy) hexane and 1,4-bis (t-butylperoxyisopropyl) benzene are preferred.

The reaction temperature of the graft reaction using the radical initiator or the graft reaction performed without using the radical initiator is usually set in the range of 120 to 350 ° C.
The content of the copolymer (B) in the composition of the present invention is 1 to 100 parts by weight, preferably 2 to 50 parts by weight, more preferably 5 to 5 parts by weight, based on 100 parts by weight of the copolymer (A). It is in the range of 40 parts by weight. When the content of the copolymer (B) is within the above range, the effect of improving the dynamic magnification and the compression set is excellent.

<Silica (C)>
The silica (C) used in the present invention is not particularly limited as long as it can be blended with a general rubber composition, and may be surface-treated. By using silica (C), the dynamic magnification and compression set of the obtained vibration-proof rubber can be improved.

The average particle size of the silica (C) is preferably 1 to 50 nm, more preferably 2 to 45 nm, and even more preferably 5 to 40 nm. When the average particle size is within the above range, the dispersibility of silica (C) in the composition is excellent. Further, the specific surface area of the silica (C) (BED method) is preferably 50 m ² / g or more, more preferably 100 to 400 m ² / g.

Examples of commercially available silica (C) products include 50, 130, 200, and A200 of Aerosil series manufactured by Nippon Aerosil Co., Ltd.
The content of silica (C) in the composition of the present invention ranges from 1 to 100 parts by weight, preferably 5 to 60 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of the copolymer. Is. When the content of the hydrophobic silica (B) is within the above range, the effect of improving the dynamic magnification and the compression set is excellent.

<Zinc oxide (D)>
Examples of the zinc oxide (D) that can be used in the present invention include those commercially available under the names of zinc oxide, active zinc oxide, composite zinc oxide, surface-treated zinc oxide, and composite activated zinc oxide. Be done. Among these, active zinc oxide is preferable because it exhibits a high activating effect.

The specific surface area of zinc oxide (D) is preferably from 1 to 100 m ² / g, in particular in the range of 10 to 80 m ² / g in the case of the active zinc white is preferable. The average particle size of zinc oxide (D) is preferably in the range of 0.01 to 100 μm, and particularly preferably in the range of 0.05 to 20 μm in the case of active zinc oxide. When the specific surface area and the average particle size are within the above ranges, a high activation effect is exhibited.

Such zinc oxide (D) acts as a vulcanization accelerator during molding, and when a fatty acid is present, forms a complex with the zinc oxide (D) to increase the activity of the vulcanization accelerator and improve the vulcanization rate. Zinc oxide (D) also acts as a bulking agent. Zinc oxide (D) may be used alone or in combination of two or more.

The content of zinc oxide (D) in the composition of the present invention is preferably 0.2 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the copolymer (A). It is preferably in the range of 1 to 8 parts by weight. When the content of zinc oxide (D) is within the above range, an anti-vibration rubber having excellent anti-vibration characteristics can be obtained.

<Other ingredients>
In addition to the above-mentioned components (A) to (D), the composition of the present invention is a rubber compounding agent known per se, for example, organic peroxide, α, β-, as long as the object of the present invention is not impaired. Metal salts of unsaturated organic acids, carbon blacks, softeners, anti-aging agents, cross-linking aids, cross-linking accelerators, fillers, processing aids, activators, antioxidants, foaming agents, plasticizers, tackifiers, etc. Can be appropriately blended.

≪Organic peroxide≫
When the composition of the present invention contains an organic peroxide as a cross-linking agent, a conventionally known organic peroxide usually used for cross-linking rubber can be used as the organic peroxide. ..

