TWI765009B - Ethylene. Alpha-olefins. Non-conjugated polyene copolymer, its production method and use - Google Patents

Abstract

An object of the present invention is to provide a novel ethylene·α which contains a specific non-conjugated polyene such as VNB as a copolymerization component, has a small content of long-chain branches, has excellent curing properties when cross-linked with peroxide, and is good in processability. - Olefin·non-conjugated polyene copolymer. The ethylene·α-olefin·non-conjugated polyene copolymer of the present invention is characterized by having derived from ethylene (A), an α-olefin (B) having 3 to 20 carbon atoms, and a molecule containing in the molecule a compound selected from the group consisting of the following general The partial structure of the group constituted by the formulae (I) and (II) is a total of two or more structural units of the non-conjugated polyene (C), and satisfies specific requirements.

Description

Ethylene·α-olefin·non-conjugated polyene copolymer, its production method and use

The present invention relates to a novel ethylene·α-olefin·non-conjugated polyene copolymer, its production method and use.

Ethylene·α-olefin rubber, represented by ethylene·propylene·non-conjugated diene copolymer rubber (EPDM), has no unsaturated bonds in the main chain of its molecular structure. It is a rubber that has excellent heat resistance and weather resistance, so it is widely used in automotive parts, wire materials, construction and civil engineering materials, industrial parts, and various resin modification materials.

烯(以下亦稱為「VNB」)等非共軛多烯作為共聚合成分的情況，已知其交聯速度快。 In the case of cross-linking ethylene·α-olefin-based rubber with peroxide, especially in the case of containing 5-vinyl-2-nor

When a non-conjugated polyene such as ene (hereinafter also referred to as "VNB") is used as a copolymerization component, it is known that the crosslinking speed is high.

However, the ternary copolymers of ethylene·α-olefin·VNB produced by using existing catalysts often have long-chain branches generated by the terminal vinyl group of VNB. At this time, most of the terminal vinyl group of VNB in the copolymer is consumed, the effect of improving the crosslinking speed is insufficient, and the processability during molding or the physical properties after processing may be reduced due to long chain branching. Such long-chain branching is also generated when a palladium-based catalyst is used, and in particular, when a metallocene-based catalyst is used for polymerization, the content of long-chain branching tends to increase.

In Patent Document 1 and Patent Document 2, it is described that the use of a metallocene system The ethylene-based copolymer containing structural units derived from ethylene, α-olefin and VNB, which is polymerized by the catalyst; Patent Document 1 describes that the copolymer is suitable for foam molding; Patent Document 2 describes that it can be formed into surface appearance, strength properties, Rubber moldings with excellent heat aging resistance and light resistance, and small compression set. However, the ethylene-based copolymerization system obtained by these techniques has a larger content of long chain branches.

烯(ENB)之單體單位的聚合物的方法，並記載有以高VNB含有率製造低分支度之EPDM聚合物。然而，專利文獻3記載之EPDM聚合物中，由於共聚合體每1分子之二烯個數過多，故有使用其所得之成形體不具有充分耐熱老化性的問題。 Patent Document 3 describes the use of a Group 4 metal compound having a single cyclopentadienyl ligand and a monosubstituted nitrogen ligand as a catalyst system, an alumoxane and a catalyst activator to produce a catalyst containing Ethylene, alpha-olefins, VNB and 5-ethylene-2-nor

A method of polymerizing a monomer unit of ene (ENB) is described, and it is described that a low branched EPDM polymer is produced with a high VNB content. However, in the EPDM polymer described in Patent Document 3, since the number of dienes per molecule of the copolymer is too large, there is a problem that the molded article obtained by using the same does not have sufficient heat aging resistance.

Under such circumstances, the emergence of a novel ethylene-α-olefin-based rubber containing a non-conjugated polyene such as VNB as a copolymerization component and having a small content of long-chain branches is desired.

In addition, conventionally, styrene-butadiene rubber (SBR) is widely used for tire applications such as automobiles. Diene-based rubbers such as styrene-butadiene rubber have insufficient weather resistance alone, so when tires and other applications are used outdoors for a long time, in order to improve the weather resistance, amine-based anti-aging agents or paraffin-based waxes are usually added. etc. to use. However, in diene-based rubber products formulated with amine-based antiaging agents or paraffin-based waxes, these components may ooze out to the surface and discoloration may occur over time. In addition, during storage in stores, etc., appearance deterioration such as discoloration and dusting due to oozing may occur, resulting in a decrease in product value. Therefore, it is desired to improve the weather resistance by the rubber component itself.

In order to solve this problem, it has been reviewed to formulate ethylene-propylene and diene rubber (EPDM) for styrene-butadiene rubber to improve weather resistance. When styrene-butadiene rubber and EPDM are thermally cross-linked, Phase separation easily occurs, and there is a problem that sufficient fatigue resistance cannot be obtained.

The applicant of the present application proposed a rubber composition containing a random copolymer rubber composed of structural units derived from ethylene, α-olefin, and a specific triene compound, a diene-based rubber, carbon black, and a vulcanizing agent (refer to Patent Document 4) . In this rubber composition, since the ethylene·α-olefin·triene random copolymer rubber exhibits a vulcanization rate almost as fast as that of the diene rubber, phase separation with the diene rubber is unlikely to occur, and the two The original excellent mechanical strength of olefin rubber is suitable for tire sidewall applications.

In addition, the applicant of the present application discovered and proposed a non-conjugated polyene-based copolymer containing a structural unit derived from an α-olefin and a structural unit derived from a non-conjugated polyene, and a softener. The rubber composition of rubber is suitable for the formation of tires excellent in braking performance and fuel efficiency (refer to Patent Documents 5 and 6).

At present, in tire manufacturing, an uncrosslinked composition mainly composed of diene-based rubber such as styrene-butadiene-based rubber or natural rubber is molded into a sheet shape, etc., and only the surface is subjected to electron beam treatment. After cross-linking to prevent sag, it is assembled into a tire shape, mainly using the step of sulfur cross-linking.

Furthermore, diene-based rubbers such as natural rubber (NR), styrene-butadiene rubber (SBR), butadiene rubber (BR), etc., are known to be excellent in dynamic fatigue resistance and dynamic characteristics, and are used. It is used as raw rubber for automobile tires and anti-vibration rubber. However, nowadays, the environments in which these rubber products are used are greatly changed, and the heat resistance and weather resistance of the rubber products are required to be improved. However, in the past, the superior machinery possessed by the current diene-based rubbers has not been maintained It is a rubber with good weather resistance under the characteristics, fatigue resistance and dynamic characteristics.

In addition, the diene-based rubber with excellent mechanical properties, dynamic fatigue resistance and dynamic properties, and the ethylene-carbon number of ethylene-propylene and non-conjugated diene copolymer rubber (EPDM) with excellent heat resistance and weather resistance Various examinations have been carried out on the blended rubber compositions of α-olefin and non-conjugated polyene copolymers of 3 to 20. However, the level of dynamic characteristics possessed by ethylene, α-olefin having 3 to 20 carbon atoms, and non-conjugated polyene copolymers is different from the level of dynamic characteristics possessed by diene-based rubbers. A blended rubber composition showing uniform physical properties. In addition, the dynamic characteristics of automobile tires depend on the material that deteriorates fuel consumption. The index is the tanδ (loss tangent) value. The lower the tanδ value, the better the dynamic characteristics.

On the other hand, with regard to anti-vibration rubber products for automobiles, due to the high temperature in the engine room, the anti-vibration rubber products based on natural rubber, which is a diene-based rubber, have not been able to obtain fatigue resistance that can withstand practical use. However, the appearance of a novel rubber material having superior heat resistance and having mechanical properties, dynamic properties, and fatigue resistance equal to or higher than those of diene-based rubbers has been desired.

In general, in order to improve dynamic properties, it is necessary to increase the crosslinking density. However, according to the existing technology, if the dynamic properties of ethylene, α-olefin with 3 to 20 carbon atoms, and non-conjugated polyene copolymers are to be equal to those of diene rubbers such as NR, the crosslinking density becomes too high. As a result, mechanical properties such as tensile elongation at break deteriorate, and physical properties such as dynamic properties cannot be taken into consideration.

In addition, in the vibration-proof rubber composed of ethylene·α-olefin·non-conjugated polyene copolymer, in order to improve the vibration-proof characteristics, that is, to reduce the dynamic amplification ratio, it is considered to use a copolymer with a high molecular weight and suppress the amount of filler used. , It is effective to increase the cross-linking density, and various reviews are carried out for its methods.

However, the high molecular weight ethylene·α-olefin·non-conjugated polyene copolymer has the problem of difficulty in kneading due to the high viscosity of the polymer itself. In addition, in order to improve the anti-vibration properties, it is required to further increase the crosslinking density as described above, but there is a problem that mechanical properties such as elongation are reduced due to this. In addition, among the anti-vibration rubber products, a high degree of heat resistance is particularly required in applications such as anti-vibration rubber for automobiles, especially muffler hangers.

Under such circumstances, the applicant of the present application proposed: ethylene·α, which contains a specific non-conjugated polyene such as VNB as a copolymerization component, has a small content of long-chain branches, and is excellent in curing properties when cross-linked with peroxide. - Olefin·non-conjugated polyene copolymer; composed of this copolymer, phase separation does not occur during manufacture, improves the weather resistance of rubber components such as styrene-butadiene-based rubber or natural rubber, prevents deterioration of appearance, and has weather resistance A cross-linked molded product with excellent properties; and containing this copolymer, the cross-link density is easily increased, the vibration-proof properties are excellent, and the elongation is not easily reduced even if the cross-link density is increased. Sufficient strength is obtained, and heat resistance is also excellent, and it is suitable for producing a resin composition of vibration-proof rubber products (refer to Patent Document 7).

However, since the ethylene·α-olefin·non-conjugated polyene copolymer obtained in Patent Document 7 is narrow in molecular weight distribution (Mw/Mn) of about 2, the workability and the like are not necessarily sufficient. In addition, the conventional EPDM polymer containing many low molecular weight components suffers from problems such as reduced crosslinking density and stickiness.

[Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2011-231260

Patent Document 2: International Publication No. 2009/072503

Patent Document 3: Japanese Patent Publication No. 2007-521371

Patent Document 4: Japanese Patent Laid-Open No. 2001-123025

Patent Document 5: International Publication No. 2005/105912 Specification

Patent Document 6: International Publication No. 2005/105913 Specification

Patent Document 7: International Publication No. 2015/122495

An object of the present invention is to provide a novel ethylene that contains a specific non-conjugated polyene such as VNB as a copolymerization component, has a small content of long chain branches, is excellent in curing properties when cross-linked with a peroxide, and has good processability. Alpha-olefin·non-conjugated polyene copolymer, production method and use of the ethylene·α-olefin·non-conjugated polyene copolymer.

Another object of the present invention is to provide a cross-linked molded body excellent in weather resistance without phase separation during production, improving the weather resistance of rubber components such as styrene-butadiene rubber and natural rubber, preventing appearance deterioration.

Furthermore, the object of the present invention is to provide a cross-linking density that is easy to increase and has excellent vibration-proof properties, and that the elongation is not easily reduced even when the cross-linking density is increased. It has excellent properties and is suitable for resin compositions for the manufacture of anti-vibration rubber products, as well as anti-vibration rubber products.

The inventors of the present invention have made intensive studies in order to achieve the above-mentioned problems, and as a result, they have found that an ethylene·α-olefin·non-conjugated polyene copolymer obtained by copolymerization using a specific catalyst under special conditions exhibits bimodality. It has a broad molecular weight distribution, contains structural units from specific non-conjugated polyenes such as VNB, and has few long-chain branches. It can be cross-linked by peroxide at a relatively fast speed, and has good processability. The characteristics after cross-linking are also Excellent, and the present invention was completed.

Furthermore, the present inventors have found that a cross-linked molded product obtained by cross-linking a composition containing the above-mentioned ethylene·α-olefin·non-conjugated polyene copolymer and a rubber component such as a diene rubber can be used in the production of The present invention has been completed without phase separation during, especially during cross-linking, and excellent in weather resistance.

The ethylene·α-olefin·non-conjugated polyene copolymer of the present invention is characterized by having derived from ethylene (A), an α-olefin (B) having 3 to 20 carbon atoms, and a molecule containing in the molecule a compound selected from the group consisting of the following general The partial structure of the group constituted by the formulae (I) and (II) is a total of two or more structural units of the non-conjugated polyene (C), and satisfies the following requirements (i) to (vii).

(i) The molar ratio of ethylene/α-olefin is 40/60 to 99.9/0.1.

(ii) The weight fraction of the structural unit derived from the non-conjugated polyene (C) is 0.07% by weight to 10% by weight in 100% by weight of the ethylene·α-olefin·non-conjugated polyene copolymer.

(iii) Weight average molecular weight (Mw) of ethylene·α-olefin·non-conjugated polyene copolymer, weight fraction of constituent units derived from non-conjugated polyene (C) (weight fraction of (C) (weight fraction) %)), and the molecular weight of the non-conjugated polyene (C) (the molecular weight of (C)) satisfy the following formula (1).

4.5≦Mw×(C) weight fraction/100/(C) molecular weight≦40...Formula (1)

(iv) Complex viscosity η ^* ₍ ω _=0.1) (Pa·sec) at frequency ω=0.1rad/s and frequency ω=100rad/s obtained by linear viscoelasticity measurement (190°C) using a rheometer The ratio of complex viscosity η ^* ₍ ω ₌₁₀₀₎ (Pa·sec) at time P(η ^* ₍ ω _=0.1) /η ^* ₍ ω ₌₁₀₀₎ ), limiting viscosity [η], the above are derived from non-conjugated The weight fraction of the constituent unit of the olefin (C) (the weight fraction of (C)) satisfies the following formula (2).

Weight fraction of P/([η] ^2.9 )≦(C)×6...Formula (2)

(v) The ratio (molecular weight distribution: Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is in the range of 8 to 30.

(vi) The above-mentioned number average molecular weight (Mn) is 30,000 or less.

(vii) The graph obtained by GPC measurement shows two or more peaks, and the area of the peak appearing on the side with the smallest molecular weight is 20% or less of the entire peak area.

According to the present invention, there is provided a novel ethylene·α-olefin·non-copolymer that contains a specific non-conjugated polyene such as VNB as a copolymerization component, has a small content of long-chain branches, and is excellent in curing properties when cross-linked with a peroxide. Conjugated polyene copolymer, production method and application of the ethylene·α-olefin·non-conjugated polyene copolymer.

In addition, the ethylene·α-olefin·non-conjugated polyene copolymerization system of the present invention is excellent in formability, crosslinking characteristics, hardening characteristics and processability, and the resulting formed system has an excellent balance of physical properties such as mechanical properties and is excellent in heat aging resistance. In particular, the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention exhibits an unexpectedly excellent effect of high crosslinking density after crosslinking, even if it contains low molecular weight components and has good processability.

In addition, according to the present invention, it is possible to provide a product that does not undergo phase separation, exhibits excellent weather resistance even when used in applications such as exposure to outside air or sunlight for a long time, and does not cause deterioration of appearance due to bleeding of additives and the like. A crosslinked molded body and a method for producing the same. In addition, according to the method for producing a cross-linked molded article of the present invention, by using a composition having extremely excellent cross-linking properties for cross-linking, cross-linking can be performed even if only electron beam cross-linking is required, and high temperature and long-term exposure can be avoided. The cross-linking can prevent the phase inside the cross-linked shaped body The resulting cross-linked molding system has excellent mechanical properties and surface properties, as well as excellent weather resistance, and can be suitable for applications requiring weather resistance such as tire component applications or wire coating applications.

Furthermore, according to the present invention, the crosslinking density can be easily increased, and the elongation is not easily reduced even when the crosslinking density is increased, and even with a molecular weight in a range where kneading is easy, a molding with sufficient strength and heat resistance can be obtained. It is a resin composition suitable for the manufacture of anti-vibration rubber products. That is, according to the present invention, it is possible to provide a resin composition and an anti-vibration rubber product having a remarkable effect of simultaneously achieving vibration-proof properties and heat aging resistance, and having excellent balance of mechanical properties such as kneading properties, vibration-proof properties, and elongation. In addition, the anti-vibration rubber product of the present invention has good rubber properties, excellent anti-vibration properties, and excellent heat resistance, and can be suitably used for anti-vibration rubber products for automobiles, especially muffler hangers that require high heat resistance. use.

