JP7141930B2 - Ethylene-based copolymer composition and hose products - Google Patents

Description

The present invention relates to an ethylene-based copolymer composition containing an ethylene-based copolymer, specific magnesium hydroxide and zinc (meth)acrylate, and uses thereof, and more particularly, to an ethylene-based copolymer composition excellent in bagging properties. Related to things and hose products.

Ethylene-based copolymers such as ethylene/α-olefin copolymers, such as ethylene/α-olefin/non-conjugated polyene copolymers, do not have unsaturated bonds in the main chain, so compared to diene rubbers, It has excellent weather resistance, heat resistance, and ozone resistance, and is widely used for automobile industrial parts, industrial rubber products, electrical insulating materials, civil engineering and construction materials, and rubber products such as rubber-coated cloth.

When an ethylene/α-olefin copolymer is used for a hose, a rubber composition is generally used in which an ethylene/propylene copolymer is the main component and a reinforcing material such as carbon black is blended therein.

In Patent Document 1, ethylene and an α-olefin having 3 to 20 carbon atoms are used as means for improving the volume resistivity without deteriorating the moldability and preventing corrosion and deterioration of the hose due to the minute current flowing through the vehicle body. - A rubber composition for automotive water-system hoses containing a non-conjugated polyene copolymer, a graft-modified ethylene/α-olefin copolymer grafted with an unsaturated carboxylic acid or a derivative thereof, and a reinforcing material such as carbon black has been disclosed. there is

Furthermore, in recent years, the following requirements for automobiles have increased, and further heat aging resistance is required for rubber compositions for automobile water-system hoses, which are materials in engine compartments.
1) Shrinking the engine room due to the expansion of the cabin area to improve ride comfort 2) Covering the engine and its surrounding parts with sound insulation materials due to the tightening of noise regulations in Japan, Europe and other countries. In order to manufacture it, after kneading with a kneader or other kneader, further kneading with an open roll and ribbon production for extruder feed are performed, but for heat aging resistance, secondary materials such as carbon black and oil are filled. A phenomenon in which the reduced amount (low-filled) compound does not wrap around the roll sufficiently and falls off from the roll surface, so-called bagging, makes it difficult to produce a ribbon for extruder feed, leading to a decrease in production efficiency.

JP 2018-119097 A

When bagging occurs, good hose compositions cannot be prepared, making it difficult to produce high performance hose products.
Hose compositions are desired to have higher bagging resistance than conventional hose compositions.
An object of the present invention is to provide a composition having a better balance between bagging resistance and heat aging resistance than conventional EPDM rubber compositions for automobile water-based hoses.

As a result of intensive research to solve the above problems, the present inventors added magnesium hydroxide and zinc (meth)acrylate having specific properties to an ethylene/α-olefin/non-conjugated polyene copolymer. As a result, the inventors have found that a composition having excellent bagging resistance can be obtained, and have completed the present invention.

That is, the present invention relates to, for example, the following items [1] to [8].
[1] Ethylene having a structural unit derived from ethylene (a1), a structural unit derived from an α-olefin having 3 to 20 carbon atoms (a2), and a structural unit derived from a non-conjugated polyene (a3) α-olefin/non-conjugated polyene copolymer (A), and 1-100 parts by weight per 100 parts by weight of said ethylene/α-olefin/non-conjugated polyene copolymer (A), having an aspect ratio of 5-100 Magnesium hydroxide (C) having and 0.2 to 50 parts by weight of zinc (meth)acrylate (D) with respect to 100 parts by weight of the ethylene/α-olefin/non-conjugated polyene copolymer (A) An ethylene-based copolymer composition comprising:
[2] The ethylene-based copolymer composition according to item [1], wherein the copolymer (A) satisfies the following conditions (i) to (vii):
(i) the molar ratio [(a1)/(a2)] of structural units derived from ethylene (a1) to structural units derived from α-olefin (a2) is 40/60 to 99.9/0. is 1;
(ii) the weight fraction of structural units derived from the non-conjugated polyene (a3) is 0.07% by mass to 10% by mass in 100% by mass of the copolymer (A);
(iii) the weight average molecular weight (Mw) of the copolymer (A), the weight fraction of the constituent units derived from the non-conjugated polyene (a3) (the weight fraction (% by mass) of (a3)), and the non-conjugated The molecular weight of the polyene (a3) (molecular weight of (a3)) satisfies the following formula (1);
4.5≦Mw×weight fraction of (a3)/100/molecular weight of (a3)≦40 (1)
(iv) Complex viscosity η ^* ₍ ω _{= 0.1)} (Pa sec) at frequency ω = 0.1 rad/s, obtained by linear viscoelasticity measurements (190°C) using a rheometer, and frequency ω = The ratio P ( η ^* ₍ ω _=0.1) / η ^* ₍ ω ₌₁₀₀₎ ) to the complex viscosity η ^* ₍ ω ₌₁₀₀₎ (Pa·sec) at 100 rad/s, the intrinsic viscosity [ η] , and the non- The weight fraction of structural units derived from the conjugated polyene (a3) (the weight fraction of (a3)) satisfies the following formula (2);
P/([ η] ^2.9 )≦(a3) weight fraction×6 (2)
(v) the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) (molecular weight distribution; Mw/Mn) is in the range of 8 to 30;
(vi) the number average molecular weight (Mn) is 30,000 or less;
(vii) A chart obtained by GPC measurement shows two or more peaks, and the area of the peak appearing on the side of the lowest molecular weight is in the range of 1 to 20% of the total peak area.
[3] Item [1], wherein the non-conjugated polyene (a3) contains a total of two or more partial structures selected from the group consisting of the following general formulas (I) and (II) in the molecule, or The ethylene-based copolymer composition according to [2].

［４］ 前記非共役ポリエン（ａ３）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エチレン系共重合体組成物。
［５］ 前記α－オレフィン（ａ２）がプロピレン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エチレン系共重合体組成物。
［６］ ホース用である項［１］～［５］のいずれか一項に記載のエチレン系共重合体組成物。
［７］ 項［１］～［６］のいずれか一項に記載のエチレン系共重合体組成物の架橋体。
［８］ 項［７］に記載の架橋体を含むホース製品。

[4] The ethylene copolymer composition according to any one of [1] to [3], wherein the non-conjugated polyene (a3) contains 5-vinyl-2-norbornene (VNB). things .
[5] The ethylene-based copolymer composition according to any one of items [1] to [4], wherein the α-olefin (a2) is propylene.
[6] The ethylene-based copolymer composition according to any one of items [1] to [5], which is used for hoses.
[7] A crosslinked product of the ethylene copolymer composition according to any one of [1] to [6].
[8] A hose product containing the crosslinked product according to item [7].

The ethylene-based copolymer composition of the present invention has excellent bagging resistance, as well as excellent heat aging resistance and extrudability. By using the ethylene copolymer composition of the present invention, it is possible to produce hose products with high performance.

FIG. 1 is a photograph showing evaluation criteria for bagging resistance. FIG. 1 (1-1) shows a specific embodiment with a score of 1, ``the composition does not wrap around the roll at all and is immediately bagged''. FIG. 1 (1-2) shows a specific embodiment with a score of 2, ``the composition temporarily wraps around the roll, but immediately separates from the roll surface and is bagged''. FIG. 1 (1-3) shows a specific embodiment with a score of 3: "The composition winds around the roll and often separates from the bank portion, but does not bag." FIG. 1 (1-4) shows a specific embodiment with a score of 4: "The composition easily winds around the roll and very rarely separates from the bank portion, but does not bag." FIG. 1 (1-5) shows a specific embodiment with a score of 5, "The composition easily winds around the roll, does not separate from the bank portion, and does not bag." FIG. 2 is a schematic diagram of a continuous polymerization apparatus used in Examples.

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

Examples of the α-olefin (a2) include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene and the like. Among these, α-olefins having 3 to 8 carbon atoms such as propylene, 1-butene, 1-hexene and 1-octene are preferred, and propylene is particularly preferred. Such an α-olefin is preferable because the raw material cost is relatively low, the resulting copolymer (A) exhibits excellent mechanical properties, and a molded article 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 α-olefin (a2) having 3 to 20 carbon atoms, and two or more α-olefins having 3 to 20 carbon atoms. - It may contain structural units 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 non-conjugated unsaturated bonds. and a compound containing two or more in the molecule.

上記非共役ポリエン（ａ３）としては、５－ビニル－２－ノルボルネン（ＶＮＢ）、ノルボルナジエン、１，４－ヘキサジエン、ジシクロペンタジエンなどが挙げられる。これらのうちでは、入手容易性が高く、重合後の架橋反応時に過酸化物との反応性が良好で、重合体組成物の耐熱性が向上しやすいことから、非共役ポリエン（ａ３）がＶＮＢを含むことが好ましく、非共役ポリエン（ａ３）がＶＮＢであることがより好ましい。非共役ポリエン（ａ３）は一種単独で用いても、二種以上を用いてもよい。

Examples of the non-conjugated polyene (a3) include 5-vinyl-2-norbornene (VNB), norbornadiene, 1,4-hexadiene and dicyclopentadiene. Among these, the non-conjugated polyene (a3) is the VNB because it is easily available, has good reactivity with peroxides during the crosslinking 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 (a1), (a2), and (a3), a partial structure selected from the group consisting of the general formulas (I) and (II). It may have a structural unit derived from the 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, 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 - includes norbornene and the like. Among these, ENB is preferable because it is easily available, has high reactivity with sulfur and a vulcanization accelerator during the crosslinking reaction after polymerization, is easy to control the crosslinking rate, and is easy to obtain good mechanical properties. . 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 ratio is not particularly limited as long as the object of the present invention is not impaired, but usually 0 to 20% by mass, preferably 0 to 8% by mass, more preferably about 0.01 to 8% by mass (however, the weight of (a1), (a2), (a3), and (a4) Let the sum of the ratios be 100% by mass).