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) hexin-3,2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane, α , Α'-Bis (t-butylperoxy-m-isopropyl) benzene, t-butylhydroperoxide and other alkyl peroxides;
t-Butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxymaleic acid, t-butyl peroxyneodecanoate, t-butyl peroxybenzoate, di-t-butyl peroxyphthalate Peroxyesters such as;
Examples thereof include ketone peroxides such as dicyclohexanone peroxide. These can be used alone or in combination of two or more. Among these, organic peroxides having a 1-minute half-life temperature of 130 to 200 ° C. are preferable, for example, dicumyl peroxide, di-t-butyl peroxide, di-t-butyl peroxide-3,3,5-trimethyl. Cyclohexane, t-butyl cumyl peroxide, di-t-amyl peroxide and t-butyl hydroperoxide are preferred.

The organic peroxide has 100 weights of the above-mentioned copolymer (A) in the composition of the present invention from the viewpoint of obtaining the desired physical properties by sufficient cross-linking, preventing adverse effects due to excessive decomposition products, and cost. It is preferably used in the range of 1 to 10 parts by weight, more preferably 2 to 8 parts by weight.

≪Metal salts of α, β-unsaturated organic acids≫
When the composition of the present invention contains a metal salt of an α, β-unsaturated organic acid, the dynamic fatigue resistance and the abrasion resistance of the composition can be improved in a well-balanced manner.

Examples of metal salts of α, β-unsaturated organic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, etacrilic acid, vinyl-acrylic acid, itaconic acid, methylitaconic acid, aconic acid, methylaconic acid, and the like. Metallic salts of acids such as crotonic acid, alpha-methyl crotonic acid, cinnamic acid and 2,4-dihydroxy cinnamic acid. These salts can be zinc, cadmium, calcium, magnesium, sodium or aluminum salts, but zinc salts are particularly preferred. Preferred metal salts of α, β-unsaturated organic acids are zinc diacrylate and zinc dimethacrylate, and particularly preferably zinc dimethacrylate. The metal salts of α, β-unsaturated organic acids can be used alone or in combination of two or more.

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

≪Carbon black≫
When the composition of the present invention contains a specific amount of carbon black, it is possible to obtain a rubber composition having improved workability of the composition and improved mechanical properties such as tensile strength, tear strength, and abrasion resistance. can.

Examples of carbon black include Asahi # 55G, Asahi # 60G (all manufactured by Asahi Carbon Co., Ltd.), Seest (SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, MT, G-SO, etc.). (Above, known products such as Tokai Carbon Co., Ltd.) can be used. These can be used alone or in combination. Further, those surface-treated with a silane coupling agent or the like can also be used.

The carbon black is preferably in the range of 0.1 to 100 parts by weight, more preferably 0.5 to 50 parts by weight, and particularly preferably 1 to 20 parts by weight with respect to 100 parts by weight of the copolymer rubber (A). Used in. When the blending amount of carbon black is within the above range, a rubber composition excellent in dynamic magnification (dynamic elastic modulus / static elastic modulus), workability, mechanical properties and the like can be obtained.

≪Softening agent≫
As the softener, a known softener used in a general rubber composition can be used. Specifically, petroleum-based softeners such as process oils, lubricating oils, liquid paraffins, petroleum asphalts, and vaseline; coultar-based softeners such as coulthal and coultar pitch; , Fat oil-based softeners such as coconut oil; Thor oil; Sub (factis); Rows such as beeswax, carnauba wax, lanolin; ricinolic acid, palmitic acid, stearic acid, barium stearate, calcium stearate, zinc laurate, etc. Stearic acid and fatty acid salt; synthetic polymer substances such as petroleum resin, atactic polypropylene, and kumaron inden resin. Among them, petroleum-based softeners are preferable, process oils are more preferable, paraffin-based process oils, naphthen-based process oils, aroma-based process oils and the like are more preferable, and paraffin-based process oils are particularly preferable. These softeners may be used alone or in combination of two or more.

The softening agent is preferably used in the range of 20 to 150 parts by weight, more preferably 20 to 80 parts by weight, and particularly preferably 20 to 70 parts by weight with respect to 100 parts by weight of the copolymer rubber (A). When the blending amount of the softening agent (E) is within the above range, a rubber composition having less tack and excellent processability, heat aging resistance, mechanical properties and the like can be obtained.