1~13‧‧‧Tube

C‧‧‧polymerization reactor

D‧‧‧Phase Separator

E‧‧‧Funnel

F‧‧‧pump

G‧‧‧Heat exchanger

H‧‧‧Heat exchanger

I‧‧‧Heat exchanger

J‧‧‧Heat exchanger

K‧‧‧Heat exchanger

Fig. 1 is a schematic diagram of a continuous polymerization apparatus used in the examples.

The present invention will be described in detail below.

[Ethylene・α-olefin・Non-conjugated polyene copolymer]

The ethylene·α-olefin·non-conjugated polyene copolymer (ethylene·α-olefin·non-conjugated polyene copolymer (S)) of the present invention has α derived from ethylene (A) and having 3 to 20 carbon atoms. - Olefin (B), and a structural unit containing in the molecule two or more non-conjugated polyene (C) in total of partial structures selected from the group consisting of the following general formulae (I) and (II).

[hua 2]

Examples of the α-olefin (B) having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, etc. Among these, α-olefins having 3 to 8 carbon atoms such as propylene, 1-butene, 1-hexene, and 1-octene are preferable, and propylene is particularly preferable. Such α-olefin-based raw materials are relatively inexpensive, and the obtained ethylene·α-olefin·non-conjugated polyene copolymer exhibits excellent mechanical properties, and furthermore, a molded body with rubber elasticity can be obtained, which is preferable. One of these α-olefins may be used alone, or two or more of them may be used.

That is, the ethylene·α-olefin·non-conjugated polyene copolymerization system of the present invention contains at least one structural unit derived from α-olefin (B) having 3 to 20 carbon atoms, and may also contain two or more types of structural units derived from Constituent unit of α-olefin (B) having 3 to 20 carbon atoms.

烯(VNB)、降

二烯、1,4-己二烯、二環戊二烯等。此等之中，由取得容易性高、聚合後之交聯反應時與過氧化物之反應性良好、聚合體組成物之耐熱性容易提升而言，較佳係非共軛多烯(C)含有VNB，更佳係非共軛多烯(C)為VNB。非共軛多烯(C)可單獨使用1種，亦可使用2種以上。 Examples of the non-conjugated polyene (C) containing in the molecule two or more partial structures selected from the group consisting of general formulae (I) and (II) in total include 5-vinyl-2-nor

alkene (VNB),

Diene, 1,4-hexadiene, dicyclopentadiene, etc. Among them, the non-conjugated polyene (C) is preferred in terms of high availability, good reactivity with peroxides in the crosslinking reaction after polymerization, and easy improvement in the heat resistance of the polymer composition It contains VNB, more preferably the non-conjugated polyene (C) is VNB. A non-conjugated polyene (C) may be used individually by 1 type, and may use 2 or more types.

The ethylene·α-olefin·non-conjugated polyene copolymerization system of the present invention is in addition to the constituent units derived from ethylene (A), α-olefin (B) having 3 to 20 carbon atoms, and the above-mentioned non-conjugated polyene (C) In addition, it may further contain a structural unit derived from a non-conjugated polyene (D) containing only one partial structure selected from the group consisting of the general formulae (I) and (II) in the molecule. bit. A non-conjugated polyene (D) may be used individually by 1 type, and may use 2 or more types.

烯(ENB)、5-亞甲基-2-降

烯、5-(2-丙烯基)-2-降

烯、5-(3-丁烯基)-2-降

烯、5-(1-甲基-2-丙烯基)-2-降

烯、5-(4-戊烯基)-2-降

烯、5-(1-甲基-3-丁烯基)-2-降

烯、5-(5-己烯基)-2-降

烯、5-(1-甲基-4-戊烯基)-2-降

烯、5-(2,3-二甲基-3-丁烯基)-2-降

烯、5-(2-乙基-3-丁烯基)-2-降

烯、5-(6-庚烯基)-2-降

烯、5-(3-甲基-5-己烯基)-2-降

烯、5-(3,4-二甲基-4-戊烯基)-2-降

烯、5-(3-乙基-4-戊烯基)-2-降

烯、5-(7-辛烯基)-2-降

烯、5-(2-甲基-6-庚烯基)-2-降

烯、5-(1,2-二甲基-5-己烯基)-2-降

烯、5-(5-乙基-5-己烯基)-2-降

烯、5-(1,2,3-三甲基-4-戊基)-2-降

烯等。此等之中，由取得容易性高、於聚合後之交聯反應時與硫或硫化促進劑間之反應性高、容易控制交聯速度、容易得到良好之機械物性而言，較佳為ENB。 As such a non-conjugated polyene (D), for example, 5-ethylene-2-nor

Alkene (ENB), 5-methylene-2-nor

Alkene, 5-(2-propenyl)-2-nor

alkene, 5-(3-butenyl)-2-nor

Alkene, 5-(1-methyl-2-propenyl)-2-nor

alkene, 5-(4-pentenyl)-2-nor

alkene, 5-(1-methyl-3-butenyl)-2-nor

alkene, 5-(5-hexenyl)-2-nor

alkene, 5-(1-methyl-4-pentenyl)-2-nor

alkene, 5-(2,3-dimethyl-3-butenyl)-2-nor

alkene, 5-(2-ethyl-3-butenyl)-2-nor

alkene, 5-(6-heptenyl)-2-nor

alkene, 5-(3-methyl-5-hexenyl)-2-nor

alkene, 5-(3,4-dimethyl-4-pentenyl)-2-nor

alkene, 5-(3-ethyl-4-pentenyl)-2-nor

alkene, 5-(7-octenyl)-2-nor

alkene, 5-(2-methyl-6-heptenyl)-2-nor

alkene, 5-(1,2-dimethyl-5-hexenyl)-2-nor

alkene, 5-(5-ethyl-5-hexenyl)-2-nor

Alkene, 5-(1,2,3-trimethyl-4-pentyl)-2-nor

ene, etc. Among these, ENB is preferred in terms of high availability, high reactivity with sulfur or a vulcanization accelerator in the crosslinking reaction after polymerization, easy control of the crosslinking speed, and easy acquisition of good mechanical properties .

The ethylene·α-olefin·non-conjugated polyene copolymer of the present invention contains a non-conjugated polyene derived from a molecule containing only one partial structure selected from the group consisting of the above-mentioned general formulae (I) and (II) In the case of the constituent unit of (D), the ratio thereof is not particularly limited within the range that does not impair the purpose of the present invention, and is usually about 0 to 20% by weight, preferably 0 to 8% by weight, more preferably about 0.01 to 8% by weight The weight fraction of (wherein, the sum of the weight fractions of (A), (B), (C), and (D) is assumed to be 100% by weight).

The ethylene·α-olefin·non-conjugated polyene copolymerization system of the present invention has, as described above, derived from ethylene (A), α-olefin (B) having 3 to 20 carbon atoms, and the above-mentioned non-conjugated polyene (C) , and optionally a copolymer of the constituent unit of the above-mentioned non-conjugated polyene (D), which satisfies the following requirements (i) to (vii).

(i) The molar ratio of ethylene/α-olefin is 40/60 to 99.9/0.1.

(ii) The weight fraction of the structural unit derived from the non-conjugated polyene (C) is 0.07% by weight to 10% by weight.

(iii) Weight average molecular weight (Mw) of ethylene·α-olefin·non-conjugated polyene copolymer, weight fraction of constituent units derived from non-conjugated polyene (C) (weight fraction of (C) (weight fraction) %)), and the molecular weight of the non-conjugated polyene (C) (the molecular weight of (C)) satisfy the following formula (1).

4.5≦Mw×(C) weight fraction/100/(C) molecular weight≦40...Formula (1)

(iv) Complex viscosity η ^* ₍ ω _=0.1) (Pa·sec) at frequency ω=0.1rad/s and frequency ω=100rad/s obtained by linear viscoelasticity measurement (190°C) using a rheometer The ratio of complex viscosity η ^* ₍ ω ₌₁₀₀₎ (Pa·sec) at time P(η ^* ₍ ω _=0.1) /η ^* ₍ ω ₌₁₀₀₎ ), limiting viscosity [η], the above are derived from non-conjugated The weight fraction of the constituent unit of the olefin (C) (the weight fraction of (C)) satisfies the following formula (2).

Weight fraction of P/([η] ^2.9 )≦(C)×6...Formula (2)

(v) The ratio (molecular weight distribution: Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is in the range of 8 to 30.

(vi) The above-mentioned number average molecular weight (Mn) is 30,000 or less.

(vii) The graph obtained by GPC measurement shows two or more peaks, and the area of the peak appearing on the side with the smallest molecular weight is 20% or less of the entire peak area.

In this specification, the "α-olefin having 3 to 20 carbon atoms" is also simply referred to as "α-olefin".

<Requirements (i)>

Requirement (i) is to limit the molar ratio of ethylene/α-olefin in the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention to be 40/60~99.9/0.1, and the molar ratio is preferably 50/50~90/10, better 55/45~85/15, even better 55/45~78/22. When the ethylene·α-olefin·non-conjugated polyene copolymerization system of the present invention is used as a raw material for a cross-linked molded body, the obtained cross-linked molded body exhibits superior rubber elasticity, superior mechanical strength and flexibility, so it is preferable .

Furthermore, the amount of ethylene (content of the constituent unit derived from ethylene (A)) and the amount of α-olefin (content of the constituent unit derived from α-olefin (B)) in the ethylene·α-olefin·non-conjugated polyene copolymer It can be obtained by ¹³ C-NMR.

<Requirements (ii)>

Requirement (ii) is that in the ethylene·α-olefin·non-conjugated polyene copolymer specified in the present invention, the weight fraction of the constituent unit derived from the non-conjugated polyene (C) is based on the ethylene·α-olefin·non-conjugated polyene. The range of 0.07% by weight to 10% by weight in 100% by weight of the conjugated polyene copolymer (that is, in 100% by weight of the total of the weight fractions of the total constituent units). The weight fraction of the constituent unit derived from the non-conjugated polyene (C) is preferably 0.1% by weight to 8.0% by weight, more preferably 0.5% by weight to 5.0% by weight.

If the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention satisfies the requirement (ii), the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention has sufficient hardness and excellent mechanical properties, so it is relatively It is preferred; when peroxide is used for cross-linking, it shows a faster cross-linking speed. The ethylene·α-olefin·non-conjugated polyene copolymer of the present invention is suitable for producing cross-linked molded articles, so it is relatively good.

Furthermore, the amount of non-conjugated polyene (C) in the ethylene·α-olefin·non-conjugated polyene copolymer (the content of the constituent unit derived from the non-conjugated polyene (C)) can be determined by ¹³ C-NMR beg.

<Requirements (iii)>

Requirement (iii) is that the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention satisfies the weight average molecular weight (Mw) of the ethylene·α-olefin·non-conjugated polyene copolymer, and the The weight fraction of the constituent units derived from the non-conjugated polyene (C) (weight fraction of (C): % by weight) and the molecular weight of the non-conjugated polyene (C) (the molecular weight of (C)) satisfy the following Relation (1).

4.5≦Mw×(C) weight fraction/100/(C) molecular weight≦40...Formula (1)

In the case where the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention satisfies the requirement (iii), the content of the structural unit of the non-conjugated polyene (C) derived from VNB or the like is appropriate and exhibits sufficient crosslinking performance At the same time, in the case of using the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention to produce a cross-linked molded body, it is preferable because the cross-linking speed is excellent and the molded body after cross-linking exhibits superior mechanical properties.

More preferably, the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention satisfies the following relational formula (1').

4.5≦Mw×(C) weight fraction/100/(C) molecular weight≦35...Formula (1’)

Furthermore, the weight-average molecular weight (Mw) of the ethylene·α-olefin·non-conjugated polyene copolymer can be determined in terms of polystyrene by gel permeation chromatography (GPC).

The ethylene·α-olefin·non-conjugated polyene copolymerization system of the present invention satisfies the above formula (1) or (1') in the case of "Mw×(C) weight fraction/100/(C) molecular weight" When the degree of crosslinking becomes appropriate, it is possible to manufacture a molded product with an excellent balance of mechanical properties and heat aging resistance. In "Mw×(C) weight fraction/100/(C) molecular weight" When the amount is too small, the cross-linking property may be insufficient and the cross-linking speed may become slow, and if the amount is too large, excessive cross-linking may occur and the mechanical properties may be deteriorated.

<Requirements (iv)>

Requirement (iv) is the complex viscosity of the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention at a frequency of ω=0.1rad/s obtained by measuring the linear viscoelasticity (190°C) using a rheometer The ratio of η ^* ₍ ω _=0.1) (Pa‧sec) to the complex viscosity η ^* ₍ ω ₌₁₀₀₎ (Pa‧sec) at frequency ω=100rad/s P(η ^* ₍ ω _=0.1) /η ^* ₍ ω ₌₁₀₀₎ ), the limiting viscosity [η], and the weight fraction (weight fraction of (C): wt %) of the constituent unit derived from the non-conjugated polyene (C) described above satisfy the following formula (2).

Weight fraction of P/([η] ^2.9 )≦(C)×6...Formula (2)

Here _{, the ratio P} ^{( η * (} _{ω = 0.1)} /η ^* ₍ ω ₌₁₀₀₎ ) represents the frequency dependence of viscosity, P/([η] ^2.9 ) on the left side of formula (2) is affected by short chain branching or molecular weight, etc. A tendency to show higher values when there are more branches. Generally speaking, the ethylene·α-olefin·non-conjugated polyene copolymer contains more structural units derived from the non-conjugated polyene, the more long-chain branching tends to be contained, but the ethylene·α of the present invention tends to contain more long-chain branches. The -olefin·non-conjugated polyene copolymer is considered to satisfy the above formula (2) because the long chain branch is less than that of the conventional ethylene·α-olefin·non-conjugated polyene copolymer. In the present invention, the P value is measured using a viscoelasticity measuring device Ares (manufactured by Rheometric Scientific) under the conditions of 190° C., strain of 1.0%, and frequency changed. The ratio of complex viscosity at /s time (η ^* ratio).

The ethylene·α-olefin·non-conjugated polyene copolymer of the present invention preferably satisfies the following formula (2').

The weight fraction of P/([η] ^2.9 )≦(C)×5.7...Formula (2')

Also, the limiting viscosity [η] means the value measured in decalin at 135°C.

<Requirements (v)>

Requirement (v) is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention as measured by gel permeation chromatography (GPC). (Molecular weight distribution: Mw/Mn) is in the range of 8 to 30. The molecular weight distribution (Mw/Mn) is preferably in the range of 9-28, more preferably 10-26.

When the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention satisfies the requirement (v), since it contains a low molecular weight component in an appropriate amount, the processability is good.

Furthermore, the weight-average molecular weight (Mw) and number-average molecular weight of the ethylene·α-olefin·non-conjugated polyene copolymer can be obtained from the polystyrene-converted values measured by gel permeation chromatography (GPC). .

<Requirements (vi)>

Requirement (vi) is that the above-mentioned number average molecular weight (Mn) of the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention is specified to be 30,000 or less. The above-mentioned 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 ethylene·α-olefin·non-conjugated polyene copolymer of the present invention satisfies the requirement (vi), since it contains a low molecular weight component in an appropriate amount, the processability is good.

<Requirements (vii)>

Requirement (vii) is that the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention shows two or more peaks on the graph obtained by GPC measurement, and the molecular weight is the smallest side. The area of the crest that appears is less than 20% of the area of the entire crest. The area of the peak which appears on the side with the smallest molecular weight is preferably 2 to 18%, more preferably 3 to 16%, relative to the entire peak area.

When the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention satisfies the requirement (vii), the molecular weight distribution of the copolymer exhibits multimodality such as bimodality, and contains a high molecular weight component and a low molecular weight component in an appropriate ratio , the workability becomes good.