The above copolymer (A) preferably satisfies the following requirements (i) to (vii) (hereinafter also referred to as requirements (i) to (vii), respectively).
(i) The molar ratio [(a1)/(a2)] of structural units derived from ethylene (a1) to structural units derived from α-olefin (a2) is 40/60 to 99.9/0. 1.
(ii) The weight fraction of structural units derived from the non-conjugated polyene (a3) is 0.07% by mass to 10% by mass in 100% by mass of the copolymer (A).
(iii) the weight average molecular weight (Mw) of the copolymer (A), the weight fraction of the constituent units derived from the non-conjugated polyene (a3) (the weight fraction (% by mass) of (a3)), and the non-conjugated The molecular weight of the polyene (a3) (the molecular weight of (a3)) satisfies the following formula (1).
4.5≦Mw×weight fraction of (a3)/100/molecular weight of (a3)≦40 (1)
(iv) Complex viscosity η ^* ₍ ω _{= 0.1)} (Pa sec) at frequency ω = 0.1 rad/s, obtained by linear viscoelasticity measurement (190°C) using a rheometer, and frequency ω = The ratio P (η ^* ₍ ω _{= 0.1)} / η ^* ₍ ω _{= 100)} ) to the complex viscosity η ^* ₍ ω _{= 100)} (Pa sec) at 100 rad/s, the intrinsic viscosity [η], and the non- The weight fraction of structural units derived from the conjugated polyene (a3) (the weight fraction of (a3)) satisfies the following formula (2).
P/([η] ^2.9 )≦(a3) weight fraction×6 (2)
(v) The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) (molecular weight distribution; Mw/Mn) is in the range of 8-30.
(vi) The number average molecular weight (Mn) is 30,000 or less.
(vii) A chart obtained by GPC measurement shows two or more peaks, and the area of the peak appearing on the side of the lowest molecular weight is in the range of 1 to 20% of the total peak area.

≪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. , this molar ratio is preferably from 50/50 to 90/10, more preferably from 55/45 to 85/15, even more preferably from 55/45 to 78/22.

By using the copolymer (A) that satisfies the requirement (i), an ethylene copolymer composition excellent in rubber elasticity, mechanical strength and flexibility can be obtained. The amount of ethylene (content of structural units derived from ethylene (a1)) and the amount of α-olefin (content of structural units derived from α-olefin (a2)) in the copolymer (A) are ¹³ C- It can be determined by NMR.

≪Requirement (ii)≫
Requirement (ii) is that the weight fraction of structural units derived from the non-conjugated polyene (a3) is in 100% by mass of the copolymer (A) (that is, in the total 100% by mass of the weight fraction of all structural units) , in the range of 0.07% by mass to 10% by mass. The weight fraction of structural units derived from the non-conjugated polyene (a3) is preferably 0.1% by mass to 8.0% by mass, more preferably 0.5% by mass to 5.0% by mass.

The copolymer (A) that satisfies the requirement (ii) has sufficient hardness and excellent mechanical properties, and exhibits a high cross-linking speed when cross-linked using a peroxide. The amount of the non-conjugated polyene (a3) in the copolymer (A) (content of structural units derived from the non-conjugated polyene (a3)) can be determined by ¹³ C-NMR.

≪Requirement (iii)≫
Requirement (iii) is, in the copolymer (A), the weight average molecular weight (Mw) of the copolymer (A), and the number of structural units derived from the non-conjugated polyene (a3) in the copolymer (A) It specifies that the weight fraction (weight fraction of (a3): mass %) and the molecular weight of the non-conjugated polyene (a3) (molecular weight of (a3)) satisfy the above formula (1). The above formula (1) of requirement (iii) is preferably the following formula (1').
4.5≦Mw×weight fraction of (a3)/100/molecular weight of (a3)≦35 (1′)

By satisfying the requirement (iii), the copolymer (A) has an appropriate content of structural units derived from the non-conjugated polyene (a3), exhibits sufficient cross-linking performance, and has an excellent cross-linking speed. Ethylene-based copolymer compositions can be produced that exhibit excellent mechanical properties. The weight average molecular weight (Mw) of the copolymer (A) can be obtained as a polystyrene-equivalent numerical value measured by gel permeation chromatography (GPC).

In the copolymer (A), when "Mw x (a3) weight fraction/100/(a3) molecular weight" satisfies the above formula (1) or (1'), the degree of crosslinking is appropriate, and mechanical It is possible to produce an ethylene-based copolymer composition having well-balanced physical properties and heat aging resistance. If the value of "Mw x weight fraction of (a3)/100/molecular weight of (a3)" is too low, the crosslinkability may be insufficient, resulting in a slow crosslinking rate. , the mechanical properties may deteriorate due to excessive cross-linking.

≪Requirement (iv)≫
Requirement (iv) is the complex viscosity η ^* ₍ ω _{= 0.1 )} (Pa·sec) and the ratio P(η ^* ₍ ω _=0.1) /η ^* ₍ ω ₌₁₀₀₎ of the complex viscosity η ^* ₍ ω ₌₁₀₀₎ (Pa·sec) at the frequency ), the intrinsic viscosity [η], and the weight fraction of the structural unit derived from the non-conjugated polyene (a3) (the weight fraction of (a3): mass%) satisfy the above formula (2). It is specific. The above formula (2) of requirement (iv) is preferably the following formula (2').
P/([η] ^2.9 )≦(a3) weight fraction×5.7 (2′)

Here _, ^the ratio _P ⁽ _η ^* _{( ω =0.1)} /η ^* ₍ ω ₌₁₀₀₎ ) represents the frequency dependence of viscosity, and P/([η] ^2.9 ) on the left side of equation (2) represents factors such as short chain branching and molecular weight. Although there is an effect, it tends to show a high value when there are many long chain branches. In general, ethylene/α-olefin/non-conjugated polyene copolymers tend to contain more long-chain branches as they contain more structural units derived from non-conjugated polyene. It is thought that the above formula (2) can be satisfied by having fewer long-chain branches than conventionally known ethylene/α-olefin/non-conjugated polyene copolymers.

In the present invention, the P value is a complex viscosity at 0.1 rad/s obtained by performing measurements using a 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) is obtained. In addition, the intrinsic viscosity [η] means a value measured in decalin at 135°C.

≪Requirement (v)≫
Requirement (v) is the ratio (molecular weight distribution; Mw/ Mn) is in the range of 8-30. The molecular weight distribution (Mw/Mn) is preferably in the range of 9-28, more preferably 10-26.

When the above copolymer (A) satisfies the requirement (v), it contains an appropriate amount of low-molecular-weight components, resulting in good processability.
The weight-average molecular weight (Mw) and number-average molecular weight of the copolymer (A) can be obtained as polystyrene equivalent values measured by gel permeation chromatography (GPC).

≪Requirement (vi)≫
Requirement (vi) specifies that the number average molecular weight (Mn) of the copolymer (A) is 30,000 or less. The number average molecular weight (Mn) is preferably in the range of 3,000 to 26,000, more preferably 6,000 to 23,000.
When the above copolymer (A) satisfies the requirement (vi), it contains an appropriate amount of low-molecular-weight components, resulting in good processability.

<<Requirement (vii)>>
Requirement (vii) is that the chart obtained by GPC measurement of the copolymer (A) shows two or more peaks, and the area of the peak appearing on the side with the lowest molecular weight is 20% or less of the total peak area. It identifies something. The area of the peak appearing on the side of the lowest molecular weight is preferably 2 to 18%, more preferably 3 to 16%, relative to the total peak area.

When the copolymer (A) satisfies the requirement (vii), the molecular weight distribution of the copolymer (A) exhibits multimodality such as bimodality, and a high molecular weight component and a low molecular weight component are separated. If it is contained in an appropriate ratio, the workability becomes good.
The above copolymer (A) preferably satisfies requirements (viii) to (x) in addition to requirements (i) to (vii).

≪Requirement (viii)≫
The above copolymer (A) has a long chain branch number (LCB _1000C ) per 1000 carbon atoms obtained by 3D-GPC and a natural logarithm [Ln (Mw)] of the weight average molecular weight (Mw). , preferably satisfies the following formula (3), and more preferably satisfies the following formula (3′).
LCB _1000C ≤ 1-0.07 x Ln (Mw) (3)
LCB _1000C ≤ 1-0.071 x Ln (Mw) (3')

The upper limit of the long-chain branch content per unit carbon number of the copolymer (A) is specified by the above formula (3) or (3').
Such a copolymer (A) contains a small proportion of long chain branches, is excellent in curing properties when cross-linking is performed using a peroxide, and is an ethylene copolymer composition excellent in heat aging resistance. can get things.

Here, Mw and the number of long chain branches per 1000 carbon atoms (LCB _1000C ) can be determined by structural analysis using 3D-GPC. In this specification, specifically, it was determined 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 intrinsic viscosity was determined with a viscometer. The main measurement conditions are as follows.
Detector: Built-in differential refractometer/GPC device
Two-angle light scattering photometer PD2040 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
(Each one has an inner diameter of 7.8mmφ x length of 300mm)
Temperature: 140℃
Mobile phase: 1,2,4-trichlorobenzene (containing 0.025% BHT)
Injection Volume: 0.5mL
Sample concentration: ca 1.5mg/mL
Sample filtration: Filtration with a sintered filter with a pore size of 1.0 μm

In the above, the dn/dc value necessary for determining the absolute molecular weight was determined for each sample from the dn/dc value 0.053 of standard polystyrene (molecular weight 190000) and the response intensity of the differential refractometer per unit injection mass.
The long chain branching parameter g'i for each eluted component was calculated from the following formula (v-1) from the relationship between the intrinsic viscosity obtained from the viscometer and the absolute molecular weight obtained from the light scattering photometer.

ここで、［η］=ＫＭ^v；ｖ＝0.725の関係式を適用した。

Here, the relation [η]=KM ^v ; v=0.725 was applied.

In addition, each average value of g' was calculated from the following formulas (v-2), (v-3), and (v-4). Note that the trendline assumed to have only short-chain branches was determined for each sample.