≪Anti-aging agent≫
As the anti-aging agent, a known anti-aging agent used in a general rubber composition can be used. Specific examples thereof include sulfur-based anti-aging agents, phenol-based anti-aging agents, and amine-based anti-aging agents.

In the present invention, the anti-aging agent may be used alone, but it is preferable to use two or more in combination from the viewpoint of maintaining heat-resistant aging property for a long time at high temperature.
In the present invention, the sulfur-based antiaging agent is preferably 0.2 to 10 parts by weight, more preferably 0.2 to 8 parts by weight, particularly preferably 0. It can be used in the range of 2 to 6 parts by weight. It is preferable to use a sulfur-based antiaging agent in the above range because it has a large effect of improving heat aging resistance and does not inhibit the cross-linking of the composition of the present invention.

The phenolic antiaging agent is preferably 0.2 to 5 parts by weight, more preferably 0.5 to 4 parts by weight, and particularly preferably 0.5 to 3 parts by weight with respect to 100 parts by weight of the copolymer (A). It can be used in the range of parts. It is preferable to use a phenolic antiaging agent in the above range because it has a large effect of improving heat aging resistance and does not inhibit the cross-linking of the composition of the present invention.

The amine-based antiaging agent is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 4 parts by weight, and particularly preferably 0.2 to 3 parts by weight, based on 100 parts by weight of the copolymer (A). Used in the range of parts. It is preferable to use an amine-based antiaging agent in the above range because it has a large effect of improving heat aging resistance and does not inhibit the cross-linking of the composition of the present invention.

≪Crosslinking aid≫
Specific examples of the cross-linking aid 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. System compounds: Divinylbenzene and the like can be mentioned. Such a cross-linking aid is preferably used in an amount of 0.5 to 2 mol, more preferably about equimolar to 1 mol of the organic peroxide used.

≪Filler≫
Examples of the filler include activated calcium carbonate, light calcium carbonate, heavy calcium carbonate, talc, clay and the like. These fillers may be used alone or in combination of two or more. Such a filler is preferably used in the range of 1 to 500 parts by weight, more preferably 1 to 400 parts by weight, still more preferably 1 to 300 parts by weight with respect to 100 parts by weight 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 anti-vibration rubber can be improved.

≪Processing aid≫
As the processing aid, those generally blended in rubber as a processing aid can be widely used. Specific examples thereof include ricinolic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, zinc laurate or esters. These processing aids may be used alone or in combination of two or more. The processing aid can be appropriately blended in an amount of preferably 30 parts by weight or less, more preferably 25 parts by weight or less, still more preferably 20 parts by weight or less with respect to 100 parts by weight of the copolymer rubber (A). .. When the blending amount of the processing aid is within the above range, the processability such as kneading processability, extrusion processability, and injection moldability is excellent.

≪Activator≫
Examples of the activator include glycols such as polyethylene glycol and diethylene glycol; amines such as di-n-butylamine and triethanolamine. These activators may be used alone or in combination of two or more. The activator is preferably in the range of 0.2 to 15 parts by weight, preferably 0.3 to 10 parts by weight, and more preferably 0.5 to 8 parts by weight with respect to 100 parts by weight of the copolymer rubber (A). Can be appropriately blended with.

<Preparation of anti-vibration rubber composition>
The composition of the present invention can be prepared by blending the above-mentioned components sequentially or simultaneously by a known method.

In order to produce a crosslinked product from the composition of the present invention, an uncrosslinked rubber composition is prepared once, and then the rubber composition is molded into an intended shape, as in the case of crosslinking a known rubber composition. After that, cross-linking may be performed. The rubber composition may be prepared, molded, and crosslinked separately or continuously.

The crosslinkable rubber composition of the present invention uses, for example, an internal mixer (sealed mixer) such as a Banbury mixer, a kneader, or an intermix to adjust each of the above-mentioned components, preferably 80 to 190 ° C., more preferably. Is kneaded at a temperature of 80 to 170 ° C., preferably for 2 to 20 minutes, more preferably 3 to 10 minutes, and then using a roll such as an open roll or a kneader, at a roll temperature of 40 to 80 ° C. for 3 to 30. It can be prepared by kneading for minutes and then extruding / dispensing the kneaded product. Further, when the kneading temperature in the internal mixers is low, a vulcanization accelerator or the like may be kneaded at the same time.