The ethylene·α-olefin·non-conjugated polyene copolymer of the present invention is preferably the natural logarithm of the number of long chain branches per 1000 carbon atoms (LCB _1000C ) obtained by 3D-GPC and the weight average molecular weight (Mw) [Ln(Mw)] satisfies the following formula (3).

LCB _1000C ≦1-0.07×Ln(Mw)...Formula (3)

By the above formula (3), the upper limit of the content of long chain branches per unit carbon number of the ethylene·α-olefin·non-conjugated polyene copolymer is specified.

This ethylene·α-olefin·non-conjugated polyene copolymerization system contains a small proportion of long chain branches, and has excellent hardening properties when using peroxide for cross-linking. Sex is superior, so it is better.

More preferably, the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention satisfies the following formula (3').

LCB _1000C ≦1-0.071×Ln(Mw)...Formula (3')

Here, Mw and the number of long chain branches per 1000 carbon atoms (LCB _1000C ) can be obtained by a structural analysis method using 3D-GPC. In this specification, specifically, it is calculated|required as follows.

Using a 3D-high temperature GPC apparatus PL-GPC220 type (manufactured by Polymer Laboratories), the absolute molecular weight distribution was obtained, and the limiting viscosity was obtained by a viscometer. The main measurement conditions are as follows.

Detector: Built-in refractometer/GPC device

2-Angle Light Scattering Photometer PD2040 Type (manufactured by Precison Detectors)

Bridge Viscometer Model PL-BV400 (manufactured by Polymer Laboratories)

×長度300mm) Column: TSKgel GMHHR-H(S)HT × 2 + TSKgel GMHHR-M(S) × 1 (any one has an inner diameter of 7.8mm

×Length 300mm)

Temperature: 140℃

Mobile phase: 1,2,4-trifluorobenzene (containing 0.025% BHT)

Injection volume: 0.5mL

Sample concentration: ca 1.5mg/mL

Sample Filtration: Filtration through a 1.0 μm pore size sintered filter

The dn/dc value necessary to determine the absolute molecular weight depends on the dn/dc value of standard polystyrene (molecular weight 190,000) of 0.053 and the response intensity of the differential refractometer per unit injection mass, and is determined for each sample.

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

[η] ^i,br ): The measured limiting viscosity of the i-th slice component

[η] ^{i, lin} ): The limiting viscosity when it is assumed that the i-th slice component does not have a long-chain branch structure and only shows a short-chain branch structure

Here, the relational expression of [n]=KM ^v ; v=0.725 is applied. This formula is called the Mark-Houwink-Sakurada formula, where K is the solvent constant and M is the average molecular weight.

In addition, each average value of g' is calculated from the following formulae (v-2), (v-3) and (v-4). In addition, the Trendline when it is assumed to have only short chain branches is determined for each sample.

C ⁱ : the concentration of each eluting component

M ⁱ : absolute molecular weight of each eluted component

Furthermore, the number of branch points ^BrNo per molecular chain, the number of long chain branches LCB _1000C per 1000 carbon atoms, and the degree of branching λ per unit molecular weight were calculated using g'w. BrNo was calculated using Zimm-Stockmayer's formula (v-5), and LCB _1000C and λ were calculated using formulas (v-6) and (v-7). g is the long-chain branching parameter obtained from the inertia radius Rg, and the following simple correlation is applied between g' obtained from the limiting viscosity.

g=g'( ^1/ ε)

ε (construction factor) = 0.5~1.5 (usually 0.75)

The ε in the formula has various values proposed according to the molecular shape, and the calculation is performed here assuming that ε=1 (also g'=g).

[Number 3]

λ=BrNo/M…(V-6)

LCB _1000C =λ×14000…(V-7)

In formula (V-7), 14000 represents the molecular weight of 1000 parts in methylene (CH ₂ ) unit.

In the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention, the limiting viscosity [η] is preferably 0.1-5 dL/g, more preferably 0.5-5.0 dL/g, still more preferably 0.9-4.0 dL/g .

The weight average molecular weight (Mw) of the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention is preferably 10,000-600,000, more preferably 30,000-500,000, still more preferably 50,000-400,000.

The ethylene·α-olefin·non-conjugated polyene copolymer of the present invention preferably satisfies the above-mentioned limiting viscosity [η] and weight average molecular weight (Mw) at the same time.

In the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention, the non-conjugated polyene (C) preferably contains VNB, more preferably VNB. That is, in the above formula (1), formula (2), formula (4) described later, etc., it is preferable that "weight fraction of (C)" is "weight fraction of VNB" (% by weight).

The ethylene·α-olefin·non-conjugated polyene copolymerization system of the present invention is as described above, in addition to the above-mentioned structural units derived from (A), (B) and (C), it is preferably further 0% by weight~ 20 wt % (wherein, the sum of the weight fractions of (A), (B), (C), and (D) is set to 100 wt %) contains the above-mentioned non-conjugated polyene (D)-derived constituent units. In this case, it is preferable to satisfy the following requirement (viii).

<Requirements (viii)>

Weight average molecular weight (Mw) of ethylene·α-olefin·non-conjugated polyene copolymer, Weight fraction of constituent units derived from non-conjugated polyene (C) (weight fraction of (C) (% by weight)), weight fraction of constituent units derived from non-conjugated polyene (D) ((D) (% by weight)), the molecular weight of the non-conjugated polyene (C) (the molecular weight of (C)), and the molecular weight of the non-conjugated polyene (D) (the molecular weight of (D)) satisfy the following formula (4) ).

4.5≦Mw×{(weight fraction of (C)/100/molecular weight of (C))+(weight fraction of (D)/100/molecular weight of (D))}≦45... Formula (4)

In the formula (4), the content of the non-conjugated diene (the sum of (C) and (D)) in one molecule of the specific copolymer.

When the ethylene·α-olefin·non-conjugated polyene copolymer containing the above-mentioned structural unit derived from (D) satisfies the formula (4), since the formed body obtained from the ethylene·α-olefin·non-conjugated polyene copolymer Shows superior mechanical properties and heat aging resistance, so it is better.

If the requirement (viii) is not satisfied, in the formula (4) "Mw × {((C) weight fraction/100/(C) molecular weight) + ((D) weight fraction/100/(D) When the molecular weight of the In addition, there are cases where the heat aging resistance deteriorates.

<Requirements (ix)>

The ethylene·α-olefin·non-conjugated polyene copolymer of the present invention is not particularly limited, but the complex viscosity at the frequency ω=0.01rad/s obtained by measuring the linear viscoelasticity (190°C) using a rheometer η ^* (ω _=0.01 )(Pa·sec) and complex viscosity η ^* (ω ₌₁₀ )(Pa·sec) at frequency ω=10rad/s, iodine from appearance of non-conjugated polyene (C) It is preferable to satisfy the following formula (5).

Log{η ^* (ω _=0.01 )}/Log{η ^* (ω ₌₁₀ )}≦0.0753×{Iodine value from the appearance of the non-conjugated polyene (C)}+1.42... Formula (5)

Here, the complex viscosity η ^* (ω _=0.01 ) and the complex viscosity η ^* (ω ₌₁₀ ) are set to the complex viscosity η ^* (ω _=0.1 ) and the complex viscosity η ^* except in the requirement (iv) Except for the measurement frequency of (ω ₌₁₀₀ ), the rest were obtained in the same manner.

In addition, the iodine value derived from the appearance of the non-conjugated polyene (C) is obtained by the following formula.

Iodine value from the appearance of (C)=weight fraction of (C)×253.81/(C) molecular weight

In the above formula (5), the left side represents the shear rate dependence as an indicator of the amount of long chain branches, and the right side represents an indicator of the content of non-conjugated polyene (C) which is not consumed by long chain branches during polymerization. When the requirement (ix) is satisfied and the above formula (5) is satisfied, the degree of long-chain branching is not too high, which is preferable. On the other hand, in the case where the above formula (5) is not satisfied, it can be seen that the non-conjugated polyene (C) to be copolymerized has a large proportion consumed in the formation of long chain branches.

The ethylene·α-olefin·nonconjugated polyene copolymer of the present invention preferably contains a sufficient amount of constituent units derived from the nonconjugated polyene (C), and the constituents derived from the nonconjugated polyene (C) in the copolymer The weight fraction per unit (weight fraction (weight %) of (C)) and the weight average molecular weight (Mw) of the copolymer preferably satisfy the following formula (6).

The weight fraction of 6-0.45×Ln(Mw)≦(C)≦10...Formula (6)

In the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention, the number (n _c ) of constituent units derived from the non-conjugated polyene (C) per unit of the weight average molecular weight (Mw) is preferably 6 1 or more, more preferably 6 or more and 40 or less, particularly preferably 7 or more and 39 or less, and most preferably 10 or more and 38 or less.

As described above, the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention contains a sufficient amount of structural units derived from non-conjugated polyene (C) such as VNB, and has a small content of long chain branches, Excellent hardening properties when cross-linked with peroxides Furthermore, it has excellent formability and workability, excellent balance of physical properties such as mechanical properties, and especially excellent heat aging resistance. In particular, even though the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention has good processability due to the inclusion of low molecular weight components, it exhibits an unexpectedly excellent effect of high crosslinking density after crosslinking. Generally, when there are many low molecular weight components, the crosslinking density tends to decrease. However, in the case of the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention, since the low molecular weight components are also crosslinked, it is presumed that This unexpected and excellent effect can be obtained. Therefore, the conventional EPDM containing many low-molecular-weight components can exhibit the effect that the problems such as stickiness and the like that are common in the conventional EPDM do not occur.

Furthermore, in the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention, the number (n _D ) of constituent units derived from the non-conjugated polyene (D) per unit of the weight-average molecular weight (Mw) is preferably 29 or less, more preferably 10 or less, and even more preferably less than 1.

In the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention, the content of the constituent units derived from the non-conjugated polyene (D) such as ENB is suppressed within a range that does not impair the purpose of the present invention, It is not easy to post-crosslink and has sufficient heat aging resistance, so it is preferable.

Here, in the weight average molecular weight (Mw) per unit of the ethylene·α-olefin·non-conjugated polyene copolymer, the number (n C ) of the constituent units derived from the non-conjugated polyene (C) or the number (n _C ) derived from the non-conjugated polyene The number (n _D ) of the constituent units of the polyene (D) can be determined by the molecular weight of the non-conjugated polyene (C) or (D), and the composition of the non-conjugated polyene (C) or (D) in the copolymer The weight fraction per unit (weight fraction of (C) or (D) (weight %)) and the weight average molecular weight (Mw) of the copolymer are obtained by the following formula.

(n _C )=(Mw)×{(C) weight fraction/100}/Molecular weight of non-conjugated polyene (C)

(n _D )=(Mw)×{(D) weight fraction/100}/Molecular weight of non-conjugated polyene (D)

In the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention, the number of respective constituent units derived from the non-conjugated polyenes (C) and (D) per unit of weight average molecular weight (Mw) When (n _C ) and (n _D ) satisfy the above ranges, the ethylene·α-olefin·non-conjugated polyene copolymer system has less long-chain branch content, and has excellent curing properties when cross-linked with peroxide, and can be molded It is preferred because of its good properties and processability, excellent balance of physical properties such as mechanical properties, and less occurrence of post-crosslinking, especially excellent heat aging resistance.

[Manufacture of ethylene·α-olefin·non-conjugated polyene copolymer]

The ethylene·α-olefin·non-conjugated polyene copolymerization system of the present invention is composed of ethylene (A), α-olefin (B) having 3 to 20 carbon atoms, the above-mentioned non-conjugated polyene (C), and optionally A copolymer obtained by copolymerizing the units constituted by the above-mentioned non-conjugated polyene (D).

The ethylene·α-olefin·non-conjugated polyene copolymerization system of the present invention can be prepared by any method as long as the above-mentioned requirements (i) to (vii) are satisfied. It is obtained by copolymerizing monomers, more preferably by copolymerizing monomers in the presence of a polymerization catalyst system containing a dimetallocene compound, and more preferably by being included in a polymerization catalyst system containing a specific dimetallocene compound. obtained by the method of carrying out the step (1) of copolymerizing in the presence of a catalyst and the method of carrying out the step (2) of deactivating the above-mentioned polymerization catalyst by adding alcohol as a catalyst deactivator.

<Dimetallocene compound>

The ethylene·α-olefin·non-conjugated polyene copolymer of the present invention is preferably in the presence of a polymerization catalyst containing at least one metallocene compound selected from the compounds represented by the following general formula [A1] , obtained by copolymerization of monomers. If the copolymerization of monomers is carried out using such a metallocene compound-containing polymerization catalyst system, the resulting copolymerization The long-chain branching contained in the complex is suppressed, and the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention which satisfies the above-mentioned requirements can be easily prepared.

In the above formula [A1], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group, or a compound other than a silicon-containing group. Heteroatomic group; two adjacent groups in R ¹ ~R ⁴ can also bond with each other to form a ring.

烷基、金剛烷基、苯 基、鄰甲苯基、間甲苯基、對甲苯基、二甲苯基、異丙基苯基、第三丁基苯基、萘基、聯苯基、聯三苯基、菲基、蒽基、苄基、異丙苯基；包括甲氧基、乙氧基、苯氧基等之含氧基、硝基、氰基、N-甲基胺基、N,N-二甲基胺基、N-苯基胺基等之含氮基、硼烷三基、二硼烷基等之含硼基、磺醯基、次磺醯基等之含硫基者亦可列舉為烴基。 The hydrocarbon group is preferably a hydrocarbon group with 1 to 20 carbon atoms, for example, an alkyl group with 1 to 20 carbon atoms, an aralkyl group with 7 to 20 carbon atoms, and an aryl group with 6 to 20 carbon atoms. , or substituted aryl (aryl) groups, etc. For example: methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, n-pentyl, neopentyl base, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, 3-methylpentyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1- Methyl-1-propylbutyl, 1,1-propylbutyl, 1,1-dimethyl-2-methylpropyl, 1-methyl-1-isopropyl-2-methylpropyl base, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norm

Alkyl, adamantyl, phenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, cumyl, tert-butylphenyl, naphthyl, biphenyl, triphenyl , phenanthryl, anthracenyl, benzyl, cumyl; including methoxy, ethoxy, phenoxy and other oxygen-containing, nitro, cyano, N-methylamine, N,N- Nitrogen-containing groups such as dimethylamino and N-phenylamino groups, boron-containing groups such as boranetriyl and diboranyl groups, and sulfur-containing groups such as sulfonyl groups and sulfenyl groups can also be listed. is a hydrocarbon group.

The hydrogen atom of the above-mentioned hydrocarbon group may also be substituted by a halogen atom, for example, trifluoromethyl, trifluoromethylphenyl, pentafluorophenyl, chlorophenyl and the like.

Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, and a hydrocarbon-substituted silyloxy group. such as methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, diphenylsilyl Methylphenylsilyl, dimethyl tert-butylsilyl, dimethyl(pentafluorophenyl)silyl, etc.

R6 and ^R11 are the same atom or the same group selected from hydrogen atom, hydrocarbon group, silicon-containing group and heteroatom-containing group other ^than silicon-containing group ^{; R7} and R10 are selected from hydrogen atom, hydrocarbon group, silicon-containing group and the same atom or the same group selected from the heteroatom-containing groups other than the silicon-containing group; R ⁶ and R ⁷ can also be bonded to each other to form a ring, and R ¹⁰ and R ¹¹ can also be bonded to each other to form a ring. However, not all of R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are 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 represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or non-conjugated diene with 4 to 20 carbon atoms, an anionic ligand, or a neutral ligand that can be coordinated by isolated electron pairs; j represents an integer from 1 to 4; when j is an integer of 2 or more , the complex numbers Q may be the same or different.

The halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.

The hydrocarbon group is preferably a hydrocarbon group with 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2 - Dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, second-butyl, third Butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl, benzyl, etc. , preferably methyl, ethyl, and benzyl.