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

Furthermore, using g'w, the branching point number BrNo per molecular chain, the long chain branching number LCB _1000C per 1000 carbons, and the branching degree λ per unit molecular weight were calculated. Zimm-Stockmayer's formula (v-5) was used to calculate BrNo, and the following formulas (v-6) and (v-7) were used to calculate LCB _1000C and λ. g is the long chain branching parameter determined from the radius of gyration Rg, and the following simple correlation is made with g' determined from the intrinsic viscosity. Various values have been proposed for ε in the formula depending on the shape of the molecule. Here, the calculation was performed assuming 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 x 14000 (V-7)
In formula (V-7), "14000" represents the molecular weight of 1000 methylene (CH ² ) units.

The intrinsic 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, and still more preferably 50,000 to 400,000. be.

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

As described above, the copolymer (A) further includes structural units derived from the non-conjugated polyene (a4) in addition to the structural units derived from (a1), (a2) and (a3). , 0% by mass to 20% by mass (where the sum of the weight fractions of (a1), (a2), (a3), and (a4) is 100% by mass). In this case, it is preferable to satisfy the following requirement (ix).

≪Requirement (ix)≫
The weight average molecular weight (Mw) of the copolymer (A), the weight fraction of structural units derived from the non-conjugated polyene (a3) (the weight fraction (mass%) of (a3)), and the non-conjugated polyene ( Weight fraction of structural units derived from a4) (weight fraction (mass%) of (a4)), molecular weight of non-conjugated polyene (a3) (molecular weight of (a3)), and non-conjugated polyene (a4) The molecular weight (the molecular weight of (a4)) satisfies the following formula (4).
4.5≦Mw×{(weight fraction of (a3)/100/molecular weight of (a3))+(weight fraction of (a4)/100/molecular weight of (a4))}≦45 (4)
Formula (4) specifies the content of non-conjugated diene (the sum of (a3) and (a4)) in one molecule of the copolymer.

When the copolymer (A) containing the structural unit derived from (a4) above satisfies the formula (4), an ethylene copolymer composition excellent in mechanical properties and heat aging resistance can be obtained.
Requirement (ix) is not satisfied, and "Mw × {(weight fraction of (a3)/100/molecular weight of (a3)) + (weight fraction of (a4)/100/(a4)" in formula (4) If the value of "molecular weight of (molecular weight)}" is too low, i.e., if the content of the non-conjugated diene is too low, sufficient crosslinking may not be achieved and appropriate mechanical properties may not be obtained. If the content of the conjugated diene is too high, the cross-linking may be excessive and the mechanical properties may be deteriorated, and the heat aging resistance may be deteriorated.

≪Requirement (x)≫
The copolymer (A) is not particularly limited, but the complex viscosity η ^* ₍ ω _{= 0.01)} (Pa·sec), the complex viscosity η ^* ₍ ω _{= 10)} (Pa·sec) at frequency ω = 10 rad/s, and the apparent iodine number derived from the non-conjugated polyene (a3) , preferably satisfies the following formula (5).
Log{η ^* ₍ ω _=0.01) }/Log{η ^* ₍ ω ₌₁₀₎ }≦0.0753×{apparent iodine value derived from non-conjugated polyene (a3)}+1.42 (5)

where the complex viscosity η ^* ₍ ω _=0.01) and the complex viscosity η ^* ₍ ω ₌₁₀₎ are measured with the complex viscosity η ^* ₍ ω _=0.1) and the complex viscosity η ^* ₍ ω ₌₁₀₀₎ in requirement (iv) Other than the frequency, it is obtained in the same way. Also, the apparent iodine value derived from the non-conjugated polyene (a3) is determined 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 shear rate dependence as an index of the amount of long chain branching, and the right side represents an index of the content of non-conjugated polyene (a3) that is not consumed as long chain branching during polymerization. When the copolymer (A) satisfies the above formula (5), it is preferable because the degree of long chain branching is not too high. On the other hand, when the above formula (5) is not satisfied, it can be seen that a large proportion of the copolymerized non-conjugated polyene (a3) was consumed to form long chain branches.

Furthermore, the copolymer (A) preferably contains a sufficient amount of structural units derived from the non-conjugated polyene (a3). More preferably, the weight fraction (the weight fraction (mass %) of (a3)) and the weight average molecular weight (Mw) of the copolymer satisfy the following formula (6).
6-0.45 × Ln (Mw) ≤ (a3) weight fraction ≤ 10 (6)

In the copolymer (A), the number (n _a3 ) of structural units derived from the non-conjugated polyene (a3) per weight average molecular weight (Mw) is preferably 6 or more, more preferably 6. 40 or less, more preferably 7 or more and 39 or less, particularly preferably 10 or more and 38 or less.

Such a copolymer (A) contains a sufficient amount of structural units derived from a non-conjugated polyene (a3) such as VNB, has a low long-chain branch content, and is crosslinked using a peroxide. It has excellent curing properties, good moldability, excellent balance of physical properties such as mechanical properties, and is particularly excellent in heat aging resistance.

In the copolymer (A), the number (n _a4 ) of structural units derived from the non-conjugated polyene (a4) per weight average molecular weight (Mw) is preferably 29 or less, more preferably 10. Below, it is more preferably less than one.

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

Here, the number of structural units derived from the non-conjugated polyene (a3) (n _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 structural units derived from the non-conjugated polyene (a3) or (a4) in the copolymer ((a3) or ( It can be determined by the following formula from the weight fraction (% by mass) of a4) and the weight average molecular weight (Mw) of the copolymer (A).
(n _a3 )=(Mw)×{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)

In the copolymer (A), the numbers (n _a3 ) and (n _a4 ) of the respective structural units derived from the non-conjugated polyenes (a3) and (a4) per weight average molecular weight (Mw) are When the above range is satisfied, the copolymer (A) has a low content of long chain branches, excellent curing properties when crosslinking is performed using a peroxide, good moldability, mechanical properties, etc. It is preferable because it has an excellent balance of physical properties, is resistant to post-crosslinking, and is particularly excellent in heat aging resistance.

<Preparation of copolymer (A)>
The copolymer (A) is obtained by copolymerizing monomers comprising ethylene (a1), α-olefin (a2), non-conjugated polyene (a3), and optionally non-conjugated polyene (a4). It is a copolymer.

The above copolymer (A) may be prepared by any method as long as it satisfies the above requirements (i) to (vii). Preferably, it is obtained by copolymerizing monomers in the presence of a catalyst system containing a metallocene compound, and is obtained by copolymerizing in the presence of a polymerization catalyst containing a specific metallocene compound. and step (2) of adding alcohol as a catalyst deactivator to deactivate the polymerization catalyst.

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

式［Ａ１］中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁸、Ｒ⁹およびＲ¹²はそれぞれ独立に水素原子、炭化水素基、ケイ素含有基またはケイ素含有基以外のヘテロ原子含有基を示し、Ｒ¹～Ｒ⁴のうち隣接する二つの基同士は互いに結合して環を形成していてもよい。

In formula [A1], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² are each independently a hydrogen atom, a hydrocarbon group, a silicon-containing group, or a hetero group other than a silicon-containing group. It represents an atom-containing group, and two adjacent groups among 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, specifically, an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, Examples include an aryl group or a substituted aryl group. For example, 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, xylyl group, isopropylphenyl group, t-butylphenyl group, naphthyl group, biphenyl group, ter Examples include phenyl group, phenanthryl group, anthracenyl group, benzyl group, cumyl group, oxygen-containing groups such as methoxy group, ethoxy group, phenoxy group, nitro group, cyano group, N-methylamino group, N,N- Hydrocarbon groups also include those containing nitrogen-containing groups such as dimethylamino group and N-phenylamino group, boron-containing groups such as boranetriyl group and diboranyl group, and sulfur-containing groups such as sulfonyl group and sulfenyl group.

Hydrogen atoms in the above hydrocarbon groups may be substituted with halogen atoms, and examples thereof include a trifluoromethyl group, a trifluoromethylphenyl group, a pentafluorophenyl group, and a chlorophenyl group.

Examples of silicon-containing groups include silyl groups, siloxy groups, hydrocarbon-substituted silyl groups, and hydrocarbon-substituted siloxy groups. For example, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group, dimethyl(pentafluorophenyl ), silyl groups, and the like.

R ⁶ and R ¹¹ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group, and R ⁷ and R ¹⁰ are a hydrogen atom, a hydrocarbon the same atom or the same group selected from a heteroatom ^- containing group other than a silicon ^- containing group, a silicon-containing group, and a silicon-containing group ^; R ¹¹ may combine with 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.
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 non-conjugated diene having 4 to 20 carbon atoms, an anionic ligand or a neutral ligand capable of coordinating with a lone pair; and j represents an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Q may be the same or different.

A halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom.
As the hydrocarbon group, a hydrocarbon group having 1 to 10 carbon atoms is preferable, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, 2-methylpropyl group and 1,1-dimethylpropyl group. , 2,2-dimethylpropyl group, 1,1-diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, sec-butyl group, t-butyl group, 1,1-dimethylbutyl 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, ethyl benzyl group.

As the neutral conjugated or non-conjugated diene having 4 to 20 carbon atoms, a neutral conjugated or non-conjugated diene having 4 to 10 carbon atoms is preferred. Specific examples of neutral conjugated or non-conjugated dienes are s-cis- or s-trans-η ⁴ -1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4-diphenyl- 1,3-butadiene, s-cis- or s-trans-η ⁴ -3-methyl-1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4-dibenzyl-1,3- butadiene, s-cis- or s-trans-η ⁴ -2,4-hexadiene, s-cis- or s-trans-η ⁴ -1,3-pentadiene, s-cis- or s-trans-η ⁴ - 1,4-ditolyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4-bis(trimethylsilyl)-1,3-butadiene and the like.

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

Specific examples of neutral ligands capable of coordinating with a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine, or tetrahydrofuran, diethyl ether, dioxane, 1,2- Ethers such as dimethoxyethane are included.