[Vibration-proof rubber and its manufacturing method]
The anti-vibration rubber of the present invention comprises a crosslinked product of the composition of the present invention. In addition, the method for producing an anti-vibration rubber of the present invention includes a step of cross-linking the composition of the present invention.

In the above-mentioned cross-linking, the uncross-linked rubber composition of the present invention is molded into an intended shape by various molding methods using an extrusion molding machine, a calendar roll, a press, an injection molding machine, a transfer molding machine, etc., and at the same time as molding. Alternatively, it can be carried out by introducing the molded product into a cross-linking tank and heating it at a temperature of 100 to 270 ° C. for 1 to 40 minutes, or by irradiating it with radiation such as light, γ-ray, or electron beam. It can also be crosslinked at room temperature.

A mold may be used for such a cross-linking step, or the cross-linking may be performed without using a mold. When a mold is not used, the molding and cross-linking steps are usually carried out continuously. Examples of the heating method in the cross-linking tank include a method using a heating tank such as hot air, a glass bead fluid bed, UHF (ultra high frequency electromagnetic wave), steam, and LCM (heat molten salt tank).
The anti-vibration rubber of the present invention can be suitably used for anti-vibration rubber products for automobile parts, more specifically, muffler hangers.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. The evaluation method of each physical property in the following Examples and Comparative Examples 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 / non-conjugated polyene copolymer was determined by the value measured by ^{13 C-NMR.} The measured values were measured using an ECX400P type nuclear magnetic resonance apparatus (manufactured by JEOL Ltd.) at a measurement temperature of 120 ° C., a measurement solvent: orthodichlorobenzene / deuterated benzene = 4/1, and an integration number of 8000 times. It was obtained by measuring the ¹³ C-NMR spectrum of the polymer.

<Iodine value>
The iodine value of the ethylene / α-olefin / non-conjugated polyene copolymer rubber was determined by the titration method. Specifically, it was measured by the following method.
Dissolve 0.5 g of ethylene / α-olefin / non-conjugated polyene copolymer rubber in 60 ml of carbon tetrachloride, add a small amount of whistle reagent and 20% potassium iodide solution, and a 0.1 mol / L sodium thiosulfate solution is suitable. I decided. A starch indicator was added near the end point, and the mixture was adjusted until the lilac disappeared while stirring well, and the g number of iodine was calculated as the amount of halogen consumed per 100 g of the sample.

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

<Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn)>
The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) are polystyrene-equivalent numerical 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 monodisperse polystyrene.
Equipment: Gel permeation chromatograph Alliance GP2000 type (manufactured by Waters),
Analytical device: Empourer2 (manufactured by Waters),
Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HTL x 2 (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: Monodisperse polystyrene (manufactured by Tosoh),
Molecular weight conversion: Old method EPR conversion / Calibration method considering viscosity.

<Complex viscosity η ^* >
As a leometer, a viscoelasticity measuring device Ares (manufactured by Rheometric Scientific) was used, and the complex viscosity η ^* ₍ ω _{= 0.01)} at a frequency of ω = 0.01 rad / s under the conditions of 190 ° C. and 1.0% strain. Complex viscosity η ^* ₍ ω _{= 0.1)} at frequency ω = 0.1 rad / s, complex viscosity η ^* ₍ ω _{= 10) at} frequency ω = 10 rad / s, and complex viscosity η ^{* at frequency ω = 100 rad / s} ₍ Ω _{= 100)} (both units are Pa · sec) was measured. Also, from the obtained results, the P value (η ^* ₍ ω _{= 0.1)} / η ^* ₍ 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 was measured by the method described above.
<Evaluation of unvulcanized rubber physical properties>
(1) Mooney viscosity (ML (1 + 4) 125 ° C.)
The Mooney viscosity (ML (1 + 4) 125 ° C.) at 125 ° C. was measured under the condition of 125 ° C. using a Mooney viscometer (SMV202 type manufactured by Shimadzu Corporation) in accordance with JIS K6300.