A neutral conjugated or non-conjugated diene having 4 to 20 carbon atoms, preferably a neutral conjugated or non-conjugated diene having 4 to 10 carbon atoms. Specific examples of neutral conjugated or non-conjugated dienes include, for example, s-cis- or s-trans-n ⁴ -1,3-butadiene, s-cis- or s-trans-n ^4-1,4 -Diphenyl-1,3-butadiene, s-cis- or s-trans-n ^4-3 -methyl-1,3-pentadiene, s-cis- or s-trans-n ⁴ -1,4-dibenzyl-1,3-butadiene, s-cis- or s-trans-n ⁴ -2,4-hexadiene, s-cis formula- or s-trans-n ⁴ -1,3-pentadiene, s-cis- or s-trans-n ⁴ -1,4-xylyl-1,3-butadiene, s -cis- or s-trans-n ⁴ -1,4-bis(trimethylsilyl)-1,3-butadiene, etc.

Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy, and phenoxy; carboxylate groups such as acetate and benzoate; methanesulfonate and tosylate. and other sulfonate groups, etc.

烷、1,2-二甲氧基乙烷等醚類。 Specific examples of neutral ligands that can coordinate with isolated electron pairs include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine;

alkane, 1,2-dimethoxyethane and other ethers.

Examples of the cyclopentadienyl group having substituents R ¹ to R ⁴ in the above formula [A1] include unsubstituted cyclopentadienyl groups in which R ¹ to R ⁴ are hydrogen atoms, and 3-tert-butylcyclopentadiene. , 3-methylcyclopentadienyl, 3-trimethylsilylcyclopentadienyl, 3-phenylcyclopentadienyl, 3-adamantylcyclopentadienyl, 3-pentylcyclopentadienyl Dialkenyl, 3-cyclohexylcyclopentadienyl and other 3-position monosubstituted cyclopentadienyl; 3-tert-butyl-5-methylcyclopentadienyl, 3-tert-butyl-5- Ethylcyclopentadienyl, 3-phenyl-5-methylcyclopentadienyl, 3,5-di-tert-butylcyclopentadienyl, 3,5-dimethylcyclopentadienyl , 3-phenyl-5-methylcyclopentadienyl, 3-trimethylsilyl-5-methylcyclopentadienyl, etc. 3,5-position disubstituted cyclopentadienyl, etc., but not limited to this. From the viewpoints of the ease of synthesis of the metallocene compound, the production cost, and the copolymerization ability of the non-conjugated polyene, a cyclopentadienyl group in which unsubstituted R ¹ to R ⁴ are hydrogen atoms) is preferred.

The indenyl group of formula [A1] with substituents R ⁵ to R ¹² includes, for example, unsubstituted indenyl groups in which R ⁵ to R ¹² are hydrogen atoms, 2-methyl indenyl groups, 2-tert-butyl indenyl groups, 2-phenylindenyl and other 2-position mono-substituted indenyl; 4-methyl indenyl, 4-tert-butyl indenyl, 4-phenylindenyl and other 4-substituted indenyl; or 2,7-diyl 2,7-position or 3,6-position disubstituted styrenyl group, such as tert-butyl-indenyl group, 3,6-di-tert-butyl-indyl group, etc.; 2,7-dimethyl-3,6-di-tert-butyl group Four-substituted indenyl groups at positions 2, 3, 6, and 7, such as pyrenyl, 2,7-diphenyl-3,6-di-tert-butylindenyl, etc.; or as the following general formulas [VI], [V-II] The 2, ³ , ⁶ , and ⁷ -position tetra-substituted ^peryl groups are shown, but are not limited thereto.

[hua 4]

In formulas [VI] and [V-II], R ⁵ , R ⁸ , R ⁹ , and R ¹² have the same definitions as in the above general formula [A1]; R ^a , R ^b , R ^c , R ^d , R ^e , R ^f , R ^g and R ^h are independently hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, and may be bonded to adjacent substituents to form a ring. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, and n-pentyl. In addition, in formula [VI], R ^x and R ^y are independently hydrocarbon groups having 1 to 3 carbon atoms or may have an unsaturated bond, and R ^x may also form a double bond with the carbon to which R ^a or R ^c is bonded. R ^y can also form a double bond together with the carbon to which ^Re or R ^g is bonded, preferably both R ^x and R ^y are saturated or unsaturated hydrocarbon groups with 1 or 2 carbon atoms.

The compound represented by the above general formula [V-I] or [V-II] can be specifically exemplified by the octamethyl octahydrodibenzoinyl group represented by the formula [V-III], the tetramethyl tenacyl group represented by the formula [V-IV] Dihydrodi Benzophenylyl, octamethyltetrahydrodicyclopentadienoprenyl group represented by formula [V-V], hexamethyldihydrodicyclopentadienoptenylyl group represented by formula [V-VI], formula [V -VII] represented by b,h-dibenzophentenyl.

[Chemical 9]

The ^{dimetallocene} compounds represented by the above general formula [A1] containing these phenylene groups are all non-conjugated polyenes with excellent copolymerization ability. The transition metal compounds of the 6-position disubstituted indenyl group, the 2,3,6,7-position tetra-substituted indenyl group, and the 2,3,6,7-position tetrasubstituted indenyl group represented by the general formula [VI] are particularly advantageous. When Y ¹ is a carbon atom, R ⁵ to R ¹² are unsubstituted phenylene groups, 3,6-position disubstituted phenylene groups, 2,3,6,7-position tetra-substituted phenylene groups, the above general formula [ The dimetallocene compound of the 2,3,6,7-position tetra-substituted perylene group represented by VI] is particularly excellent.

In addition, in the present invention, in the dimetallocene compound represented by the general formula [A1], when Y ¹ is a silicon atom and all R ⁵ to R ¹² are hydrogen atoms, R ¹³ and R ¹⁴ are preferably selected from Groups other than methyl, butyl, phenyl, silicon-substituted phenyl, cyclohexyl, and benzyl; Y ¹ is a silicon atom, and R ⁶ and R ¹¹ are both tertiary butyl, R ⁵ , R ⁷ , R ⁸ When , R ⁹ , R ¹⁰ , R ¹² are not tert-butyl groups, R ¹³ and R ¹⁴ are preferably groups other than benzyl and silicon-substituted phenyl groups; Y ¹ is a carbon atom, and R ⁵ to R When all ¹² are hydrogen atoms, R ¹³ and R ¹⁴ are preferably selected from methyl, isopropyl, tert-butyl, isobutyl, phenyl, p-tert-butylphenyl, p-n-butyl Groups other than phenyl, silicon-substituted phenyl, 4-biphenyl, p-tolyl, naphthyl, benzyl, cyclopentyl, cyclohexyl, xylyl; Y ¹ is a carbon atom, R ⁶ and R ¹¹ is a common group selected from tert-butyl, methyl or phenyl, and when R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹² are different groups or atoms, R ¹³ , R ¹⁴ is preferably selected from groups other than methyl, phenyl, p-tert-butylphenyl, p-n-butylphenyl, silicon-substituted phenyl, and benzyl; where Y ¹ is a carbon atom, and R ⁶ is Dimethylamino, methoxy or methyl, when R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are groups or atoms different from R ⁶ , R ¹³ and R ¹⁴ are preferred Be selected from groups other than methyl and phenyl; in Y ¹ is a carbon atom, a peryl group, and the position formed by R ⁵ ～R ¹² is b, h-dibenzoyl or a, i-dibenzoyl In the case of a perylene group, R ¹³ and R ¹⁴ are preferably selected from groups other than methyl and phenyl.

Hereinafter, specific examples of the dimetallocene compound represented by the above-mentioned general formula [A1] in the present invention are illustrated, but the scope of the present invention is not limited by these.

As a specific example of the dimetallocene compound represented by the general formula [A1] in the present invention, when Y ¹ is a silicon atom, for example, diphenylsilylidene (cyclopentadienyl) (2,7 -Di-tert-butyl-intenyl) zirconium dichloride, diphenylsilylidene (cyclopentadienyl) (3,6-di-tert-butyl indyl) zirconium dichloride, diphenylene Silyl(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylinyl)zirconium dichloride, diphenylsilylidene(cyclopentadienyl) (2,7-diphenyl-3,6-di-tert-butyl-perylene) zirconium dichloride, diphenylsilylidene (cyclopentadienyl) (octamethyloctahydrodibenzopyranyl) base) zirconium dichloride, diphenylsilylidene (cyclopentadienyl) (tetramethyldodecahydrodibenzoyl) zirconium dichloride, diphenylsilylidene (cyclopentadienyl) Alkenyl) (Octamethyltetrahydrodicyclopentadienoptenyl) zirconium dichloride, Diphenylsilylidene (cyclopentadienyl) (hexamethyldihydrodicyclopentadienoptenyl) base) zirconium dichloride, diphenylsilylidene (cyclopentadienyl) (b,h-dibenzoyl) zirconium dichloride, bis(p-tolyl)silylidene (cyclopentadienyl) Dienyl)(Pylenyl)zirconium dichloride, Di(p-tolyl)silylidene(cyclopentadienyl)(2,7-di-tert-butylphenylenyl)zirconium dichloride, Di(p-tolyl)silylidene (cyclopentadienyl) p-Tolyl)silylidene(cyclopentadienyl)(3,6-di-tert-butylphenylenyl)zirconium dichloride, bis(p-tolyl)silylidene(cyclopentadienyl) (2,7-Dimethyl-3,6-di-tert-butylintenyl)zirconium dichloride, bis(p-tolyl)silylidene(cyclopentadienyl)(2,7-diphenylene) bis(p-tolyl)silylidene(cyclopentadienyl)(octamethyloctahydrodibenzointenyl)dichloride Zirconium dichloride, bis(p-tolyl)silylidene (cyclopentadienyl) (tetramethyldodecahydrodibenzoyl) zirconium dichloride, bis(p-tolyl)silylidene (cyclopentadienyl) pentadienyl)(octamethyltetrahydrodicyclopentadienoptenyl)zirconium dichloride, bis(p-tolyl)silylidene(cyclopentadienyl)(hexamethyldihydrobicyclo) Pentadienoyl) zirconium dichloride, bis(p-tolyl)silylidene(cyclopentadienyl)(b,h-dibenzoyl) zirconium dichloride, bis(m-tolyl) )silylidene(cyclopentadienyl)(phenylene) zirconium dichloride, bis(m-tolyl)silylidene(cyclopentadienyl)(2,7-di-tert-butylphenylene) ) zirconium dichloride, bis(m-tolyl)silylidene(cyclopentadienyl)(3,6-di-tert-butylphenylenyl)zirconium dichloride, bis(m-tolyl)silylidene bis(m-tolyl)silylidene(cyclopentadienyl) )(2,7-diphenyl-3,6-di-tert-butylintenyl)zirconium dichloride, bis(m-tolyl)silylidene(cyclopentadienyl)(octamethyloctahydro) Dibenzoyl) zirconium dichloride, bis(m-tolyl)silylidene(cyclopentadienyl)(tetramethyldodecahydrodibenzoyl) zirconium dichloride, bis(m-toluene) yl)silylidene (cyclopentadienyl) (octamethyltetrahydro) Dicyclopentadienoptenyl)zirconium dichloride, bis(m-tolyl)silylidene(cyclopentadienyl)(hexamethyldihydrodicyclopentadienoptenyl)zirconium dichloride , bis (m-tolyl) silylidene (cyclopentadienyl) (b, h-dibenzoyl) zirconium dichloride, etc.

In the case where Y ¹ is a carbon atom, for example: diphenylmethylene (cyclopentadienyl) (3,6-di-tert-butylinyl) zirconium dichloride, diphenylmethylene (Cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylintenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(2,7 -Diphenyl-3,6-di-tert-butylintenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzointenyl)dichloride Zirconium, diphenylmethylene (cyclopentadienyl) (tetramethyldodecahydrodibenzoyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (octamethyl) THF Phenylmethylene(cyclopentadienyl)(b,h-dibenzoyl)zirconium dichloride, bis(p-tolyl)methylene(cyclopentadienyl)(2,7-dichloride) tertiary butyl intenyl) zirconium dichloride, bis(p-tolyl) methylene (cyclopentadienyl) (3,6-di-tert-butyl indyl) zirconium dichloride, bis(p-toluene) base) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-tert-butylinyl) zirconium dichloride, bis (p-tolyl) methylene (cyclopentyl) Dienyl)(2,7-diphenyl-3,6-di-tert-butylintenyl)zirconium dichloride, bis(p-tolyl)methylene(cyclopentadienyl)(octamethyl) Octahydrodibenzoyl) zirconium dichloride, bis(p-tolyl)methylene(cyclopentadienyl)(tetramethyldodecahydrodibenzoyl) zirconium dichloride, bis(p-tolyl) Tolyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentadienoptenyl)zirconium dichloride, bis(p-tolyl)methylene(cyclopentadienyl)( Hexamethyldihydrodicyclopentadienyl)zirconium dichloride, bis(p-tolyl)methylene(cyclopentadienyl)(b,h-dibenzoindenyl)zirconium dichloride , bis (m-tolyl) methylene (cyclopentadienyl) (peryl) zirconium dichloride, bis (m-tolyl) methylene (cyclopentadienyl) (2,7-two third Butylphenylinyl)zirconium dichloride, bis(m-tolyl)methylene(cyclopentadienyl)(3,6-di-tertbutylinyl)zirconium dichloride, bis(m-tolyl) Methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylphenylenyl)zirconium dichloride, bis(m-tolyl)methylene(cyclopentadiene) base)(2,7-diphenyl-3,6-di-tert-butylintenyl)zirconium dichloride, bis(m-tolyl)methylene(cyclopentadienyl)(octamethyloctahydro) Dibenzoyl) zirconium dichloride, bis(m-tolyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzoyl) zirconium dichloride, bis(m-tolyl) ) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentadienoptenyl) zirconium dichloride, bis (m-tolyl) methylene (cyclopentadienyl) (hexamethyl) dihydrodicyclopentadienyl) zirconium dichloride, bis (m-tolyl) methylene (cyclopentadienyl) (b, h-dibenzoyl phenyl) zirconium dichloride, di (p-tert-butylphenyl)methylene(cyclopentadienyl)(3,6-ditertiary Butylphenylinyl)zirconium dichloride, bis(p-tert-butylphenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylphenylinyl) ) zirconium dichloride, bis(p-tertbutylphenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tertbutylphenylenyl)dichloride Zirconium, bis(p-tert-butylphenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzoyl) zirconium dichloride, bis(p-tert-butylphenyl)idene Methyl(cyclopentadienyl)(tetramethyldodecahydrodibenzoyl)zirconium dichloride, bis(p-tert-butylphenyl)methylene(cyclopentadienyl)(octamethyl) tetrahydrodicyclopentadienyl) zirconium dichloride, bis(p-tert-butylphenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentadienyl) base) zirconium dichloride, bis(p-tert-butylphenyl)methylene(cyclopentadienyl)(b,h-dibenzoyl) zirconium dichloride, bis(4-biphenyl) ) methylene (cyclopentadienyl) (2,7-di-tert-butylinyl) zirconium dichloride, bis (4-biphenyl) methylene (cyclopentadienyl) (3, 6-Di-tert-butylphenylinyl) zirconium dichloride, bis(4-biphenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butyl) ylphenyl) zirconium dichloride, bis(4-biphenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylinyl) dichloride zirconium chloride, bis(4-biphenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzoinyl)zirconium dichloride, bis(4-biphenyl)methylene( Cyclopentadienyl)(tetramethyldodecahydrodibenzoyl)zirconium dichloride, bis(4-biphenyl)methylene(cyclopentadienyl)(octamethyltetrahydrobicyclo) Pentadienoptenyl) zirconium dichloride, bis(4-biphenyl)methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentadienoptenyl) zirconium dichloride, Bis(4-biphenyl)methylene(cyclopentadienyl)(b,h-dibenzoyl)zirconium dichloride, bis(p-chlorophenyl)methylene(cyclopentadienyl) ) (Phenyl) zirconium dichloride, bis (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-di-tert-butylphenyl) zirconium dichloride, bis (p-chlorobenzene) yl)methylene(cyclopentadienyl)(3,6-di-tert-butylintenyl)zirconium dichloride, bis(p-chlorophenyl)methylene(cyclopentadienyl)(2, 7-Dimethyl-3,6-di-tert-butylintenyl)zirconium dichloride, bis(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3 , 6-di-tert-butyl-indenyl) zirconium dichloride, bis(p-chlorophenyl) methylene (cyclopentadienyl) (octamethyl octahydrodibenzoinyl) zirconium dichloride, Bis(p-chlorophenyl)methylene(cyclopentadienyl)(tetramethyldodecahydrodibenzoyl) zirconium dichloride, bis(p-chlorophenyl)methylene(cyclopentadiene) yl)(octamethyltetrahydrodicyclopentadienoyl)zirconium dichloride, bis(p-chlorophenyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentadiene) Phenyl) zirconium dichloride, bis(p-chlorophenyl)methylene(cyclopentadienyl)(b,h-dibenzoyl) zirconium dichloride, bis(m-chlorophenyl)idene Methyl (cyclopentadienyl) (intenyl) zirconium dichloride, bis (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-di-tert-butyl indyl) dichloride Zirconium dichloride, bis(m-chlorophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylinyl)zirconium dichloride, bis(m-chlorophenyl)methylene(cyclopentadienyl) pentadienyl)(2,7-dimethyl-3,6-di-tert-butylintenyl)zirconium dichloride, bis(m-chlorophenyl)methylene(cyclopentadienyl)(2 ,7-diphenyl-3,6-di-tert-butylintenyl) zirconium dichloride, bis(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzo Phenyl) zirconium dichloride, bis (m-chlorophenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzoyl) zirconium dichloride, bis (m-chlorophenyl) Methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentadienyl) zirconium dichloride, bis (m-chlorophenyl) methylene (cyclopentadienyl) (hexamethyl) dihydrodicyclopentadienyl) zirconium dichloride, bis(m-chlorophenyl) methylene (cyclopentadienyl) (b,h-dibenzoindenyl) zirconium dichloride, bis(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(peryl)zirconium dichloride, bis(m-trifluoromethylphenyl)methylene(cyclopentadienyl)( 2,7-Di-tert-butyl-intenyl) zirconium dichloride, bis(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(3,6-di-tert-butyl-intenyl) Zirconium dichloride, bis(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tertbutylintenyl)zirconium dichloride , bis (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-tert-butylphenyl) zirconium dichloride, bis (m- Trifluoromethylphenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzophentenyl)zirconium dichloride, bis(m-trifluoromethylphenyl)methylene(cyclopentadienyl) Dienyl)(tetramethyldodecahydrodibenzointenyl)zirconium dichloride, bis(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(octamethyltetrahydrobicyclo) Pentadienoptenyl) zirconium dichloride, bis(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentadienoptenyl) dichloride Zirconium, bis(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(b,h-dibenzoylphenyl)zirconium dichloride, bis(2-naphthyl)methylene(cyclopentadienyl) Pentadienyl)(2,7-di-tert-butylintenyl)zirconium dichloride, bis(2-naphthyl)methylene(cyclopentadienyl)(3,6-di-tert-butyl) Phenyl) zirconium dichloride, bis(2-naphthyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-tertbutylphenylenyl) zirconium dichloride , bis (2-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-tert-butylphenyl) zirconium dichloride, bis (2-naphthyl) ) methylene(cyclopentadienyl)(octamethyloctahydrodibenzoinyl)zirconium dichloride, bis(2-naphthyl)methylene(cyclopentadienyl)(tetramethyldecyl) Dihydrodibenzoyl) zirconium dichloride, bis (2-naphthyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentadienyl) zirconium dichloride, bis(2-naphthyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentadienoptenyl)zirconium dichloride, bis(2-naphthyl)methylene(cyclopentadienyl) Dienyl) (b,h-dibenzoyl) zirconium dichloride and the like.