The cyclopentadienyl group having substituents R ¹ to R ⁴ in the above formula [A1] includes 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-position 1-substituted 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 3,5-disubstituted cyclopentadienyl groups such as -trimethylsilyl-5-methylcyclopentadienyl group can be mentioned, but not limited thereto. An unsubstituted cyclopentadienyl group (R ¹ to R ⁴ are hydrogen atoms) is preferred from the viewpoints of ease of synthesizing metallocene compounds, production costs, and copolymerization ability of non-conjugated polyenes.

As the fluorenyl group having substituents R ⁵ to R ¹² in formula [A1],
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-position 1-substituted fluorenyl groups such as 4-methylfluorenyl group, 4-t-butylfluorenyl group, 4-phenylfluorenyl group,
or 2,7- or 3,6-disubstituted fluorenyl groups such as 2,7-di-t-butylfluorenyl group and 3,6-di-t-butylfluorenyl group,
2,3,6,7-position 4 such as 2,7-dimethyl-3,6-di-t-butylfluorenyl group and 2,7-diphenyl-3,6-di-t-butylfluorenyl group a substituted fluorenyl group,
Alternatively, R ⁶ and R ⁷ are bonded together to form a ring, and R ¹⁰ and R ¹¹ are bonded together to form a ring, as represented by general formulas [VI] and [V-II] below. Examples include 2,3,6,7-disubstituted fluorenyl groups, but are not limited to these.

式[V－I]、[V－II]中、Ｒ⁵、Ｒ⁸、Ｒ⁹、Ｒ¹²は前記一般式［Ａ１］における定義と同様であり、
Ｒ^a、Ｒ^b、Ｒ^c、Ｒ^d、Ｒ^e、Ｒ^f、Ｒ^gおよびＲ^hは、それぞれ独立に水素原子または炭素数１～５のアルキル基であり、隣接した置換基と互いに結合して環を形成していてもよい。前記アルキル基としては、具体的にはメチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｔ－ブチル基、アミル基、ｎ－ペンチル基を例示できる。また、式[V－I]中、Ｒ^xおよびＲ^yはそれぞれ独立に炭素数１～３の不飽和結合を有してもよい炭化水素基であり、Ｒ^xがＲ^aまたはＲ^cが結合した炭素と共同して二重結合を形成していてもよく、Ｒ^yがＲ^eまたはＲ^gが結合した炭素と共同して二重結合を形成していてもよく、Ｒ^xおよびＲ^yがともに炭素数１または２の飽和あるいは不飽和の炭化水素基であることが好ましい。

In formulas [VI] and [V-II], R ⁵ , R ⁸ , R ⁹ and R ¹² are the same as defined in formula [A1],
R ^a , R ^b , R ^c , R ^d , R ^e , R ^f , R ^g and R ^h are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms and are bonded to adjacent substituents. may form a ring. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, amyl group and n-pentyl group. In formula [V-I], R ^x and R ^y are each independently a hydrocarbon group optionally having an unsaturated bond with 1 to 3 carbon atoms, and R ^x is a bond between R ^a or R ^c R ^y may cooperate with the carbon to which R e or R g is attached to form a double bond, and R ^x and R ^y may cooperate with the carbon to which R ^e or R ^g is attached to 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 general formula [VI] or [V-II] include an octamethyloctahydrodibenzofluorenyl group represented by the formula [V-III], the formula [V- IV], octamethyltetrahydrodicyclopentafluorenyl group represented by formula [V-V], hexamethyldihydro represented by formula [V-VI] Examples include a dicyclopentafluorenyl group and a b,h-dibenzofluorenyl group represented by formula [V-VII].

Any of these metallocene compounds represented by the above general formula [A1] containing ^a fluorenyl group is excellent in the ability to copolymerize a non-conjugated polyene. 3,6-disubstituted fluorenyl groups, 2,3,6,7-disubstituted fluorenyl groups, transition metals having 2,3,6,7-disubstituted fluorenyl groups represented by the above general formula [VI] Compounds are particularly good. When Y is a carbon atom, an unsubstituted fluorenyl group, a disubstituted fluorenyl group at the 3,6 positions, a tetrasubstituted fluorenyl group at the 2,3,6,7 positions, in which R ⁵ to R ¹² are hydrogen atoms, the general formula [V A metallocene compound having a 4-substituted fluorenyl group at the 2,3,6,7 positions represented by -I] is particularly excellent.

In the present invention, in the metallocene compound represented by the general formula [A1], when Y ¹ is a silicon atom and R ⁵ to R ¹² are all hydrogen atoms, R ¹³ and R ¹⁴ are methyl a group other than a group, butyl group, phenyl group, silicon-substituted phenyl group, cyclohexyl group, benzyl group;
R ¹³ when Y ¹ is a silicon atom, both R ⁶ and R ¹¹ are t-butyl groups, and R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹² are not t-butyl groups; and R are selected from groups other than ^benzyl and silicon-substituted phenyl;
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 pn-butylphenyl, silicon-substituted phenyl, 4-biphenyl, p-tolyl, naphthyl, benzyl, cyclopentyl, cyclohexyl, xylyl groups;
Y ¹ is a carbon atom, R ⁶ and R ¹¹ are common groups selected from t-butyl group, methyl group and phenyl group, and R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹² and When different groups or atoms, R ¹³ and R ¹⁴ are selected from groups other than methyl, phenyl, pt-butylphenyl, pn-butylphenyl, silicon-substituted phenyl and benzyl. ;
Y ¹ is a carbon atom, R ⁶ is a dimethylamino group, methoxy group or methyl group, and R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are groups different from R ⁶ or when they are atoms, R ¹³ and R ¹⁴ are selected from groups other than methyl and phenyl;
When Y ¹ is a carbon atom and the moiety composed of a fluorenyl group and R ⁵ to R ¹² is b,h-dibenzofluorenyl or a,i-dibenzofluorenyl, R ¹³ and R ¹⁴ are It is preferably selected from groups other than a methyl group and a phenyl group.

Specific examples of the metallocene compound represented by the general formula [A1] are shown below, but the scope of the present invention is not particularly limited by these.
Specific examples of the metallocene compound represented by the general formula [A1] include:
When Y is a silicon atom,
diphenylsilylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride,
diphenylsilylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride,
diphenylsilylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride,
diphenylsilylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride,
diphenylsilylene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride,
diphenylsilylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride,
diphenylsilylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride,
diphenylsilylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride,
diphenylsilylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride,
di(p-tolyl)silylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,
di(p-tolyl)silylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride,
di(p-tolyl)silylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride,
di(p-tolyl)silylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride,
di(p-tolyl)silylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride,
di(p-tolyl)silylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride,
di(p-tolyl)silylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride,
di(p-tolyl)silylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride,
di(p-tolyl)silylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride,
di(p-tolyl)silylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride,
di(m-tolyl)silylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,
di(m-tolyl)silylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride,
di(m-tolyl)silylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride,
di(m-tolyl)silylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride,
di(m-tolyl)silylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride,
di(m-tolyl)silylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride,
di(m-tolyl)silylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride,
di(m-tolyl)silylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride,
di(m-tolyl)silylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride,
and di(m-tolyl)silylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride.

When 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,
and di(2-naphthyl)methylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride.

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

上記メタロセン化合物は１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。

The above metallocene compounds may be used singly or in combination of two or more.

The metallocene compound represented by the above formula [A1], which can be suitably used for preparing the above copolymer (A), can be produced by any method without particular limitation. For example, J. Organomet. Chem. , 63, 509 (1996), WO2005/100410, WO2006/123759, WO01/27124, JP-A-2004-168744, JP-A-2004-175759, JP-A-2000-212194, etc. It can be produced according to the method described in .

<<Catalyst Containing Metallocene Compound>>
Polymerization catalysts that can be suitably used for the production of the copolymer (A) include those that contain the metallocene compound [A1] described above and are capable of copolymerizing monomers.
Preferably,
(a) a metallocene compound represented by the general formula [A1];
(b) at least one selected from (b-1) an organometallic compound, (b-2) an organoaluminumoxy compound, and (b-3) a compound that reacts with the metallocene compound (a) to form an ion pair; A compound of (hereinafter also referred to as "ionized ionic compound"),
Further, if necessary
(c) a polymerization catalyst comprising a particulate carrier; Each component will be specifically described below.

<<Compound (b)>>
The compound (b) is at least one compound selected from (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound and (b-3) an ionized ionic compound, preferably at least It contains the organometallic compound (b-1).

(b-1) Organometallic compounds Examples of the organometallic compounds (b-1) include organic metals of Groups 1 and 2 and Groups 12 and 13 of the periodic table, such as the following general formulas [VII] to [IX]. compounds are used.
(b-1a) General formula: R ^a _m Al (OR ^b ) _n H _p X _q [VII]
(In formula [VII], R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is 0<m≦3, n is 0≦n<3, p is 0≦p<3, q is a number satisfying 0≦q<3, and m+n+p+q=3). Compound.

Such compounds include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, tricycloalkylaluminum, isobutylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methyl Examples include aluminum dichloride, dimethylaluminum chloride, and diisobutylaluminum hydride.
(b-1b) General formula: M ² AlR ^a ₄ [VIII]
(In the formula [VIII], M ² represents Li, Na or K, and R ^a is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4.) Complex alkylates of group metals and aluminum.

Examples of such compounds include LiAl(C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ .
(b-1c) General formula: R ^a R ^b M ³ ... [IX]
(In the formula [IX], R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ³ is Mg, Zn or Cd.).

Among the above organometallic compounds (b-1), organoaluminum compounds such as triethylaluminum, triisobutylaluminum and tri-n-octylaluminum are preferred. Such organometallic compounds (b-1) may be used singly or in combination of two or more.

(b-2) Organoaluminumoxy Compound The organoaluminumoxy 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 aluminoxanes can be produced, for example, by the following method, and are usually obtained as a solution in 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, cerous chloride hydrate, etc. A method of adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension of (1) and reacting the adsorbed water or water of crystallization with the organoaluminum compound.
(2) A method in which water, ice or steam is directly acted 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.