(2) Vulcanization induction time Using the uncrosslinked rubber compound in Examples and Comparative Examples, a vulcanization measuring device: MDR2000 (manufactured by ALPHA TECHNOLOGIES) under measurement conditions of a temperature of 170 ° C. and a time of 20 minutes. The induction time (TS1) was measured as follows.

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

(3) Vulcanization rate Using the uncrosslinked rubber compositions in Examples and Comparative Examples, the vulcanization rate was measured by a measuring device: MDR2000 (manufactured by ALPHA TECHNOLOGIES) at a temperature of 170 ° C. and a time of 20 minutes. (TC90) was measured as follows.

The torque changes obtained under the conditions of constant temperature and constant shear rate were measured. The time required to reach a torque of 90% of the difference between the maximum and minimum torque values was defined as the vulcanization rate (TC90; minutes).

<Vulcanized rubber physical characteristics>
(1) Hardness test (Duro-A hardness)
According to JIS K 6253, the hardness of the sheets (type A durometer, HA) was measured by stacking flat portions to a thickness of about 12 mm using six 2 mm vulcanized rubber sheets having a smooth surface. However, the test pieces containing foreign matter, air bubbles, and scratches were not used. The size of the measurement surface of the test piece was set so that the tip of the push needle could be measured at a position 12 mm or more 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 a No. 3 dumbbell test piece described in JIS K 6251 (2001). Using this test piece, a tensile test was conducted under the conditions of a measurement temperature of 25 ° C. and a tensile speed of 500 mm / min according to the method specified in JIS K 6251, and 25% modulus (M ₂₅ ) and 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.

<Crosslink density>
The crosslink density ν was calculated from Flory-Rehner's equation (a) using the following equilibrium swelling. V _R in the formula (a) were determined by toluene extraction in the conditions of 37 ° C. × 72h a 2mm sheet crosslinked.

<Compressive permanent strain>
The test piece for compressive permanent strain (CS) measurement was obtained by vulcanizing a right-cylindrical test piece having a thickness of 12.7 mm and a diameter of 29 mm at 170 ° C. for 15 minutes. The obtained test piece was treated according to JIS K6262 (1997) at 160 ° C. for 70 hours, and then the compression set was measured.

<Dynamic characteristics>
The test piece for measuring dynamic characteristics was obtained by vulcanizing a right-cylindrical test piece having a thickness of 12.7 mm and a diameter of 29 mm at 170 ° C. for 15 minutes. First, using a static spring tester (Instron's "Dual Column Desktop Universal Test System 5996", load cell 50 kN), static under the conditions of test temperature 23 ° C, test speed 5 mm / mim, and compression strain amount 3 mm. The spring constant (Ks) (N / mm) was measured. Subsequently, using the test piece used in the static spring test, a dynamic spring tester (“Servopulsor EHF-EM020K1-020-1A” manufactured by Shimadzu Corporation, load cell 1 kN) was used, the test temperature was 23 ° C., and the average deflection was 1. The dynamic spring constant (Kd) (N / mm) and tan δ were measured at 15 Hz (deflection amplitude ± 0.5 mm) and 100 Hz (deflection amplitude ± 0.05 mm) under .25 mm. Further, the dynamic magnification (Kd / Ks) was calculated from the obtained static spring constant (N / mm) and dynamic spring constant (N / mm).