As an example of the structural formula of the metallocene compound represented by the general formula [A1], bis(p-tolyl)methylene(cyclopentadiene)(octamethyloctahydrodibenzointenyl)dichloro Zirconium (hereinafter referred to as (A)), and bis(p-chlorophenyl)methylene (cyclopentadiene) (8 Structural formula of methyl octahydrodibenzoyl) zirconium dichloride (referred to as (B) below).

The above-mentioned compounds may be used alone or in combination of two or more.

When preparing the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention, the dimetallocene compound represented by the above formula [A1] that can be suitably used is not particularly limited, and can be produced by any method. Specifically, for example, according to J. Organomet. Chem., 63,509 (1996), WO2005/100410, WO2006/123759, WO01/27124, Japanese Patent Laid-Open No. 2004-168744, and Japanese Patent Laid-Open No. 2004 - Manufactured by the methods described in Japanese Patent Application Publication No. 175759, Japanese Patent Laid-Open Publication No. 2000-212194, and the like.

<Polymerization catalyst containing metallocene compound>

A polymerization catalyst suitable for use in the production of the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention includes, for example, the above-mentioned dimetallocene compound [A1], which can copolymerize the monomer.

Preferable examples include: (a) a metallocene compound represented by the general formula [A1]; (b) from (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) ) since At least one compound selected from the above-mentioned metallocene compound (a) which reacts to form an ion pair (hereinafter also referred to as "ionized ionic compound"); polymerization catalyst. Hereinafter, each component is demonstrated concretely.

<<Compound (b)>>

The above-mentioned 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, it contains at least one of the above-mentioned compounds Organometallic compound (b-1).

(b-1) Organometallic compound

As said (b-1) organometallic compound, the organometallic compound of group 1, 2 and group 12, 13 of the periodic table, for example, can be used specifically, for example, the following general formulas [VII] to [IX].

(b-1a) General formula: R ^a _m Al(OR ^b ) _n H _p X _q ‧‧‧[VII]

(In formula [VII], R ^a and R ^b represent hydrocarbon groups with 1 to 15 carbon atoms, preferably 1 to 4, which may be the same or different from each other; X represents a halogen atom; m is 0<m≦3, n It is an organoaluminum compound represented by 0≦n<3, p is 0≦p<3, q is a numerical value of 0≦q<3, and m+n+p+q=3).

Examples of such compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, and other trialkylaluminums; tricycloalkylaluminum, isobutylaluminum dichloride, diethylaluminum chloride, Ethyl aluminum dichloride, ethyl aluminum sesquichloride, methyl aluminum dichloride, dimethyl aluminum chloride, diisobutyl aluminum hydride.

(b-1b) General formula: M ² AlR ^a ₄ ‧‧‧[VIII]

(In formula [VIII], M ² represents Li, Na or K; R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms) A complex alkyl group of a metal of Group 1 of the periodic table and aluminum represented by matter.

As such a compound, LiAl(C ₂ H ₅ ) ₄ , LiAl(C ₇ H ₁₅ ) ₄ and the like can be exemplified.

(b-1c) General formula: R ^a R ^b M ³ ‧‧‧[IX]

(In formula [IX], R ^a and R ^b represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4, which may be the same or different from each other; M ³ represents Mg, Zn or Cd) Table Dialkyl compounds of Group 2 or Group 12 metals.

Among the above-mentioned organometallic compounds (b-1), organoaluminum compounds such as triethylaluminum, triisobutylaluminum, and tri-n-octylaluminum are preferred. Moreover, such an organometallic compound (b-1) system may be used individually by 1 type, and may be used in combination of 2 or more types.

(b-2) Organoaluminum oxy compound

The above-mentioned organoaluminum oxy compound (b-2) may be a conventionally known aluminoxane, or may be a benzene-insoluble organoaluminum oxy compound exemplified in Japanese Patent Laid-Open No. 2-78687.

A conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution in a hydrocarbon solvent.

(1) In a suspension in a hydrocarbon medium containing a compound that adsorbs water or a salt containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerium chloride hydrate, etc., A method of adding an organoaluminum compound such as trialkylaluminum, adsorbing water or crystal water, and reacting with the organoaluminum compound. (2) in benzene, toluene, B A method in which an organoaluminum compound such as trialkylaluminum directly acts on water, ice or water vapor in a medium such as ether and tetrahydrofuran.

(3) A method in which organotin oxides such as dimethyltin oxide and dibutyltin oxide are reacted with organoaluminum compounds such as trialkylaluminum in a medium such as decane, benzene, and toluene.

In addition, the above-mentioned aluminoxane may contain a small amount of an organometallic component. In addition, the solvent or the unreacted organoaluminum compound may be distilled off from the recovered solution of the aluminoxane, and then dissolved in the solvent or suspended in a poor solvent of the aluminoxane.

Specific examples of the organoaluminum compound used for preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound to which the above (b-1a) belongs.

Among them, trialkylaluminum and tricycloalkylaluminum are preferred, and among them, trimethylaluminum and triisobutylaluminum are particularly preferred.

The organoaluminum compounds described above can be used alone or in combination of two or more.

Furthermore, the benzene-insoluble organoaluminum oxy compound, which is one aspect of the organoaluminum oxy compound (b-2) used in the present invention, is the Al component dissolved in benzene at 60° C. in terms of Al atom, relative to 100 of benzene. The weight % is usually 10 wt % or less, preferably 5 wt % or less, particularly preferably 2 wt % or less, that is, preferably insoluble or poorly soluble in benzene.

As the organoaluminum oxy compound (b-2) used in the present invention, a boron-containing organoaluminum oxy compound represented by the following general formula [X] may also be mentioned.

[Chemical 12]

In formula [X], R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms; R ² to R ⁵ represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different from each other.

The boron-containing organoaluminum oxy compound represented by the general formula [X] can be obtained by using the general formula: R ¹ -B(OH) ₂ ‧‧‧[XI]

(In the formula [XI], R ¹ represents the same group as R ¹ in the general formula [X] above.)

The shown alkylboronic acid and the organoaluminum compound are produced by reacting with -80°C to room temperature in an inert solvent for 1 minute to 24 hours in an inert gas atmosphere.

Specific examples of the alkylboronic acid represented by the general formula [XI] include methylboronic acid, ethylboric acid, isopropylboric acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, Cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, 3,5-bis(trifluoromethyl)phenylboronic acid, etc.

Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These can be used individually by 1 type or in combination of 2 or more types.

Specific examples of the organoaluminum compound to be reacted with such an alkylboronic acid include the same organoaluminum compounds as exemplified as the organoaluminum compound to which the above (b-1a) belongs. Among these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferred.

As described above, the organoaluminum oxy compound (b-2) may be used alone or in combination of two or more.

(b-3) Ionized ionic compound

As the above-mentioned ionizing ionic compound (b-3), for example, Japanese Patent Laid-Open No. 1-501950, Japanese Patent Laid-Open No. 1-502036, Japanese Patent Laid-Open No. 3-179005, and Japanese Patent Laid-Open No. 3-179006 may be mentioned. , Lewis acid, ionic compound, borane compound, carboron compound, etc. described in Japanese Patent Laid-Open No. 3-207703, Japanese Patent Laid-Open No. 3-207704, USP-5321106 and the like. Moreover, for example, a heteropolymeric compound and a heteropolymeric compound can also be mentioned. Such an ionizing ionic compound (b-3) can be used individually by 1 type or in combination of 2 or more types.

Specifically, examples of Lewis acids include compounds represented by BR ₃ (R-based phenyl or fluorine may have substituents such as fluorine, methyl, and trifluoromethyl), and examples include trifluoroboron, trifluoroboron, and trifluoroboron. Phenylboron, ginseng (4-fluorophenyl)boron, ginseng (3,5-difluorophenyl)boron, ginseng (4-fluoromethylphenyl)boron, ginseng (pentafluorophenyl)boron, ginseng ( p-Tolyl) boron, para (o-tolyl) boron, para (3,5-dimethylphenyl) boron, etc.

Examples of the ionic compound include compounds represented by the following general formula [XII].

In formula [XII], examples of R ¹⁺ include H ⁺ , carbocation, oxy cation, ammonium cation, phosphonium cation, cycloheptatrienyl cation, transition metal-containing ferrocene cation, and the like. R ² to R ⁵ can be the same or different organic groups, preferably aryl groups or substituted aryl groups.

As said carbocation, trisubstituted carbocations, such as a triphenyl carbocation, a tris (methylphenyl) carbocation, a tri (dimethylphenyl) carbocation, etc. are mentioned, for example.

Specific examples of the above-mentioned ammonium cations include trimethylammonium cations, triethylammonium cations, tripropylammonium cations, tributylammonium cations, tri(n-butyl)ammonium cations and other trialkylammonium cations; N,N-dimethylanilinium cations , N,N-diethylanilinium cations, N,N,2,4,6-pentamethylanilinium cations and other N,N-dialkylanilinium cations; Dialkylammonium cations such as cyclohexylammonium cations, etc.

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

Preferable examples of R ¹⁺ are carbocations, ammonium cations, and the like, and particularly preferable are triphenylcarbocations, N,N-dimethylanilinium cations, and N,N-diethylanilinium cations.

Moreover, as an ionic compound, a trialkyl substituted ammonium salt, a N,N- dialkylanilinium salt, a dialkylammonium salt, a triarylphosphonium salt, etc. are mentioned, for example.

Specific examples of trialkyl substituted ammonium salts include: triethylammonium tetra(phenyl) boron, tripropylammonium tetra(phenyl) boron, tri(n-butyl) ammonium tetra(phenyl) boron, trimethylammonium tetra(phenyl) boron p-Tolyl) boron, trimethylammonium tetra(o-tolyl) boron, tri(n-butyl) ammonium tetra(pentafluorophenyl) boron, tripropylammonium tetra(o, p-dimethylphenyl) boron, tri(n-butyl) ammonium tetra(o, p-dimethylphenyl) boron n-butyl)ammonium tetrakis(N,N-dimethylphenyl)boron, tri(n-butyl)ammonium tetrakis(p-trifluoromethylphenyl)boron, tri(n-butyl)ammonium tetrakis(3,5 -Bis(trifluoromethyl)phenyl)boron, tri(n-butyl)ammonium tetrakis(o-tolyl)boron, etc.

Specific examples of the N,N-dialkylanilinium salt include N,N-dimethylanilinium tetrakis(phenyl)boron, N,N-diethylanilinium tetrakis(phenyl)boron, N,N-diethylanilinium tetrakis(phenyl)boron, N,2,4,6-pentamethylanilinium tetrakis (phenyl) boron, etc.

Specific examples of the dialkylammonium salt include di(1-propyl)ammonium tetrakis (pentafluorophenyl) boron, dicyclohexyl ammonium tetrakis (phenyl) boron, and the like.

Furthermore, the ionic compound can also be, for example, triphenylcarbonium (pentafluorophenyl) borate, N,N-dimethylanilinium (pentafluorophenyl) borate, ferrocene (pentafluorophenyl) borate. Fluorophenyl) borate, triphenylcarbonium pentaphenylcyclopentadiene complex, N,N-diethylanilinium pentaphenylcyclopentadiene complex, the following formula [XIII] or [ XIV] boron compounds, etc. Also, Et in the formula represents an ethyl group.

Specific examples of the borane compound include decaborane; Bis[tri(n-butyl)ammonium]nonaborate, bis[tri(n-butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium]undecaborate, bis[tri(n-butyl)ammonium] ) ammonium] dodecaborate, bis[tri(n-butyl) ammonium] decachlorodecaborate, bis[tri(n-butyl) ammonium] dodecachlorododecaborate and other salts of anions; tris(n-butyl) Metal boranes such as bis(dodecahydrododecaborate) cobaltate (III), bis[tri(n-butyl)ammonium]bis(dodecahydrododecaborate) nickelate (III) Anionic salts, etc.