In addition, the aluminoxane may contain a small amount of organometallic components. Alternatively, the solvent or the unreacted organoaluminum compound may be removed by distillation from the recovered aluminoxane solution, and then redissolved in the solvent or suspended in a poor solvent for the aluminoxane.

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

Among these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum and triisobutylaluminum are particularly preferred.
The organoaluminum compounds as described above may be used singly or in combination of two or more.

In the benzene-insoluble organoaluminumoxy compound, which is one embodiment of the organoaluminumoxy compound (b-2) used in the present invention, the Al component dissolved in benzene at 60° C. is Usually 10% by mass or less, preferably 5% by mass or less, and particularly preferably 2% by mass or less, that is, those that are insoluble or sparingly soluble in benzene are preferred.

Examples of the organoaluminumoxy compound (b-2) used in the present invention include an organoaluminumoxy compound 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 formula [X], R ¹ represents a hydrocarbon group having ¹ to 10 carbon atoms; ~10 hydrocarbon groups are shown.

The organoaluminumoxy compound containing boron represented by the general formula [X] is
General formula: R ¹ -B(OH) ₂ ... [XI]
(In formula [XI], R1 represents the same group as R1 in general formula [X].)
An alkylboronic acid represented by
and an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of −80° C. to room temperature for 1 minute to 24 hours.

Examples of alkylboronic acids 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 cyclohexylboronic acid. , phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, 3,5-bis(trifluoromethyl)phenylboronic acid and the like.

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

Examples of the organoaluminum compound to be reacted with such an alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (b-1a) above. Among these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable.
The organoaluminumoxy compound (b-2) as described above may be used alone or in combination of two or more.

(b-3) Ionized ionic compound As the ionized ionic compound (b-3), JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-H9 3-179006, JP-A-3-207703, JP-A-3-207704, USP5321106, Lewis acids, ionic compounds, borane compounds and carborane compounds. In addition, heteropolycompounds and isopolycompounds may also be mentioned. Such ionized ionic compounds (b-3) may be used singly or in combination of two or more.

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

式[XII]中、Ｒ¹⁺としては、Ｈ⁺、カルボニウムカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオン、遷移金属を有するフェロセニウムカチオンなどが挙げられる。Ｒ²～Ｒ⁵は、互いに同一でも異なっていてもよく、有機基、好ましくはアリール基または置換アリール基である。

In formula [XII], R ¹⁺ includes H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, and the like. R ² to R ⁵ may be the same or different and are organic groups, preferably aryl groups or substituted aryl groups.

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

Specific 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;
di(isopropyl)ammonium cations, dialkylammonium cations such as dicyclohexylammonium cations, and the like.

Specific 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.

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

Specific examples of trialkyl-substituted ammonium salts include triethylammoniumtetra(phenyl)boron, tripropylammoniumtetra(phenyl)boron, tri(n-butyl)ammoniumtetra(phenyl)boron, trimethylammoniumtetra(p-tolyl) Boron, trimethylammoniumtetra(o-tolyl)boron, tri(n-butyl)ammoniumtetra(pentafluorophenyl)boron, tripropylammoniumtetra(o,p-dimethylphenyl)boron, tri(n-butyl)ammoniumtetra( N,N-dimethylphenyl)boron, tri(n-butyl)ammoniumtetra(p-trifluoromethylphenyl)boron, tri(n-butyl)ammoniumtetra(3,5-ditrifluoromethylphenyl)boron, tri(n -butyl)ammoniumtetra(o-tolyl)boron and the like.

Specific examples of N,N-dialkylanilinium salts include N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)boron, N,N,2,4,6 -pentamethylanilinium tetra(phenyl)boron and the like.

Specific examples of dialkylammonium salts include di(1-propyl)ammoniumtetra(pentafluorophenyl)boron, dicyclohexylammoniumtetra(phenyl)boron and the like.

Furthermore, as ionic compounds, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, ferroceniumtetra(pentafluorophenyl)borate, triphenylcarbeniumpentaphenyl Cyclopentadienyl complexes, N,N-diethylanilinium pentaphenylcyclopentadienyl complexes, boron compounds represented by the following formula [XIII] or [XIV], and the like can also be mentioned. In addition, in the following formula, Et represents an ethyl group.

Specific examples of borane compounds include decaborane;
Bis[tri(n-butyl)ammonium]nonaborate, bis[tri(n-butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium]undecaborate, bis[tri(n-butyl)ammonium]dodecaborate , salts of anions such as bis[tri(n-butyl)ammonium]decachlorodecaborate, bis[tri(n-butyl)ammonium]dodecachlorododecaborate;
metal borane anions such as tri(n-butyl)ammonium bis(dodecahydride dodecaborate) cobaltate (III) and bis[tri(n-butyl)ammonium] bis(dodecahydride dodecaborate) nickelate (III); Examples include salt.

Specific examples of carborane compounds include 4-carbanonabolane, 1,3-dicarbanonabolane, 6,9-dicarbadecaborane, dodecahydride-1-phenyl-1,3-dicarbanonabolane, and dodecahydride. -1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarboundecaborane, 2,7-dicarboundecaborane , undecahydride-7,8-dimethyl-7,8-dicarbaundecaborate, dodecahydride-11-methyl-2,7-dicarbaundecaborate, tri(n-butyl)ammonium 1-carbadecaborate, tri (n-butyl) ammonium-1-carbaundecaborate, tri(n-butyl) ammonium-1-carbadodecaborate, tri(n-butyl) ammonium-1-trimethylsilyl-1-carbadecaborate, tri(n- butyl)ammonium bromo-1-carbadodecaborate, tri(n-butyl)ammonium-6-carbadecaborate, tri(n-butyl)ammonium-7-carbaundecaborate, tri(n-butyl)ammonium-7, 8-dicarbaundecaborate, tri(n-butyl)ammonium-2,9-dicarbaundecaborate, tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, tri(n -Butyl)ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri(n-butyl) ) ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri(n-butyl)ammonium salts of anions such as undecahydride-4,6-dibromo-7-carbaundecaborate;
Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate) Ferrate (III), Tri(n-butyl)ammonium bis(undecahydride-7,8-dicarboundecaborate) cobaltate(III), Tri(n-butyl)ammonium bis(undecahydride-7) ,8-dicarbaundecaborate)nickelate (III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate)cuprate(III), tri(n-butyl) Ammonium bis(undecahydride-7,8-dicarbaundecaborate)aurate (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) Ferrate (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) chromate (III), tri(n-butyl)ammonium bis( Tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III), tris[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate) chromate (III) , bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboundecaborate) manganate (IV), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbohydrate) boundecaborate) cobaltate (III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboundecaborate)nickelate (IV) and the like, and salts of metal carborane anions. be done.

The heteropoly compound consists of atoms selected from silicon, phosphorus, titanium, germanium, arsenic and tin and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus tungstic acid, germanotungstic acid, stannotungstic acid, phosphomolybdovanadate, phosphotungstovanadate, germanotungstovanadate, phosphomolybdotungstovanadate, germanomolybdotungstovanadate, phosphomolybdotungstic acid , phosphomolybdoniobic acid, and salts of these acids, such as metals of Groups 1 and 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and organic salts such as triphenylethyl salts can be used, but are not limited to these.

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

In the present invention, as the polymerization catalyst, the metallocene compound (a) represented by the general formula [A1], an organometallic compound (b-1) such as triisobutylaluminum, an organoaluminumoxy compound (b- 2), and an ionizing ionic compound (b-3) such as triphenylcarbenium tetrakis(pentafluorophenyl)borate, a very high polymerization activity is obtained in the production of the copolymer (A). can be shown.

(c) Particulate Carrier The particulate carrier (c) used as needed in the present invention is an inorganic compound or an organic compound, and is a granular or particulate solid.

As the inorganic compound, porous oxides, inorganic halides, clays, clay minerals or ion-exchange layered compounds are preferred. Specific examples thereof include those described in WO2015/122495.

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

Among these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, hectorite, teniolite and synthetic mica.
Examples of organic compounds include granular or particulate solids with particle sizes ranging from 10 to 300 μm. Specifically, (co)polymers produced mainly from α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, and styrene can be exemplified as a (co)polymer produced as a main component, and a modified product thereof.

The metallocene catalyst used in the present invention is a metallocene compound (a) and at least one selected from an organometallic compound (b-1), an organoaluminumoxy compound (b-2) and an ionized ionic compound (b-3). In addition to the seed compound (b) and the optionally used carrier (c), a specific organic compound component (d) can also be included, if desired.

(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 and sulfonates.

<<Method and conditions for producing copolymer (A)>>
The copolymer (A) comprises ethylene (a1), an α-olefin having 3 to 20 carbon atoms (a2), a non-conjugated polyene (a3), and optionally a non-conjugated polyene (a4). It can be produced by copolymerizing the following monomers.

When such monomers are copolymerized, the method of use and order of addition of each component constituting the polymerization catalyst described above can be arbitrarily selected, and the following methods (1) to (5) are exemplified.
(1) A method of adding the metallocene compound (a) alone to a polymerization vessel.
(2) A method in which the metallocene compound (a) and the compound (b) are added in any order to the polymerization vessel.
(3) A method of adding the catalyst component in which the metallocene compound (a) is supported on the carrier (c) and the compound (b) in an arbitrary order to the polymerization reactor.
(4) A method in which the catalyst component in which the compound (b) is supported on the carrier (c) and the metallocene compound (a) are added in any order to the polymerization reactor.
(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 polymerization reactor.

In each of the above methods (2) to (5), at least two of the metallocene compound (a), compound (b) and carrier (c) may be contacted in advance.
In the above methods (4) and (5) in which the compound (b) is supported, the unsupported compound (b) may be added in any order as necessary. In this case, the compound (b) may be the same as or different from the compound (b) supported on the carrier (c).