[Production Example 1] Production of ethylene / propylene / VNB copolymer (A-1) Using a polymerizer having a volume of 300 L equipped with a stirring blade, ethylene, propylene, 5-vinyl-2-norbornene (5-vinyl-2-norbornene) ( The polymerization reaction of VNB) was carried out at 87 ° C. Using hexane (feed amount: 32.6 L / h) as the polymerization solvent, the ethylene feed amount was 3.6 kg / h, the propylene amount was 6.1 kg / h, and the VNB feed amount was 290 g / h. The hydrogen feed amount was continuously supplied to the polymerizer so as to be 6.3 NL / h. Feed amount using di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride as the main catalyst while maintaining the polymerization pressure at 1.6 MPaG and the polymerization temperature at 87 ° C. It was continuously supplied to the polymerizer so as to be 0.0015 mmol / h. Further, the _{feed amount of (C 6} H ₅ ) ₃ CB (C ₆ F ₅ ) ₄ as a cocatalyst is 0.0075 mmol / h, and the feed amount of triisobutylaluminum (TIBA) as an organoaluminum compound is 20 mmol / h. Each was continuously supplied to the polymerizer.

In this way, a solution containing 15.2% by mass of an ethylene / propylene / VNB copolymer formed from ethylene, propylene and VNB was obtained. A small amount of methanol was added to the polymerization reaction solution extracted from the lower part of the polymer to stop the polymerization reaction, the ethylene / propylene / VNB copolymer was separated from the solvent by steam stripping treatment, and then the pressure was reduced at 80 ° C. for 24 hours. It was dry.

By the above operation, an ethylene / propylene / VNB copolymer (A-1) formed from ethylene, propylene and VNB was obtained at a rate of 4.7 kg / h. The physical characteristics of the obtained copolymer (A-1) were measured by the method described above. The results are shown in Table 1.

[Example 1]
As a first step, 100 parts by weight of the ethylene / propylene / VNB copolymer (A-1) obtained in Production Example 1 as the copolymer (A) using a BB-4 type Banbury mixer (manufactured by Kobe Steel). Was kneaded for 1 minute, and then, as a copolymer (B), a maleic anhydride-modified ethylene 1-butene copolymer (Toughmer (registered trademark) MH7020, manufactured by Mitsui Chemicals Co., Ltd., MFR (190 ° C., 2) .16 kg): 0.7 g / 10 min, density: 873 kg / m ³ ) 10 parts by weight, silica (Aerozil 200, manufactured by Nippon Aerozil Co., Ltd.) 30 parts by weight, active zinc flower (MEMA-Z 102, Inoue Lime Industry) 5 parts by weight (manufactured by Co., Ltd.), 5 parts by weight of carbon black (Siest G-SO, manufactured by Tokai Carbon Co., Ltd.), 50 parts by weight of paraffin-based process oil (Diana Process PW-380, manufactured by Idemitsu Kosan Co., Ltd.) and 1 part by weight of stearic acid was added, and the mixture was kneaded at 140 ° C. for 2 minutes. Then, the ram was raised and cleaned, and further kneaded for 1 minute and discharged at about 150 ° C. to obtain the first-stage formulation.

Next, as the second step, the formulation obtained in the first step is subjected to 6-inch roll (manufactured by Nippon Roll Co., Ltd., front roll surface temperature 50 ° C., rear roll surface temperature 50 ° C., front roll). 16 rpm, rear roll rotation speed 18 rpm), add 4 parts by weight of dicumylperoxide (DCP-40C, manufactured by Kayaku Akzo), knead for 10 minutes, and knead the uncrosslinked rubber compound. Got The physical properties of unvulcanized rubber were evaluated using this rubber compound.

This kneaded product was dispensed into a sheet and pressed at 170 ° C. for 10 minutes using a 100-ton press molding machine to prepare a vulcanized rubber sheet having a thickness of 2 mm. Using this, the physical properties of vulcanized rubber were evaluated, and the crosslink density, compression set, and dynamic magnification were measured. The results are shown in Table 2.

[Example 2 and Comparative Example 1]
In the same manner as in Example 1, the uncrosslinked rubber compound was not used, except that the types and amounts of the compounds to be blended in the first and second steps were as shown in Table 2. A crosslinked rubber sheet and a vulcanized rubber sheet were obtained and evaluated. The results are shown in Table 2.