Specific examples of the carboron compound include 4-carbonaborane, 1,3-dicarbonaborane, 6,9-dicarbonadecaborane, dodecahydro-1-phenyl-1,3-dicarbon Nonaborane, dodecahydro-1-methyl-1,3-dicarbonaborane, undecahydro-1,3-dimethyl-1,3-dicarbonaborane, 7,8-dicarbonaborane Carboundecaborane, 2,7-Dicarbundecaborane, Undecahydro-7,8-dimethyl-7,8-didecabundecane, dodecahydro-11-methyl-2 ,7-Dicarbonundecaborane, Tris(n-butyl)ammonium-1-carbodecaborate, Tris(n-butyl)ammonium-1-carbundecaborate, Tris(n-butyl)ammonium-1 -Carbododecaborate, Tris(n-butyl)ammonium-1-trimethylsilyl-1-carbodecaborate, Tris(n-butyl)ammonium bromide-1-carbodecaborate, Tris(n-butyl) ) Ammonium-6-carbadecaborate, tris(n-butyl)ammonium-7-carbaundecaborate, tris(n-butyl)ammonium-7,8-didecadecaborate, tris(n-butyl) ) Ammonium-2,9-dicarbonundecaborate, tri(n-butyl)ammonium dodecahydro-8-methyl-7,9-dicarbonundecaborate, tris(n-butyl)ammonium undecanoate Hydro-8-ethyl-7,9-dicarbonundecaborate, tri(n-butyl)ammonium undecahydro-8-butyl-7,9-dicarbonundecaborate, tris(n-butyl) ) Ammonium undecahydro-8-allyl-7,9-dicarbonundecaborate, tri(n-butyl)ammonium undecahydro-9-trimethylsilyl-7,8-dicarbonundecaborate , Tri(n-butyl)ammonium undecahydro-4,6-dibromo-7-carbonundecaborate and other salts of anions; tri(n-butyl)ammonium bis(nonahydro-1,3-dicarbonone) borate) cobaltate (III), tri(n-butyl)ammonium bis(undecahydro-7,8-dicarbonundecaborate)ferrite (III), tri(n-butyl)ammonium bis(undecahydro-7,8-dicarbonundecaborate) (undecahydro-7,8-dicarbonundecaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydro-7,8-dicarbonundecaborate)nickelate (III), tri(n-butyl)ammonium bis(undecahydro-7,8-dicarbonundecaborate) cuprate (III), tri(n-butyl)ammonium bis(undecahydro-7, 8-Dicarbonundecaborate) aurate (III), tri(n-butyl)ammonium bis(nonahydro-7,8-dimethyl-7,8-dicarbonundecaborate) ferrite (III), tri(n-butyl)ammonium bis(nonahydro-7,8-dimethyl-7,8-dicarbonundecaborate) chromate (III), tri(n-butyl)ammonium bis(nonahydro-7,8-dimethyl-7,8-dicarbonundecaborate) (Tribromooctahydro-7,8-dicarbonundecaborate)cobaltate(III), sam[tri(n-butyl)ammonium]bis(undecahydro-7-carbonundecaborate)chromic acid Salt (III), bis[tri(n-butyl)ammonium]bis(undecahydro-7-carbonundecaborate)manganate (IV), bis[tri(n-butyl)ammonium]bis(undecyl) Metal carbon such as hydrogen-7-carbonundecaborate) cobaltate (III), bis[tri(n-butyl)ammonium]bis(undecahydro-7-carbonundecaborate) nickelate (IV) salts of boron anions, etc.

The heteropolymer compound is composed of atoms selected from silicon, phosphorus, titanium, germanium, arsenic, and tin, and one or more atoms selected from vanadium, niobium, molybdenum, and tungsten. Specifically, phosphovanadic acid, germanium vanadic acid, arsenic vanadic acid, phosphoniobic acid, germanium niobic acid, silicon molybdic acid, phosphomolybdic acid, titanium molybdic acid, germanium molybdic acid, arsenomolybdic acid, tin molybdate, phosphorus Tungstic acid, germanium tungstic acid, tin tungstate, phosphomolybdic acid, phosphotungstic acid, tungstogermanic acid, phosphomolybdotungstic acid, germanium molybdenum tungstovanadic acid, phosphomolybdotungstic acid, phosphomolybdoniobic acid, and the like Salts of isoacids, such as metals of Group 1 or Group 2 of the periodic table, specifically, salts with lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc., triphenylethyl Organic salts such as base salts are not limited thereto.

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

In the present invention, as the polymerization catalyst, a metallocene compound (a) represented by the above general formula [A1], an organometallic compound (b-1) such as triisobutylaluminum, a Organoaluminum oxide compounds (b-2) such as alkanes and metallocene catalysts of ionizing ionic compounds (b-3) such as triphenylcarbonium (pentafluorophenyl) borate, etc., are used in the production of ethylene. α-olefin·non-conjugated polyene copolymer can exhibit very high polymerization activity.

(c) Particulate carrier

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

The inorganic compound is preferably a porous oxide, an inorganic halide, clay, a clay mineral or an ion-exchangeable layered compound. As such a specific example, what is described in International Patent No. WO2015/122495 can be mentioned, for example.

The clay, clay minerals, and ion-exchange layered compounds used in the present invention can be used as they are, or they can be used after ball milling, sieving, or the like. Moreover, adsorption water may be added again, or it may be used after heating and dehydration treatment. In addition, it can be used individually or in combination of 2 or more types.

Among them, clay or clay minerals are preferable, and montmorillonite, vermiculite, hectorite, lithium magnesium mica and synthetic mica are particularly preferable.

As the organic compound, for example, granular hydrocarbons are granulated or particulate solids in the range of 10 to 300 μm. Specifically, (co)polymers or vinylcyclohexenes produced by using α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene as the main component can be exemplified. Alkane; (co)polymers and modified products thereof produced with styrene as a main component.

The metallocene catalyst system used in the present invention contains a metallocene compound (a), a secondary organometallic compound (b-1), an organoaluminum oxy compound (b-2), and an ionizing ionic compound (b-3) At least one compound (b) selected from among the The body (c) may also contain a specific organic compound component (d) as needed.

(d) Organic compound components

In the present invention, the above-mentioned organic compound component (d) is used as necessary for the purpose of improving the polymerization performance and the physical properties of the resulting polymer. Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

<Manufacturing method and conditions>

The ethylene·α-olefin·non-conjugated polyene copolymer of the present invention (hereinafter sometimes referred to as "ethylene·α-olefin·non-conjugated polyene copolymer (S)") may be composed of ethylene (A), carbon atoms It is produced by copolymerizing monomers composed of the α-olefin (B) of 3 to 20, the above-mentioned non-conjugated polyene (C), and optionally the above-mentioned non-conjugated polyene (D).

When the monomer is copolymerized, the method of use and the order of addition of each component constituting the above-mentioned polymerization catalyst can be arbitrarily selected, and the following methods can be exemplified.

(1) A method of adding the metallocene compound (a) alone to a polymerizer.

(2) A method of adding the metallocene compound (a) and the compound (b) to a polymerizer in any order.

(3) A method of adding the catalyst component and the compound (b) in which the metallocene compound (a) is supported on the carrier (c) to a polymerizer in an arbitrary order.

(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 to a polymerizer in an arbitrary order.

(5) A method in which a catalyst component in which the metallocene compound (a) and the compound (b) are supported on the carrier (c) is added to a polymerizer.

In each of the methods (2) to (5) above, the metallocene compound can also be prepared in advance At least two of (a), compound (b), and carrier (c) are contacted.

In each method of the above (4) and (5) in which the compound (b) is supported, the compound (b) which is not supported may be added in an arbitrary order if necessary. In this case, the compound (b) may be the same as or different from the compound (b) carried by the carrier (c).

Furthermore, a solid catalyst component in which the metallocene compound (a) is supported on the carrier (c), and a solid catalyst component in which the metallocene compound (a) and the compound (b) are supported on the carrier (c). , the olefin can be pre-polymerized, and the catalyst component can be further supported on the pre-polymerized solid catalyst component.

In the present invention, the ethylene·α-olefin·non-conjugated polyene copolymerization system is appropriately obtained by copolymerizing monomers in the presence of the above-mentioned dimetallocene catalyst.

When the above-mentioned dimetallocene catalyst is used to carry out the copolymerization of the monomer, the dimetallocene compound (a) is usually used to be 10 ^-12 to 10 ^-2 mol, preferably 10 ^- mol per 1 liter of the reaction volume. The amount of ¹⁰ ~ 10 ^-8 moles.

The compound (b-1) is the molar ratio [(b-1)/M] of the compound (b-1) and the total transition metal atoms (M) in the metallocene compound (a), usually 0.01~ 50000, preferably 0.05~10000. The compound (b-2) is the molar ratio [(b-2)/M] of the aluminum atom in the compound (b-2) to the total transition metal (M) in the metallocene compound (a) [(b-2)/M], usually used The amount is 10 to 50,000, preferably 20 to 10,000. Compound (b-3) is the molar ratio [(b-3)/M] between compound (b-3) and the transition metal atom (M) in the metallocene compound (a), usually 1 to 20. , preferably the amount of 1~15.

In the present invention, the method for producing the ethylene·α-olefin·non-conjugated polyene copolymer can be carried out by either a liquid phase polymerization method such as solution (dissolution) polymerization or suspension polymerization or a gas phase polymerization method, and there is no particular limitation, it is preferable to obtain the following polymerization Steps in the reaction solution.

The so-called step of obtaining a polymerization reaction solution is to use an aliphatic hydrocarbon as a polymerization solvent, and in the metallocene catalyst of the present invention, preferably, R ¹³ and R ¹⁴ bound by Y ¹ in the general formula [A1] are: In the presence of a phenyl group, or a phenyl group substituted with an alkyl group or a halogen group, R ⁷ and R ¹⁰ are a transition metal compound having an alkyl substituent, in the presence of a metallocene catalyst, ethylene (A), carbon atom The α-olefin (B) of number 3 to 20 is copolymerized with a monomer composed of a non-conjugated polyene (C) and a non-conjugated polyene (D) as needed to obtain ethylene·α-olefin·non-conjugated polyene (D). The step of the polymerization reaction solution of the conjugated polyene copolymer.

As a polymerization solvent, aliphatic hydrocarbon, aromatic hydrocarbon, etc. are mentioned, for example. Specific examples include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; lipids such as cyclopentane, cyclohexane, and methylcyclopentane. Cyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as vinyl chloride, chlorobenzene, and dichloromethane can be used alone or in combination of two or more. In addition, the olefin itself can also be used as a solvent. In addition, among these, from the viewpoint of separation and purification from the obtained ethylene·α-olefin·non-conjugated polyene copolymer, hexane is preferred.

Furthermore, the polymerization temperature is usually in the range of -50 to +200°C, preferably in the range of 0 to +150°C, and more preferably in the range of +70 to +110°C, depending on the molecular weight and polymerization activity of the two metallocene catalyst systems used. Although different, from the viewpoints of catalyst activity, copolymerizability and productivity, higher temperature (+70°C or higher) is preferable.

The polymerization pressure is usually under the condition of normal pressure~10MPa gauge pressure, preferably 1.1~5MPa gauge pressure, and more preferably 1.2~2.0MPa gauge pressure. The polymerization reaction can be carried out according to any method such as batch, semi-continuous and continuous. implement. In addition, the polymerization may be divided into two or more stages with different reaction conditions and may be carried out. The present invention preferably adopts a method in which the monomer is continuously supplied to the reactor for copolymerization.

The reaction time (the average residence time when the copolymerization is carried out according to the continuous method) varies according to the catalyst concentration, polymerization temperature and other conditions, usually 0.5 minutes to 5 hours, preferably 5 minutes to 3 hours, more preferably 10 minutes ~2 hours.

The molecular weight of the obtained ethylene·α-olefin·non-conjugated polyene copolymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Moreover, it can also adjust by the quantity of the compound (b) used. Specifically, for example, triisobutylaluminum, methaluminoxane, diethylzinc, etc. may be mentioned. In the case of adding hydrogen, the amount thereof is about 0.001 to 100 NL per 1 kg of olefin.

Furthermore, the packing molar ratio of ethylene (A) and the above-mentioned α-olefin (B) (ethylene (A)/α-olefin (B)) is preferably 40/60~99.9/0.1, more preferably 50/ 50~90/10, and the best line is 55/45~85/15, and the best line is 55/45~78/22.

The loading amount of the non-conjugated polyene (C) is 100% by weight relative to the total (total monomer loading amount) of ethylene (A), α-olefin (B) and non-conjugated polyene (C), usually 0.07 ~10% by weight, preferably 0.1% by weight to 8.0% by weight, more preferably 0.5% by weight to 5.0% by weight.

In the present invention, after the step (1) of carrying out the copolymerization in the presence of the above-mentioned polymerization catalyst, it is preferable to include the step (2) of adding a catalyst inactivating agent to deactivate the above-mentioned polymerization catalyst.

As the catalyst deactivating agent, alcohols can be used, and methanol or ethanol is preferable, and ethanol is particularly preferable.

[Thermoplastic resin composition]

The thermoplastic resin composition of the present invention is characterized by containing the above-mentioned ethylene·α-olefin·non-conjugated polyene copolymer of the present invention.

The thermoplastic resin composition of the present invention may suitably contain various additives, fillers and the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention which can be formulated into the resin composition.

The thermoplastic resin composition of the present invention can be cross-linked and can be suitably used in various applications, and it is preferable to contain a cross-linking agent in the thermoplastic resin composition. As the crosslinking agent, known crosslinking agents can be used without particular limitation, and among them, organic peroxides are preferred.

When the thermoplastic resin composition of the present invention contains an organic peroxide, the content (mol) of the organic peroxide preferably satisfies the following formula (7).

Content of organic peroxide (mol)×number of oxygen-oxygen bonds in 1 molecule of organic peroxide≦(C) weight fraction/(C) molecular weight×100... Formula (7)

In the formula (7), the weight fraction of (C) represents the weight fraction (% by weight) of the constituent unit derived from the non-conjugated polyene (C) in the ethylene·α-olefin·non-conjugated polyene copolymer, The molecular weight of (C) represents the molecular weight of the non-conjugated polyene (C).

The thermoplastic resin composition of the present invention is preferably a rubber composition described later.

[rubber composition]

The ethylene·α-olefin·non-conjugated polyene copolymer of the present invention exhibits good rubber properties, and is suitable for use as a raw material for a rubber composition.

The rubber composition of the present invention is characterized by containing the ethylene·α-olefin·non-conjugated polyene copolymer (S) of the present invention. In addition, a preferable aspect of the rubber composition of the present invention (hereinafter also referred to as "rubber composition (X)") further contains a rubber component selected from the group consisting of diene rubber, butyl rubber and halogenated butyl rubber. (T), and on The content ratio (mass ratio: (S)/(T)) of the ethylene·α-olefin·non-conjugated polyene copolymer (S) to the rubber component (T) is in the range of 5/95 to 50/50.

<Rubber component (T)>

As the rubber component (T), known diene rubbers, butyl rubbers, and halogenated butyl rubbers having double bonds can be used without limitation, and these can be used alone or in combination of two or more. As the diene rubber, a polymer or copolymer rubber containing a conjugated diene compound as a main monomer is preferably used. In the present invention, the diene-based rubber also includes natural rubber (NR) and hydrogenated rubber. As the rubber component (T), an uncrosslinked one is usually used, and an iodine value of 100 or more is preferable, 200 or more is more preferable, and 250 or more is more preferable.

As such a rubber component (T), for example, natural rubber (NR), isoprene rubber (IR), styrene-butadiene rubber (SBR), butadiene rubber (BR), chloropentene rubber ( CR), acrylonitrile-butadiene rubber (NBR), nitrile rubber, hydrogenated nitrile rubber and other diene rubbers, butyl rubber and halogenated butyl rubber.

Butyl rubber and halogenated butyl rubber are generally classified as non-diene-based rubbers, but since they have unsaturated carbon bonds in the main chain like diene-based rubbers, they are compared to other non-diene rubbers such as propylene rubber. Rubbers have the same problems as diene rubbers, such as deterioration of weather resistance. In the present invention, also when butyl rubber or halogenated butyl rubber is used as the rubber component (T), the weather resistance can be improved similarly to the case of the diene rubber.