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

The above copolymer (A) can be suitably obtained by copolymerizing monomers in the presence of the above polymerization catalyst.
When olefin is polymerized using the polymerization catalyst as described above, the metallocene compound (a) is generally 10 ^-12 to 10 ^-2 mol, preferably 10 ^-10 to 10 ^-8 mol per liter of reaction volume. It is used in an amount such that

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

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

The step of obtaining a polymerization reaction solution includes using an aliphatic hydrocarbon as a polymerization solvent, the metallocene catalyst, preferably R ¹³ and R ¹⁴ bonded to Y ¹ in the general formula [A1] are phenyl groups, or , a phenyl group substituted with an alkyl group or a halogen group, and R ⁷ and R ¹⁰ in the presence of a polymerization catalyst containing a transition metal compound having an alkyl substituent, ethylene (a1), and is a step of copolymerizing a monomer consisting of the α-olefin (a2) of and the non-conjugated polyene (a3) and optionally the non-conjugated polyene (a4) to obtain a polymerization reaction solution of the copolymer (A). .

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; and benzene, toluene, and xylene. and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, which may be used singly or in combination of two or more. Also, the olefin itself can be used as a solvent. Of these, hexane is preferred from the viewpoint of separation and purification from the resulting copolymer (A).

The polymerization temperature is usually -50 to +200°C, preferably 0 to +150°C, more preferably +70 to +110°C. (+70°C or higher) is desirable from the viewpoint of catalytic activity, copolymerizability and productivity.

The polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably 1.1 to 5 MPa gauge pressure, more preferably 1.2 to 2.0 MPa gauge pressure, and the polymerization reaction is a batch system or a semi-continuous system. , continuous method. Furthermore, it is also possible to carry out the polymerization in two or more stages with different reaction conditions. In the present invention, among these methods, it is preferable to employ a method in which monomers are continuously supplied to a reactor for copolymerization.

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. , more preferably 10 minutes to 2 hours.

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

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

The amount of the non-conjugated polyene (a3) to be charged is usually 0.00% per 100% by mass of the total amount of the ethylene (a1), the α-olefin (a2) and the non-conjugated polyene (a3) (total amount of monomers charged). 07 to 10 mass %, preferably 0.1 mass % to 8.0 mass %, more preferably 0.5 mass % to 5.0 mass %.

The present invention preferably includes a step (2) of deactivating the polymerization catalyst by adding a catalyst deactivator after the step (1) of carrying out copolymerization in the presence of the polymerization catalyst.
Alcohols can be used as the catalyst deactivator, and methanol or ethanol is preferable, and ethanol is particularly preferable.

In the step (2), the catalyst deactivator is preferably 0.05 to 3.0 mol times, more preferably 0.06 to 2.5 mol times, the organometallic compound (b-1), More preferably, by adding in an amount of 0.08 to 2.0 mol times, the catalyst degenerated by the catalyst deactivator such as ethanol is slightly generated, and as a result of moderately polymerizing the low molecular weight component, the molecular weight distribution is moderate. A wide copolymer (A) can be obtained. On the other hand, if the amount of the catalyst deactivator added is too large, almost no degraded catalyst is produced and the low-molecular-weight components are hardly polymerized, so that the obtained copolymer (A) tends to have a narrow molecular weight distribution. be. In addition, if the catalyst deactivator is not added or if the amount added is too small, a large amount of alteration catalyst is generated and a large amount of low molecular weight components are polymerized, so the content of low molecular weight components in the obtained copolymer (A) tend to be too many.

<Other polymers>
The ethylene-based copolymer composition of the present invention may contain a polymer (B) other than the ethylene/α-olefin/non-conjugated polyene copolymer (A).

Examples of the other polymer (B) include ethylene/α-olefin copolymers other than the ethylene/α-olefin/non-conjugated polyene copolymer (A).
The α-olefin is usually an α-olefin having 3 to 20 carbon atoms. - Olefins are preferred, and propylene and 1-butene are particularly preferred.

Specific examples of the ethylene/α-olefin copolymer (A) preferably include an ethylene/propylene copolymer and an ethylene/1-butene copolymer.
When the ethylene-based copolymer composition of the present invention contains the other polymer (B), the content of the polymer (B) is 100 parts by weight in total of the copolymer (A) and the polymer (B). , preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight.

<<Magnesium hydroxide (C)>>
Magnesium hydroxide (C), which is one of the components contained in the ethylene-based copolymer composition of the present invention, is magnesium hydroxide having a high aspect ratio.
Magnesium hydroxide (C) has an aspect ratio of 5-100, preferably 10-90, more preferably 50-90.

Since magnesium hydroxide (C) has such a high aspect ratio, the ethylene-based copolymer composition of the present invention exhibits excellent bagging resistance. Magnesium hydroxide with an aspect ratio of less than 5 does not provide good bagging resistance.
Commercial products of magnesium hydroxide (C) having such a high aspect ratio include Kisuma 10 (manufactured by Kyowa Chemical Industry Co., Ltd.).

<<(meth)zinc acrylate (D)>>
The ethylene-based copolymer composition of the present invention contains zinc (meth)acrylate (D). "Zinc (meth)acrylate" means at least one of zinc acrylate and zinc methacrylate. Zinc methacrylate is particularly preferred as zinc (meth)acrylate (D).

Since the ethylene-based copolymer composition of the present invention contains magnesium hydroxide (C) and zinc (meth)acrylate (D) having a high aspect ratio, it exhibits excellent bagging resistance.

<Ethylene-based copolymer composition>
The ethylene-based copolymer composition of the present invention contains an ethylene/α-olefin/non-conjugated polyene copolymer (A), magnesium hydroxide (C), and zinc (meth)acrylate (D). The amount ratio of the ethylene/α-olefin/non-conjugated polyene copolymer (A), magnesium hydroxide (C) and zinc (meth)acrylate (D) is the same as the ethylene/α-olefin/non-conjugated polyene copolymer ( A) 1 to 100 parts by mass of magnesium hydroxide (C) and 0.2 to 50 parts by mass of zinc (meth)acrylate (D) per 100 parts by mass, preferably 1 to 50 parts by mass of magnesium hydroxide (C) Parts by mass, zinc (meth)acrylate (D) 0.5 to 20 parts by mass, more preferably magnesium hydroxide (C) 1 to 30 parts by mass, zinc (meth)acrylate (D) 0.5 to 10 parts by mass.

The ethylene-based copolymer composition of the present invention contains ethylene/α-olefin/non-conjugated polyene copolymer (A), magnesium hydroxide (C) and zinc (meth)acrylate (D) within the above ranges. Therefore, it has excellent bagging resistance.

In addition, the copolymer composition of the present invention contains the ethylene/α-olefin/non-conjugated polyene copolymer (A), magnesium hydroxide (C) and zinc (meth)acrylate (D), and optionally In addition to the polymer (B), softeners, fillers, cross-linking agents, other additives such as processing aids, activators, moisture absorbers, heat stabilizers, weather stabilizers, antistatic agents, coloring Agents, lubricants, thickeners and the like may be added.

When the copolymer composition of the present invention contains another polymer, the proportion of the ethylene/α-olefin/non-conjugated polyene copolymer (A) in the copolymer composition is generally 20 mass. % or more, preferably 30 to 90% by mass.

The copolymer composition of the present invention is optionally blended with an ethylene/α-olefin/non-conjugated polyene copolymer (A), magnesium hydroxide (C) and zinc (meth)acrylate (D). Other components can be prepared by kneading at a desired temperature using a kneader such as a mixer, kneader, or roll. As described above, the copolymer composition according to the present invention is excellent in bagging resistance, so that the copolymer composition can be prepared satisfactorily.

<Crosslinking agent>
Examples of cross-linking agents include organic peroxides, phenolic resins, hydrosilicone compounds, amino resins, quinones or derivatives thereof, amine compounds, azo compounds, epoxy compounds, isocyanate compounds, etc. Commonly used cross-linking agents can be mentioned. Among these, organic peroxides are preferred.

Organic peroxides include dicumyl peroxide (DCP), di-tert-butyl peroxide, 2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert- Butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butyl peroxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxy benzoate, ert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide and the like.

Among these, 2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di- (tert-butylperoxy)hexyne-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4 Bifunctional organic peroxides such as ,4-bis(tert-butylperoxy)valerate are preferred, and among them, 2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5- Di-(tert-butylperoxy)hexane is most preferred.

When an organic peroxide is used as the cross-linking agent, the amount of the ethylene/α-olefin/non-conjugated polyene copolymer (A) and the other polymer that requires cross-linking that is blended as necessary is a total of 100. It is generally 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, more preferably 0.5 to 10 parts by mass. When the amount of the organic peroxide is within the above range, the copolymer composition exhibits excellent cross-linking properties, which is preferable.

Moreover, when using an organic peroxide as a crosslinking agent, it is preferable to use a crosslinking aid together. Examples of cross-linking aids include sulfur; quinonedioxime cross-linking aids such as p-quinonedioxime; acrylic cross-linking aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; diallyl phthalate, triallyl isocyanurate, etc. Allyl cross-linking aid; maleimide cross-linking aid; divinylbenzene; zinc oxide (e.g., ZnO #1, zinc oxide type 2 (JIS standard (K-1410)), manufactured by Hakusui Tech Co., Ltd.), magnesium oxide, Metal oxides such as zinc white (for example, zinc oxide such as "META-Z102" (trade name: manufactured by Inoue Lime Industry Co., Ltd.)). The amount of the cross-linking aid compounded is generally 0.5 to 10 mol, preferably 0.5 to 7 mol, more preferably 1 to 5 mol, per 1 mol of the organic peroxide.

<Softener>
Specific examples of softening agents include petroleum-based softening agents such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and vaseline; coal tar-based softening agents such as coal tar; castor oil, linseed oil, rapeseed oil, Fatty oil-based softeners such as soybean oil and coconut oil; Waxes such as beeswax and carnauba wax; Fatty acids such as ricinoleic acid, palmitic acid, stearic acid, barium stearate and calcium stearate or salts thereof; Rosin or its derivatives; terpene resins, petroleum resins, coumarone-indene resins and other synthetic high-molecular substances; dioctyl phthalate, dioctyl adipate and other ester-based softening agents; Synthetic lubricating oils, tall oils, sub (factice) and the like are included, petroleum-based softeners are preferred, and process oils are particularly preferred.