Tables 2) to 8) are as follows.
1) Maleic anhydride-modified ethylene / 1-butene copolymer (Toughmer (registered trademark) MH7020, manufactured by Mitsui Chemicals, Inc.)
2) Hydrophilic silica (Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.)
3) Active zinc oxide (Meta-Z 102, manufactured by Inoue Lime Industry Co., Ltd.)
4) Carbon black (Seast G-SO, manufactured by Tokai Carbon Co., Ltd.)
5) Stearic acid (beads stearic acid camellia, manufactured by NOF CORPORATION)
6) Paraffin-based process oil (Diana Process PW-380, manufactured by Idemitsu Kosan Co., Ltd.)
7) Dicumylperoxide (DCP-40C, manufactured by Kayaku Akzo)

Claims (8)

A graft-modified ethylene / α-olefin copolymer (B) grafted with 100 parts by weight of an α-olefin / non-conjugated polyene copolymer (A) having ethylene / carbon atoms of 3 to 20 and an unsaturated carboxylic acid or a derivative thereof (B). Contains 1 to 100 parts by weight and 1 to 100 parts by weight of silica (C) .
The copolymer (A) satisfies the following conditions (i) to (v), and the copolymer (A) satisfies the following conditions (i) to (v).
A composition for anti-vibration rubber , wherein the non-conjugated polyene contains, in total, two or more partial structures selected from the group consisting of the following general formulas (I) and (II) in the molecule :
(I) The molar ratio [(a1) / (a2)] of the structural unit derived from ethylene (a1) to the structural unit derived from α-olefin (a2) is 40/60 to 99.9 / 0. 1;
(Ii) The content of the structural unit derived from the non-conjugated polyene (a3) is 0.07 to 10% by weight, where the total of the structural units of (a1), (a2) and (a3) is 100% by weight. ;
(Iii) Weight average molecular weight (Mw) of ethylene / α-olefin / non-conjugated polyene copolymer (A) and weight fraction of structural unit derived from non-conjugated polyene (a3) (weight fraction of (a3)) (% By weight)) and the molecular weight of the non-conjugated polyene (a3) (the molecular weight of (a3)) satisfy the following formula (1);
4.5 ≤Mw x (a3) weight fraction / 100 / (a3) molecular weight ≤40 ... (1)
^{(Iv) Complex viscosity η *} ₍ ω _{= 0.1)} (Pa · sec) at frequency ω = 0.1 rad / s and frequency ω = 100 rad obtained by linear viscous elasticity measurement (190 ° C.) using a leometer. The ratio P (η ^* ₍ ω _{= 0.1)} / η ^* ₍ ω _{= 100)} ^{) to the complex viscosity η *} ₍ ω _{= 100)} (Pa · sec) at / s, the extreme viscosity [η], and the non- 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 ) ≤ (a3) x 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) are expressed by the following formula (3). Meet.
LCB _1000C ≦ 1-0.07 × Ln (Mw)… (3)

The anti-vibration rubber composition according to claim 1, wherein the non-conjugated polyene contains 5-vinyl-2-norbornene (VNB). It said co density of the polymer (B) is, vibration damping rubber composition according to claim 1 or 2, characterized in that it is less than 860 kg / m ³ or more 880 kg / m ^3. The copolymer (B) has a melting point measured by differential scanning calorimetry (DSC) of 20 ° C. or higher and lower than 60 ° C., or no peak indicating the melting point is observed by differential scanning calorimetry (DSC). The anti-vibration rubber composition according to any one of claims 1 to 3. The anti-vibration rubber composition according to any one of claims 1 to 4 , further containing zinc oxide (D). An anti-vibration rubber comprising a crosslinked product of the anti-vibration rubber composition according to any one of claims 1 to 5. An anti-vibration rubber product for automobile parts, which comprises a crosslinked body of the anti-vibration rubber composition according to any one of claims 1 to 5. The vibration-proof rubber product for automobile parts according to claim 7 , wherein the vibration-proof rubber product for automobile parts is a muffler hanger.