In the present invention, the rubber component (T) is preferably a diene rubber, and among them, natural rubber (NR), isoprene rubber (IR), styrene-butadiene rubber (SBR), and butadiene are more preferred. Rubber (BR), especially styrene-butadiene rubber (SBR). These rubber components (T) may be used alone or in combination of two or more.

As the natural rubber (NR), natural rubber standardized by Green Book (an international quality packaging standard for various grades of natural rubber) can be used. As the isoprene rubber (IR), those having a specific gravity of 0.91 to 0.94 and a Mooney viscosity [ML ₁₊₄ (100°C), JIS K6300] of 30 to 120 are suitable.

As the styrene-butadiene rubber (SBR), those having a specific gravity of 0.91 to 0.98 and a Munich viscosity [ML ₁₊₄ (100°C), JIS K6300] of 20 to 120 are suitable. As the butadiene rubber (BR), those having a specific gravity of 0.90 to 0.95 and a Munich viscosity [ML ₁₊₄ (100°C), JIS K6300] of 20 to 120 are suitably used.

The rubber composition (X) of the present invention contains the above-mentioned ethylene·α-olefin·non-conjugated polyene copolymer (S) and the rubber component (T) as essential components, and is composed of ethylene·α-olefin·non-conjugated polyene. The mass ratio of the olefin copolymer (S) to the rubber component (T) [(S)/(T)] satisfies 5/95~50/50, preferably 15/85~45/55, more preferably 20/80~40 The amount of /60 contains these.

In the rubber composition (X) of the present invention, the total content of the ethylene·α-olefin·non-conjugated polyene copolymer (S) and the rubber component (T) is 3 mass % or more, preferably 5 mass % or more, and the upper limit is It does not specifically state, but 90 mass % or less is preferable. The rubber composition of the present invention is superior in rubber elasticity, weather resistance and ozone resistance, especially in mechanical properties, weather resistance and fatigue resistance. In addition, the rubber composition is also excellent in abrasion resistance. Therefore, if the rubber composition of the present invention is used, a tire with excellent braking performance and excellent fuel consumption performance, excellent rubber elasticity, weather resistance and ozone resistance, especially mechanical properties and fatigue resistance, can be obtained. Also, a tire excellent in wear resistance can be obtained.

<optional ingredients>

The rubber composition of the present invention (including the rubber composition (X), the same applies hereinafter) is used for compounding purposes, and may appropriately contain softeners, fillers, other resin components, and cross-linking agents within the scope of not impairing the purpose of the present invention. , foaming agent, antioxidant (stabilizer), weathering agent, can Arbitrary components such as plasticizers, colorants, and various conventionally known additives formulated in rubber compositions.

[softener]

As softeners, those formulated in conventional rubbers are widely used.

Specific examples include: petroleum-based softeners such as paraffin-based processing oils, naphthenic-based processing oils, and aromatic-based processing oils; synthetic oil-based softening materials; copolymer oligomers of ethylene and α-olefin; paraffin, wax; flowing paraffin; white oil; petrolatum; coal tar-based softeners such as coal tar, coal tar pitch, etc.; castor oil, cottonseed oil, linseed oil, rapeseed oil, coconut oil, palm oil, soybean oil, peanut oil, wood Vegetable oil-based softeners such as wax, rosin, pine oil, dipentene, pine tar, tar, etc.; substitute rubber (oil gum) for black substitute rubber, white substitute rubber, translucent substitute rubber, etc.; beeswax, carnauba wax, Waxes such as lanolin; fatty acids and fatty acid salts of ricinoleic acid, palmitic acid, myristic acid, barium stearate, calcium stearate, magnesium stearate, zinc stearate, zinc laurate, etc.; phthalate Ester plasticizers such as dioctyl acid, dioctyl adipate, dioctyl sebacate, etc.; Lavender-indene resin; phenol-formaldehyde resin; terpene-phenol resin; polyterpene resin; synthetic polyterpene resin, aromatic hydrocarbon resin, aliphatic hydrocarbon resin, aliphatic cyclic hydrocarbon resin, aliphatic-lipid Cyclic petroleum resins, aliphatic and aromatic petroleum resins, hydrogenated modified alicyclic hydrocarbon resins, hydrogenated hydrocarbon resins, liquid polybutene, liquid polybutadiene, heterocyclic polypropylene, etc. Hydrocarbon resins; etc.

Among these, petroleum-based softeners, phenol-formaldehyde resins, and petroleum-based hydrocarbon resins are preferred, petroleum-based softeners and petroleum-based hydrocarbon resins are more preferred, and petroleum-based softeners are particularly preferred.

Among the petroleum-based softeners, petroleum-based processing oils are preferred, and paraffin-based processing oils, naphthenic-based processing oils, aromatic-based processing oils, and the like are more preferred, and paraffin-based processing oils are particularly preferred.

In addition, among the petroleum-based hydrocarbon resins, an aliphatic hydrocarbon resin is preferred.

Among these softeners, paraffin-based processing oils are particularly preferred.

Furthermore, the softener may be used alone or two or more kinds may be used.

The content of the softener in the rubber composition of the present invention is 0.1 to 300 parts by weight, preferably 1 to 250 parts by weight, relative to 100 parts by weight of the ethylene·α-olefin·non-conjugated polyene copolymer. More preferably, it is 5 to 200 parts by weight. Within the above range, the rubber composition is preferable because it is excellent in molding processability such as extrusion moldability, press moldability, injection moldability, or the like, or roll processability.

[filler]

The filler is not particularly limited, but inorganic fillers are preferred because they can improve mechanical strengths such as tensile strength, tear strength, and abrasion resistance of the rubber composition.

As inorganic fillers, for example, carbon blacks such as SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, MT, etc. can be listed; these carbon blacks are surface-treated carbon blacks that are surface-treated by silane coupling agents, etc.; Silica, activated calcium carbonate, light calcium carbonate, heavy calcium carbonate, micronized talc, talc, micronized silicic acid, clay, etc.

In addition, one type of filler may be used alone, or two or more types may be used.

The content of the filler in the rubber composition of the present invention is 1-300 parts by weight, preferably 5-250 parts by weight relative to 100 parts by weight of the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention parts by weight, more preferably 10 to 200 parts by weight. Within the above range, the rubber composition has excellent kneading properties and processability, and the rubber molded body has excellent mechanical properties and compressive permanent strain, so it is preferable. In addition, a cross-linked molded body with improved mechanical properties such as tensile strength, tensile strength and abrasion resistance can be obtained, and the hardness of the cross-linked molded body can be improved without impairing other physical properties of the cross-linked molded body, thereby reducing the manufacturing cost of the cross-linked molded body. .

[Other resin components]

The rubber composition of the present invention may contain resin components other than the above-mentioned ethylene·α-olefin·non-conjugated polyene copolymer as necessary. Although it does not specifically limit as such another resin component, Polyolefin resin is preferable.

If the rubber composition of the present invention contains a polyolefin resin, the hardness of the product can be adjusted, and the viscosity of the composition at the processing temperature can be reduced, so the processability can be further improved. Moreover, since it can be handled as a thermoplastic elastomer, and the range of handling properties and kneading methods is widened, it is preferable.

As the polyolefin resin, a polyolefin resin having a number average molecular weight of 10,000 or more in terms of standard polystyrene measured by GPC is generally used.

As a polyolefin resin, an alpha-olefin homopolymer and an alpha-olefin copolymer are mentioned, for example. Examples of the α-olefin homopolymer include polyethylene, polypropylene, and the like, and examples of the α-olefin copolymer include ethylene and α-olefin copolymers having 3 to 20 carbon atoms, and ethylene and 3 to 3 carbon atoms. Alpha-olefin·non-conjugated polyene copolymer of 20 (which is different from the ethylene·α-olefin·non-conjugated polyene copolymer of the present invention). Examples of the ethylene-carbon 3-20 α-olefin copolymer include ethylene-propylene rubber (EPR), propylene-ethylene rubber (PER), ethylene-butene rubber (EBR), ethylene-octene rubber ( EOR) etc.

Moreover, as an ethylene-carbon 3-20 α-olefin-non-conjugated polyene copolymer (which is different from the ethylene-α-olefin-non-conjugated polyene copolymer of the present invention), for example Ethylene Propylene Terpolymer (EPT), Ethylene Butene Terpolymer (EBT), etc.

As the polyolefin resin, among them, polyethylene, ethylene·α-olefin copolymer, and polypropylene are preferable.

In addition, polyolefin resin may be used individually by 1 type, and may use 2 or more types.

When the rubber composition of the present invention contains a polyolefin resin, the content of the polyolefin resin is 1 to 100 parts by weight relative to 100 parts by weight of the above-mentioned ethylene·α-olefin·non-conjugated polyene copolymer, and the content of the polyolefin resin is 1 to 100 parts by weight, more than 100 parts by weight. It is preferably 5 to 80 parts by weight, more preferably 10 to 50 parts by weight. Within the above range, the hardness of the molded body formed of the rubber composition can be adjusted, and the viscosity of the composition at the processing temperature can be reduced, so that the processability can be further improved. Moreover, since it can be handled as a thermoplastic elastomer, and the range of handling properties and kneading methods is widened, it is preferable.

[Crosslinking agent]

The rubber composition of the present invention is a crosslinkable composition, and by crosslinking it, the crosslinked molded body of the present invention described later can be produced. Crosslinking can be performed by heating or the like using a crosslinking agent, or by radiation crosslinking in which crosslinking is performed by irradiation with radiation such as electron beams, X rays, γ rays, α rays, and β rays. Among radiation crosslinking, electron beam crosslinking is preferred.

The cross-linked molded body of the present invention is preferably produced by radiation cross-linking, in particular, electron beam cross-linking, and in this case, the rubber composition may not contain a cross-linking agent.

In addition, when the rubber composition is cross-linked by heating, the rubber composition preferably contains a cross-linking agent.

Examples of crosslinking agents include sulfur-based compounds, organic peroxides, phenol resins, hydropolysiloxane-based compounds, amine-based resins, quinones or derivatives thereof, amine-based compounds, azo-based compounds, and epoxy-based compounds. A crosslinking agent generally used when crosslinking rubber such as isocyanate and isocyanate. Among these crosslinking agents, sulfur-based compounds, organic peroxides, and phenol resins are preferred. Since the ethylene·α-olefin·non-conjugated polyene copolymerization system of the present invention can achieve particularly excellent cross-linking properties in the cross-linking using organic peroxides, the rubber composition of the present invention is particularly preferably containing organic peroxides. Peroxides act as crosslinking agents.

When the crosslinking agent is an organic peroxide, specific examples thereof include dicumyl peroxide, di-tert-butyl peroxide, and 2,5-di-(tert-butyl peroxide) Hexane, 2,5-dimethyl-2,5-di-(tert-butyl peroxide)hexane, 2,5-dimethyl-2,5-di-(tert-butyl peroxide) Hexyne-3, 1,3-bis(tert-butyl isopropyl peroxide)benzene, 1,1-bis(tert-butyl peroxide)-3,3,5-trimethylcyclohexane, n-Butyl-4,4-bis(over tertiary butyl) valerate oxide, benzyl peroxide, p-chlorobenzyl peroxide, 2,4-dichlorobenzyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauryl peroxide, tert-butyl cumyl peroxide, etc.

Among these, from the viewpoint of reactivity, odor properties, and coking stability, 2,5-di-(tert-butylperoxide)hexane, 2,5-dimethyl-2 ,5-di-(tert-butyl peroxide)hexane, 2,5-dimethyl-2,5-di-(tert-butyl peroxide)hexyne-3, 1,3-bis(peroxide) tert-butylisopropyl)benzene oxide, 1,1-bis(tert-butylperoxide)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(peroxide) A bifunctional organic peroxide having two peroxide bonds (-O-O-) in 1 molecule, such as tert-butyl) valerate, preferably 2,5-di-(tert-butyl peroxide) ) hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxide)hexane.

When the crosslinking agent is an organic peroxide, the compounding amount of the organic peroxide is relative to 100 parts by weight of the ethylene·α-olefin·non-conjugated polyene copolymer, usually 0.1 to 20 parts by weight, preferably 0.1 to 20 parts by weight. 0.2 to 15 parts by weight, more preferably 0.5 to 10 parts by weight. If the compounding amount of the organic peroxide is within the above-mentioned range, the surface of the obtained rubber molded body does not bloom, and the rubber composition exhibits excellent cross-linking properties, which is preferable.

When an organic peroxide is used as the crosslinking agent, the rubber composition of the present invention preferably contains the following crosslinking assistant.

When an organic peroxide is used as the crosslinking agent, the crosslinking assistants suitable for the rubber composition include sulfur; quinonedioxime-based crosslinking assistants such as p-quinonedioxime; Acrylic cross-linking aids such as trimethylolpropane trimethacrylate; allyl cross-linking aids such as diallyl phthalate and triallyl cyanurate; other maleic Imide-based cross-linking aids; divinylbenzene, etc. The compounding amount of the crosslinking aid is 1 mol relative to the organic peroxide, usually 0.5-10 mol, preferably 0.5 to 10 mol. 0.5-7 mol, more preferably 1-5 mol. In addition, the compounding amount of the crosslinking aid is 0.5 to 2 mol, preferably 0.5 to 1.5 mol, relative to 1 mol of the organic peroxide, more preferably an amount of almost equal mol.

In the rubber composition of the present invention, the compounding amount of the organic peroxide is the amount contained in the thermoplastic resin composition of the present invention, that is, the content (mol) of the organic peroxide is one that satisfies the following formula (7). quantity.

Content of organic peroxide (mol)×number of oxygen-oxygen bonds in 1 molecule of organic peroxide≦(C) weight fraction/(C) molecular weight×100... Formula (7)

In formula (7), the weight fraction of (C) is the weight fraction (% by weight) of the constituent unit derived from the non-conjugated polyene (C) in the ethylene·α-olefin·non-conjugated polyene copolymer, which is The molecular weight of (C) is represented by the molecular weight of the non-conjugated polyene (C).

In addition, one type of crosslinking agent may be used alone, or two or more types may be used.

啉、二硫化烷基酚、二硫化四甲基秋蘭姆、二硫代胺基甲酸硒等。 When the crosslinking agent is a sulfur-based compound, specific examples thereof include sulfur, sulfur chloride, sulfur dichloride, and disulfide

Phosphate, alkylphenol disulfide, tetramethylthiuram disulfide, selenium dithiocarbamate, etc.

When the crosslinking agent is a sulfur-based compound, the compounding amount of the sulfur-based compound is based on 100 parts by weight of the ethylene·α-olefin·non-conjugated polyene copolymer, usually 0.3-10 parts by weight, preferably 0.5- 7.0 parts by weight, more preferably 0.7 to 5.0 parts by weight. If the compounding amount of the sulfur-based compound is within the above-mentioned range, the surface of the obtained rubber molded body does not bloom, and the rubber composition exhibits excellent crosslinking properties, which is preferable.

When a sulfur-based compound is used as a crosslinking agent, the rubber composition of the present invention preferably contains the following crosslinking assistant.

When a sulfur-based compound is used as a crosslinking agent, the crosslinking assistant preferably contained in the rubber composition includes, for example, zinc oxide, zinc white, and the like. The dosage of cross-linking aids is relative In 100 parts by weight of ethylene·α-olefin·non-conjugated polyene copolymer, usually 1-20 parts by weight.

When a sulfur-based compound is used for the crosslinking agent, it is preferable to use sulfur and a vulcanization accelerator together.