The blending amount of the softening agent in the copolymer composition is based on a total of 100 parts by mass of the ethylene/α-olefin/non-conjugated polyene copolymer (A) and other polymer components blended as necessary. , generally 2 to 100 parts by weight, preferably 10 to 100 parts by weight.

<Inorganic filler>
Specific examples of inorganic fillers include one or more of light calcium carbonate, heavy calcium carbonate, talc, clay, and the like. Company) is preferred.

When the copolymer composition contains an inorganic filler, the amount of the inorganic filler to be blended is the ethylene/α-olefin/non-conjugated polyene copolymer (A) and other blended as necessary It is usually 2 to 50 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the polymer in total. When the blending amount is within the above range, the kneading processability of the copolymer composition is excellent, and an OA equipment roll excellent in mechanical properties can be obtained.

<Reinforcing agent>
Specific examples of reinforcing agents include carbon black, carbon black surface-treated with a silane coupling agent, silica, calcium carbonate, activated calcium carbonate, finely powdered talc, and finely powdered silicic acid. It is generally 30 to 200 parts by mass, preferably 50 to 180 parts by mass, per 100 parts by mass of the α-olefin/non-conjugated polyene copolymer (A) and optionally other polymers.

<Antiaging agent (stabilizer)>
By adding an anti-aging agent (stabilizer) to the copolymer composition according to the present invention, it is possible to prolong the life of the molded article formed therefrom. Such anti-aging agents include conventionally known anti-aging agents such as amine-based anti-aging agents, phenol-based anti-aging agents, and sulfur-based anti-aging agents.

Further, as antioxidants, aromatic secondary amine-based antioxidants such as phenylbutylamine, N,N-di-2-naphthyl-p-phenylenediamine; Phenolic antioxidants such as t-butyl-4-hydroxy)hydrocinnamate]methane; thioethers such as bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl]sulfide anti-aging agents; dithiocarbamate-based anti-aging agents such as nickel dibutyldithiocarbamate; Examples include sulfur-based anti-aging agents such as dipropionate.

These anti-aging agents can be used singly or in combination of two or more. It is usually 0.3 to 10 parts by weight, preferably 0.5 to 7.0 parts by weight, based on 100 parts by weight in total. Within this range, there is no bloom on the surface of the molded article obtained from the obtained copolymer composition, and the occurrence of vulcanization inhibition can be suppressed.

<Processing aid>
As the processing aid according to the present invention, a wide variety of processing aids generally blended with rubber can be used.
Specific examples of processing aids include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, and esters. Among these, stearic acid is preferred.

The amount of the processing aid compounded is usually 10 parts by mass or less with respect to 100 parts by mass of the ethylene/α-olefin/non-conjugated polyene copolymer (A) and other polymer contained in the copolymer composition. Preferably, it is 8.0 parts by mass or less.

<Activator>
Specific examples of active agents include amines such as di-n-butylamine, dicyclohexylamine, and monoelanolamine; diethylene glycol, polyethylene glycol, lecithin, triarylutemellilate, zinc compounds of aliphatic carboxylic acids or aromatic carboxylic acids, and the like. zinc peroxide preparations; ktadecyltrimethylammonium bromide, synthetic hydrotalcites, special quaternary ammonium compounds, and the like.

The amount of the activator compounded is usually 0.2 to 10 parts by mass, preferably 0.3, per 100 parts by mass of the ethylene/α-olefin/non-conjugated polyene copolymer (A) and other polymers. ~5 parts by mass.

<Moisture absorbent>
Specific examples of moisture absorbents include calcium oxide, silica gel, sodium sulfate, molecular sieves, zeolite, white carbon, and the like.
The amount of the moisture absorbent is usually 0.5 to 15 parts by mass, preferably 1.0 to 100 parts by mass, per 100 parts by mass of the ethylene/α-olefin/non-conjugated polyene copolymer (A) and other polymers. 12 parts by mass.

<Crosslinked product of copolymer composition>
The crosslinked product of the present invention is obtained by crosslinking the copolymer composition.
In order to produce a crosslinked product from the copolymer composition, an unvulcanized rubber composition is prepared by the above-described method in the same manner as when vulcanizing general rubber, and then this rubber composition is Vulcanization may be performed after molding the object into the intended shape.

The unvulcanized rubber composition prepared as described above can be molded and vulcanized by various molding methods. The characteristics can be exhibited most in the case.

In the case of compression molding, for example, a pre-weighed unvulcanized rubber composition is placed in a mold, and after closing the mold, the desired crosslinked product is obtained by heating at a temperature of 120 to 270° C. for 30 seconds to 120 minutes. is obtained.

In the case of injection molding, for example, a ribbon-shaped or pellet-shaped rubber composition is fed into a pot by a predetermined amount by means of a screw. Subsequently, the preheated rubber composition is fed into the mold with a plunger for 1 to 20 seconds. After injecting the rubber composition, it is heated at a temperature of 120 to 270° C. for 30 seconds to 120 minutes to obtain the desired crosslinked product.

In the case of injection molding, for example, a pre-weighed rubber composition is placed in a pot and injected into the mold by a piston in 1 to 20 seconds. By heating at a temperature of 120 to 270° C. for 30 seconds to 120 minutes after injecting the rubber composition, the desired crosslinked product can be obtained.

<Uses of the copolymer composition>
Various products can be obtained by molding the crosslinked product obtained from the copolymer composition into a desired shape.

As described above, the copolymer composition according to the present invention is excellent in bagging resistance, heat aging resistance and extrudability. Therefore, the copolymer composition of the present invention can be suitably used for hoses. A hose product having excellent performance can be obtained from the copolymer composition of the present invention.

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. The methods for evaluating physical properties in the following examples and comparative examples are as follows.

<Composition of ethylene/α-olefin/non-conjugated polyene copolymer>
The weight fraction (% by mass) of each structural unit in the ethylene/α-olefin/non-conjugated polyene copolymer was determined by ¹³ C-NMR measurement. The measured values were obtained using an ECX400P type nuclear magnetic resonance apparatus (manufactured by JEOL Ltd.) at a measurement temperature of 120°C, a measurement solvent of ortho-dichlorobenzene/deuterated benzene = 4/1, and an accumulation 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 obtained by a 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 Wiss reagent and 20% potassium iodide solution, and dissolve with 0.1 mol/L sodium thiosulfate solution. determined. Near the end point, a starch indicator was added, and the solution was titrated until the light purple color disappeared while stirring well.

<Intrinsic viscosity>
The intrinsic viscosity [η] was measured using a fully automatic intrinsic viscometer manufactured by Rigosha 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 values measured by gel permeation chromatography (GPC). The measuring equipment and conditions are as follows. Moreover, the molecular weight was calculated based on the conversion method by creating a calibration curve using commercially available monodisperse polystyrene.
Apparatus: Gel Permeation Chromatograph Alliance GP2000 (manufactured by Waters),
Analysis device: Empower2 (manufactured by Waters),
Column: TSKgel GMH6-HT × 2 + TSKgel GMH6-HTL × 2 (7.5 mm ID × 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 Corporation),
Molecular weight conversion: old method EPR conversion/calibration method considering viscosity.

<Low molecular weight component>
When the chart obtained by the above GPC measurement shows two or more peaks, the ratio (%) of the area of the peak appearing on the side with the lowest molecular weight to the total peak area is The content of low-molecular-weight components was defined as the content. In addition, when the chart obtained by GPC measurement showed only one peak, the content of the low molecular weight component was taken as 0%.

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

<Number of long chain branches per 1000 carbon atoms (LCB _1000c )>
The long chain branching number (LCB _1000c ) was measured by the method described above.

<Bagging resistance>
The bagging resistance of the composition was evaluated from the state of the composition when the formulations obtained in the first stage of Examples and Comparative Examples were kneaded with a roll. Bagging resistance was evaluated according to the following ratings 1 to 5. Examples of specific aspects corresponding to the grades 1 to 5 are shown in (1-1) to (1-5) of FIG. 1, respectively.
Rating 1: The composition does not wrap around the roll at all and is immediately bagged.
Rating 2: The composition temporarily wraps around the roll, but immediately peels off from the roll and bags.
Rating 3: The composition wraps around the roll and often peels off from the bank portion, but does not bag.
Rating 4: The composition easily winds around the roll, and very rarely peels off from the bank portion, but does not bag.
Rating 5: The composition easily winds around the roll, does not peel off from the bank portion at all, and does not bag.

<Extrudability>
First, a ribbon for extruder feed prepared using the formulations obtained in the first stage of Examples and Comparative Examples was fed to an extruder, and a hollow tube was extruded at a speed of 6 m/min. After that, the extrudability was evaluated from the surface state of the extruded tube. Extrudability was evaluated according to the following ratings 1-5.
Rating 1: The surface has undulations, has significant hangnails, and has no gloss.
Rating 2: No undulations on the surface, significant hangnails, and no gloss.
Rating 3: No undulations on the surface, fine but not significant burrs, and no gloss.
Rating 4: There is no undulation on the surface, there is almost no flaking, and there is some gloss.
Rating 5: There is no undulation on the surface, there is no burr, and the gloss is clearly present.

<Evaluation of physical properties of unvulcanized rubber>
(1) Mooney viscosity (ML (1+4) 125°C)
The Mooney viscosity at 125°C (ML(1+4) 125°C) was measured at 125°C using a Mooney viscometer (Model SMV202 manufactured by Shimadzu Corporation) in accordance with JIS K6300.

(2) Vulcanization rate Using the uncrosslinked rubber compositions in Examples and Comparative Examples, the vulcanization rate was measured under measurement conditions of a temperature of 160°C and a time of 30 minutes using a measuring device: MDR2000 (manufactured by ALPHA TECHNOLOGIES). (TC90) was measured as follows.

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

<Physical properties of vulcanized rubber>
(1) Hardness test (Duro-A hardness)
In accordance with JIS K 6253, the sheet hardness (type A durometer, HA) was measured using six 2 mm vulcanized rubber sheets with a smooth surface, the flat portions of which were stacked to a thickness of about 12 mm. However, test pieces containing foreign matter, air bubbles, and scratches were not used. In addition, the size of the measurement surface of the test piece was such that the tip of the incisor can be measured at a position 12 mm or more away from the edge of the test piece.

(2) Tensile test The vulcanized rubber sheets obtained in Examples and Comparative Examples were punched to prepare No. 3 dumbbell test pieces described in JIS K 6251 (2001). Using this test piece, according to the method specified in JIS K6251, a tensile test was performed under the conditions of a measurement temperature of 25 ° C. and a tensile speed of 500 mm / min. Modulus (M100), 200% modulus (M200), 300% modulus (M300), tensile stress at break (TB) and tensile elongation at break (EB) were measured.

<Crosslinking density>
The crosslink density ν was calculated from the following Flory-Rehner formula (a) using equilibrium swelling. V _R in the formula (a) was obtained by extracting a crosslinked 2 mm sheet with toluene under conditions of 37° C.×72 hours.

[Production Example 1]
Using the continuous polymerization apparatus shown in FIG. 2, an ethylene/propylene/VNB copolymer (A-1) was produced as follows.
In a polymerization reactor C having a volume of 300 liters, 58.3 L/hr of a dehydrated and purified hexane solvent is added from a tube ₆ , 4.5 mmol/hr of triisobutylaluminum (TiBA) is added from a tube 7, and ( _C6H5 ) _3CB ( C ₆ F ₅ ) ₄ was continuously fed at 0.150 mmol/hr and di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride at 0.030 mmol/hr. . At the same time, 6.6 kg/hr of ethylene, 9.3 kg/hr of propylene, 18 liters/hr of hydrogen, and 340 g/hr of VNB were continuously fed into the polymerization reactor C through pipes 2, 3, 4, and 5, respectively. Then, copolymerization was carried out under conditions of a polymerization temperature of 87° C., a total pressure of 1.6 MPaG, and a residence time of 1.0 hour.

The ethylene/propylene/VNB copolymer solution produced in the polymerization reactor C was continuously discharged through the pipe 8 at a flow rate of 88.0 liters/hr and heated to 170° C. (pressure was 4.1 MPaG ) and fed to the phase separator D. At this time, ethanol as a polymerization inhibitor was continuously introduced into the tube 8 in an amount of 0.1 mol times the amount of TiBA in the liquid component extracted from the polymerization reactor C.

In the phase separator D, the ethylene-propylene-VNB copolymer solution is divided into a rich phase (lower phase) containing most of the ethylene-propylene-VNB copolymer and a dilute phase (upper phase) containing a small amount of polymer. ) and separated.

The separated dense phase is led at a flow rate of 85.4 liters/hr to a heat exchanger K through a pipe 11 and further to a hopper E, where the solvent is evaporated and separated to produce an ethylene/propylene/VNB copolymer. was obtained in an amount of 7.8 kg/hr.

The physical properties of the obtained ethylene/propylene/VNB copolymer (A-1) were evaluated as described above. Table 1 shows the results. The molecular weight distribution of the copolymer (A-1) thus obtained was bimodal.

[Example 1]
As the first step, 60 parts by weight of the ethylene/propylene/VNB copolymer (A-1) obtained in Production Example 1 and the ethylene/propylene copolymer were mixed using a BB-4 type Banbury mixer (manufactured by Kobe Steel, Ltd.). 40 parts by weight was masticated for 1 minute, then 10 parts by weight of high aspect ratio magnesium hydroxide having an aspect ratio of 67 (Kisuma 10, manufactured by Kyowa Chemical Industry Co., Ltd.), 2 parts by weight of zinc methacrylate, zinc Hana (ZnO #1, manufactured by Hakusui Tech Co., Ltd.) 5 parts by weight, talc (Mistron Vapor Talc, manufactured by Nihon Mistron Co., Ltd.) 80 parts by weight, carbon black (Asahi #60UG, manufactured by Asahi Carbon Co., Ltd.) 50 parts by weight , Paraffin-based process oil (Diana Process PW-380, manufactured by Idemitsu Kosan Co., Ltd.) 24 parts by weight, primary anti-aging agent (Irganox 1010, manufactured by BASF) 3 parts by weight, secondary anti-aging agent (Sundant MB, Sanshin Kagaku Kogyo Co., Ltd.) and 1 part by weight of stearic acid were added and kneaded at 140° C. for 2 minutes. After that, the ram was raised and cleaned, and kneading was carried out for 1 minute, and the kneaded material was discharged at about 150°C to obtain the first stage compound.

Next, as the second step, the compound obtained in the first step is applied to a 6-inch roll (manufactured by Nippon Roll Co., Ltd., front roll surface temperature 50 ° C., rear roll surface temperature 50 ° C., front roll 6.8 parts by weight of dicumyl peroxide (DCP-40C, manufactured by Kayaku Akzo Co., Ltd.) was added to this and kneaded for 10 minutes to form an uncrosslinked rubber. A formulation was obtained. Using this rubber compound, unvulcanized rubber physical properties were evaluated.

This uncrosslinked rubber compound was cut into a sheet and pressed at 160° C. for 20 minutes using a 100-ton press molding machine to prepare a vulcanized rubber sheet having a thickness of 2 mm. Using this, vulcanized rubber properties were evaluated, and crosslink density, compression set and dynamic modulus were measured. Table 2 shows the results.

[Comparative Example 1]
A rubber composition and a crosslinked product were produced in the same manner as in Example 1, except that the magnesium hydroxide (C) Kisuma 10 and zinc methacrylate were not blended, and the same evaluation as in Example 1 was performed. rice field. Table 2 shows the results.

1) to 9) in Table 2 are as follows.
1) Stearic acid (bead stearic acid Tsubaki, manufactured by NOF Corporation)
2) Zinc white (ZnO#1, manufactured by Hakusui Tech Co., Ltd.)
3) Antiaging agent (Irganox 1010, manufactured by BASF)
4) Anti-aging agent (Sundant MB, manufactured by Sanshin Chemical Industry Co., Ltd.)
5) Carbon black (Asahi #60UG, manufactured by Asahi Carbon Co., Ltd.)
6) Talc (Mistron Vapor Talc, manufactured by Nippon Mistron Co., Ltd.)
7) Paraffin-based process oil (Diana Process PW-380, manufactured by Idemitsu Kosan Co., Ltd.)
8) Magnesium hydroxide (Kisuma 10, manufactured by Kyowa Chemical Industry Co., Ltd.)
9) Dicumyl peroxide (DCP-40C, manufactured by Kayaku Akzo Co., Ltd.)

C polymerization reactor D phase separator E hopper F pump G heat exchanger H heat exchanger

Claims (7)

An ethylene/α-olefin having a structural unit derived from ethylene (a1), a structural unit derived from an α-olefin having 3 to 20 carbon atoms (a2), and a structural unit derived from a non-conjugated polyene (a3). - A non-conjugated polyene copolymer (A), and 1 to 100 parts by weight of hydroxylation having an aspect ratio of 5 to 100 per 100 parts by weight of the ethylene/α-olefin/non-conjugated polyene copolymer (A) containing magnesium (C) and 0.2 to 50 parts by mass of zinc (meth)acrylate (D) relative to 100 parts by weight of the ethylene/α-olefin/non-conjugated polyene copolymer (A) ;
The ethylene -based copolymer composition, wherein the copolymer (A) satisfies the following conditions (i) to (vii):
(i) the molar ratio [(a1)/(a2)] of structural units derived from ethylene (a1) to structural units derived from α-olefin (a2) is 40/60 to 99.9/0. is 1;
(ii) the weight fraction of structural units derived from the non-conjugated polyene (a3) is 0.07% by mass to 10% by mass in 100% by mass of the copolymer (A);
(iii) the weight average molecular weight (Mw) of the copolymer (A), the weight fraction of the constituent units derived from the non-conjugated polyene (a3) (the weight fraction (% by mass) of (a3)), and the non-conjugated The molecular weight of the polyene (a3) (molecular weight of (a3)) satisfies the following formula (1);
4.5≦Mw×weight fraction of (a3)/100/molecular weight of (a3)≦40 (1)
(iv) Complex viscosity η ^* ₍ ω _{= 0.1)} (Pa sec) at frequency ω = 0.1 rad/s, obtained by linear viscoelasticity measurements (190°C) using a rheometer, and frequency ω = The ratio P ( η ^* ₍ ω _=0.1) / η ^* ₍ ω ₌₁₀₀₎ ) to the complex viscosity η ^* ₍ ω ₌₁₀₀₎ (Pa·sec) at 100 rad/s, the intrinsic viscosity [ η] , and the non- The weight fraction of structural units derived from the conjugated polyene (a3) (the weight fraction of (a3)) satisfies the following formula (2);
P/([ η] ^2.9 )≦(a3) weight fraction×6 (2)
(v) the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) (molecular weight distribution; Mw/Mn) is in the range of 8 to 30;
(vi) the number average molecular weight (Mn) is 30,000 or less;
(vii) A chart obtained by GPC measurement shows two or more peaks, and the area of the peak appearing on the side of the lowest molecular weight is in the range of 1 to 20% of the total peak area. 2. The ethylene system according to claim 1 , wherein the non-conjugated polyene (a3) contains a total of two or more partial structures selected from the group consisting of the following general formulas (I) and (II) in the molecule. Copolymer composition.

3. The ethylene copolymer composition according to claim 1, wherein the non-conjugated polyene (a3) contains 5-vinyl-2-norbornene (VNB). The ethylene copolymer composition according to any one of claims 1 to 3 , wherein the α-olefin (a2) is propylene. The ethylene copolymer composition according to any one of claims 1 to 4 , which is used for hoses. A crosslinked product of the ethylene copolymer composition according to any one of claims 1 to 5 . A hose product comprising the crosslinked body according to claim 6 .

Images