啉二硫)苯并噻唑(例如，「Nocceler-MDB-P」(商品名，三新化學工業股份有限公司製)等)、2-(2,4-二硝基苯基)巰基苯并噻唑、2-(2,6-二乙基-4-

啉基硫)苯并噻唑及二硫化二苯并噻唑等之噻唑系；二苯基胍、三苯基胍、二鄰甲苯基胍等之胍系；乙醛‧苯胺縮合物、丁基醛‧苯胺縮合物、醛胺系；2-巰基咪唑啉等咪唑啉系；二乙基硫脲、二丁基硫脲等之硫脲系；一硫化四甲基秋蘭姆、二硫化四甲基秋蘭姆(TMTD)(例如，「Nocceler TT」(商品名；大內新興(股)公司製)等)等秋蘭姆系；二甲基二硫代胺基甲酸鋅、二乙基二硫代胺基甲酸鋅、二丁基二硫代胺基甲酸鋅(ZnBDC)(例如，「Sanceler BZ」(商品名，三新化學工業公司製)等)、二乙基二硫代胺基甲酸碲等二硫酸鹽系；伸乙硫脲。N,N’-二乙基硫脲、N,N’-二丁基硫脲等硫脲系；二丁基黃原酸鋅等黃原酸鹽系；其他鋅白(例如「META-Z102」(商品名，井上石灰工業股份有限公司製)等之氧化鋅)等。 Specific examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazolesulfinamide (CBS) (for example, "Nocceler NS" (trade name, manufactured by Ouchi Shinshin Co., Ltd.), N -Oxydiethylene-2-benzothiazolesulfinamide, N,N'-diisopropyl-2-benzothiazolesulfinamide, 2-mercaptobenzothiazole (for example, "Sanceler M ” (trade name, manufactured by Sanxin Chemical Industry Co., Ltd.), etc.), 2-(4-

Linodisulfide) benzothiazole (for example, "Nocceler-MDB-P" (trade name, manufactured by Sanshin Chemical Industry Co., Ltd.), etc.), 2-(2,4-dinitrophenyl)mercaptobenzothiazole , 2-(2,6-diethyl-4-

Phytothio) thiazole series such as benzothiazole and dibenzothiazole disulfide; guanidine series such as diphenylguanidine, triphenylguanidine, di-o-tolylguanidine; acetaldehyde·aniline condensate, butyraldehyde· Aniline condensate, aldehyde amine series; imidazoline series such as 2-mercaptoimidazoline; thiourea series such as diethylthiourea and dibutylthiourea; tetramethylthiuram monosulfide, tetramethylthiuram disulfide Thiuram series such as Lamb (TMTD) (for example, "Nocceler TT" (trade name; manufactured by Ouchi Shinshin Co., Ltd.), etc.); zinc dimethyldithiocarbamate, diethyldithiocarbamate Zinc carbamate, zinc dibutyldithiocarbamate (ZnBDC) (for example, "Sanceler BZ" (trade name, manufactured by Sanshin Chemical Industry Co., Ltd.), etc.), tellurium diethyldithiocarbamate, etc. Disulfate system; Ethylthiourea. Thiourea series such as N,N'-diethylthiourea and N,N'-dibutylthiourea; xanthate series such as zinc dibutylxanthate; other zinc whites (such as "META-Z102" (trade name, Zinc Oxide, manufactured by Inoue Lime Industry Co., Ltd.), etc.

The compounding amount of these vulcanization accelerators is based on 100 parts by mass of the ethylene·α-olefin·non-conjugated polyene copolymer, usually 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass parts by mass, more preferably 0.5 to 10 parts by mass. If the compounding amount of the vulcanization accelerator is within the above-mentioned range, the surface of the obtained rubber molded body does not bloom and exhibits excellent cross-linking properties, which is preferable.

The vulcanization assistant is appropriately selected depending on the application, and can be used alone or in combination of two or more. Specific examples of the vulcanization aid include magnesium oxide, zinc white (eg, zinc oxide such as "META-Z102" (trade name, manufactured by Inoue Lime Industry Co., Ltd.)) and the like. The compounding amount is usually 1 to 20 parts by weight relative to 100 parts by weight of the ethylene·α-olefin·non-conjugated polyene copolymer.

[foaming agent]

The rubber composition of the present invention may also contain a foaming agent. Furthermore, when the rubber composition of the present invention contains a foaming agent, the above-mentioned crosslinking agent is usually also contained. By using a rubber composition containing a crosslinking agent and a foaming agent, the rubber composition can be crosslinked and foamed to obtain a foam.

Examples of the foaming agent include inorganic foaming agents such as sodium bicarbonate and sodium carbonate; N,N'-dinitrosopentamethylenetetramine, N,N'-dinitroterephthalide Nitroso compounds such as amines; azo compounds such as azodicarboxyamide (ADCA), azobisisobutyronitrile; benzenesulfohydrazine, p,p'-oxybis(benzenesulfohydrazide) (OBSH), etc Hydrazine compounds; organic foaming agents such as calcium azide, azide compounds such as 4,4'-diphenyldisulfonyl azide, etc. As a foaming agent, ADCA and OBSH are preferable. A foaming agent may be used individually by 1 type, and may use 2 or more types.

When the rubber composition of the present invention contains a foaming agent, the blending amount of the foaming agent is based on 100 parts by weight of the ethylene·α-olefin·non-conjugated polyene copolymer, usually 0.2 to 30 parts by weight, preferably 0.5 ~25 parts by weight, more preferably 0.5 to 20 parts by weight.

[foaming aids]

In the case where the rubber composition of the present invention contains a foaming agent, a foaming aid may be contained as necessary. Foaming aids show the effects of lowering the decomposition temperature of the foaming agent, promoting decomposition, and homogenizing bubbles.

Examples of such foaming aids include organic acids such as salicylic acid, phthalic acid, stearic acid, oxalic acid, and citric acid, or salts thereof, urea or derivatives thereof, and the like.

When the rubber composition of the present invention contains a foaming aid, the blending amount of the foaming aid is relative to 100 parts by weight of the ethylene·α-olefin·non-conjugated polyene copolymer, usually 0.2 to 30 parts by weight, more than 100 parts by weight. It is preferably 0.5 to 25 parts by weight, more preferably 0.5 to 20 parts by weight.

[Antioxidants]

The rubber composition of the present invention preferably contains an antioxidant from the viewpoint of prolonging the life of the material. Examples of such antioxidants include phenylnaphthylamine, 4,4'-(α,α-dimethylbenzyl)diphenylamine, N,N'-di-2-naphthyl-para- Aromatic secondary amine stabilizers such as phenylenediamine; 2,6-di-tert-butyl-4-methylphenol, tetra-[methylene-3-(3',5'-di-tert-butyl Phenol-based stabilizers such as methyl-4'-hydroxyphenyl)propionate]methane; bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-tert-butylphenyl ] sulfide-based stabilizers such as sulfide; benzimidazole-based stabilizers such as 2-mercaptobenzimidazole; dithiocarbamate-based stabilizers such as nickel dibutyldithiocarbamate; 2,2,4 - Quinoline-based stabilizers such as polymers of trimethyl-1,2-dihydroquinoline, etc. These systems can be used individually or in combination of 2 or more types.

[Processing aids]

The rubber composition of the present invention may also contain a processing aid. As processing aids, those generally formulated into rubbers as processing aids can be widely used. Specific examples thereof include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, esters, and the like. Among these, stearic acid is preferred.

When the rubber composition of the present invention contains a processing aid, the compounding amount of the processing aid is based on 100 parts by mass of the ethylene·α-olefin·non-conjugated polyene copolymer, usually 0.1 to 10 parts by weight, preferably 0.5 ~8 parts by weight, more preferably 1 to 6 parts by weight. Within the above range, the surface of the obtained rubber composition does not bloom, and further, when the rubber composition is cross-linked, no cross-linking hindrance occurs, which is preferable. Moreover, the rubber composition containing a processing aid is preferable because it is excellent in moldability such as extrusion moldability, press moldability, injection moldability, etc., and roll processability.

[surfactant]

The rubber composition of the present invention may also contain a surfactant. Examples of surfactants include di-n-butylamine, dicyclohexylamine, monoethanolamine, triethanolamine, "ACTING B" (manufactured by GIFT Pharma Co., Ltd.), "ACTING SL" (manufactured by GIFT Pharma Co., Ltd.), etc. Amines; polyethylene glycol, diethylene glycol, lecithin, triallyl trimellitate, zinc compounds of aliphatic and aromatic carboxylic acids (e.g. "Struktol activator 73", " Struktol IB531", "Struktol FA541" manufactured by Schill & Seilacher Co., Ltd.), "ZEONET ZP" (manufactured by ZEON Co., Ltd., Japan), octadecyltrimethylammonium bromide, synthetic hydrotalcite, special quaternary ammonium compounds (for example: " ARQUAD 2HF" (manufactured by LION AKZO Co., Ltd.), etc.

When the rubber composition of the present invention contains a surfactant, the interfacial activity The preparation amount of the agent is based on 100 parts by weight of the ethylene·α-olefin·non-conjugated polyene copolymer, and is usually 0.2-10 parts by mass, preferably 0.3-5 parts by mass, more preferably 0.5-4 parts by mass. The surfactant is appropriately selected depending on the application, and can be used alone or in combination of two or more.

[Anti-aging agent]

The rubber composition of the present invention may also contain an anti-aging agent. If the rubber composition of the present invention contains an anti-aging agent, the life of the product obtained from the composition can be prolonged. As the antiaging agent, a known antiaging agent such as an amine antiaging agent, a phenolic antiaging agent, a sulfur antiaging agent and the like can be used.

Specific examples of the antiaging agent include aromatic secondary amine antiaging agents such as phenylbutylamine and N,N-di-2-naphthyl-p-phenylenediamine; Phenolic antioxidants such as methyl(3,5-di-tert-butyl-4-hydroxy)hydrocinnamate]methane; bis[2-methyl-4-(3-n-alkylthiopropane) Sulfide-based antiaging agents such as acyloxy)-5-tert-butylphenyl]sulfide; dithiocarbamate antiaging agents such as nickel dibutyldithiocarbamate; 2- Sulfur-based antiaging agents such as mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, dilauryl thiodipropionate, distearyl thiodipropionate, etc.

When the rubber composition of the present invention contains an anti-aging agent, the blending amount of the anti-aging agent is based on 100 parts by weight of the ethylene·α-olefin·non-conjugated polyene copolymer, usually 0.01 to 10 parts by weight, preferably 0.01 to 10 parts by weight. 0.02 to 7 parts by weight, more preferably 0.03 to 5 parts by weight. Within the above range, the molded body obtained from the rubber composition of the present invention has excellent heat aging resistance, which is preferable.

[Quasi-antigelling agent]

The rubber composition of the present invention may also contain a quasi-anti-gelling agent. Examples of the quasi-antigelling agent include "NHM-007" (manufactured by Mitsui Chemicals).

When the rubber composition of the present invention contains a quasi-anti-gelling agent, the compounding amount of the quasi-anti-gelling agent is based on 100 parts by mass of the ethylene·α-olefin·non-conjugated polyene copolymer, usually 0.1 to 15 parts by mass , preferably 0.5 to 12 parts by mass, more preferably 1.0 to 10 parts by mass.

[Other additives]

The rubber composition of the present invention may further contain other additives. As other additives, a heat-resistant stabilizer, a weather-resistant stabilizer, an antistatic agent, a colorant, a slip agent, a tackifier, etc. are mentioned, for example.

Further, the rubber composition (X) of the present invention may contain various optional components without limitation as described above, such as the ethylene·α-olefin·non-conjugated polyene copolymer (S) and the rubber component constituting the rubber composition (X) (T) has good compatibility, and if the rubber composition (X) containing these is used, a cross-linked molded body can be produced without phase separation, and in order to copolymerize ethylene·α-olefin·non-conjugated polyene The cross-linked molded body obtained by combining (S) provides excellent weather resistance, and even if the content of the weather resistance agent or antioxidant in the rubber composition (X) is suppressed, a cross-linked molded body with excellent weather resistance can be easily obtained. Therefore, the content of additives such as weathering agents and antioxidants can be appropriately suppressed, which is not only economical, but also prevents the deterioration of the quality of the cross-linked molded product caused by exudation.

<Preparation method of rubber composition>

The rubber composition of the present invention is a rubber composition containing the above-mentioned ethylene·α-olefin·non-conjugated polyene copolymer, preferably a softener, a filler, a crosslinking agent and other components. For example, a rubber composition containing 0.1 to 300 parts by weight of a softener and 1 to 300 parts by weight of a filler relative to 100 parts by weight of the ethylene·α-olefin·non-conjugated polyene copolymer described above, and there is no method for preparing the rubber composition. Specially limited.

As a method for preparing the rubber composition, for example, each component contained in the rubber composition is used, for example, a conventional kneader such as a mixer, a kneader, and a roll, and a continuous kneader such as a twin-screw extruder is used. A method of mixing; a method of preparing a solution in which each component contained in the rubber composition has been dissolved or dispersed, and then removing the solvent, etc.

In addition, the rubber composition (X) of the present invention can be prepared by mixing the ethylene·α-olefin·non-conjugated polyene copolymer (S), the rubber component (T), and optional components as needed, simultaneously or sequentially.

The preparation method of the rubber composition (X) is not particularly limited, and the preparation method of a general rubber compound can be adopted without limitation. For example, when the rubber composition (X) of the present invention contains optional components, at least a part of the optional components may be mixed with the ethylene·α-olefin·non-conjugated polyene copolymer (S) or the rubber component (T) in advance. Alternatively, after the ethylene·α-olefin·non-conjugated polyene copolymer (S) and the rubber component (T) are prepared, optional components may be added and prepared.

For example, the ethylene·α-olefin·non-conjugated polyene copolymer (S), the rubber component (T), and other compounds as needed are prepared using closed mixers such as Banbury mixers, kneaders, and closed mixers. Other ingredients, after kneading at 80~170℃ for 3~10 minutes, add cross-linking agent as needed, and further add cross-linking accelerator, cross-linking aid, foaming agent, etc. as needed, using rollers such as open rollers Class or kneader, after kneading for 5 to 30 minutes according to the roll temperature of 40 to 80 ℃, it can be separated and prepared. The rubber composition (X) is thus obtained in the form of a generally ribbon or sheet. When the kneading temperature of the above-mentioned hermetic mixer is relatively low, the crosslinking agent, the crosslinking accelerator, the foaming agent, etc. may be kneaded at the same time.

<Cross-linked molding>

The crosslinking molding system of the present invention is obtained by crosslinking the above-mentioned rubber composition of the present invention. Also, at the time of crosslinking, a metal mold may or may not be used. When a metal mold is not used, the rubber composition is usually continuously molded and cross-linked.

As a method of crosslinking the rubber composition, (a) the rubber composition containing the crosslinking agent is usually preliminarily formed by a molding method such as extrusion molding, press molding, injection molding, or by roll processing, as desired or (b) pre-forming the rubber composition containing the cross-linking agent according to the same method as the method (a), and then irradiating electrons bundle method.

Furthermore, in the method (a), the crosslinking agent in the rubber composition is heated to cause a crosslinking reaction to obtain a crosslinked body. Moreover, in the method (b), a crosslinking reaction is induced by an electron beam, and a crosslinked body is obtained. In the method (b), the preformed rubber composition is usually irradiated with 0.1 to 10 MeV according to the amount of radiation absorbed by the rubber composition, which is usually 0.5 to 36 Mrad, preferably 0.5 to 20 Mrad, and more preferably 1 to 10 Mrad. Electron beam of energy.

In addition, the crosslinking of the rubber composition (X) can be carried out by forming the uncrosslinked rubber composition (X) using an extrusion molding machine, a calender, a press, an injection molding machine, a transfer molding machine, or the like. The machine is preliminarily formed into a desired shape by various forming methods, and the formed product is introduced into a cross-linking tank for heating at the same time of forming, or irradiated with radiation such as electron beam, X-ray, γ-ray, α-ray and β-ray. , whereby the radiation crosslinking of the crosslinking proceeds. As a method of molding or pre-molding, extrusion molding, injection molding, injection molding, blow molding, extrusion blow molding, press molding, vacuum molding, calender molding, foam molding, etc., can be suitably used. man of desired shape know how to form. In addition, when the cross-linked molded product is a foamed body, the uncross-linked rubber composition prepared with a foaming agent is foamed and molded, and then cross-linked by electron beam irradiation or heating, or after foaming It can be produced by allowing crosslinking to proceed at the same time as molding. In addition, the step of crosslinking the rubber composition (X) may be performed by combining crosslinking by heating and electron beam crosslinking.

In the case of crosslinking the above-mentioned rubber composition (X) by heating, it is preferable to use a rubber composition (X) generally containing a crosslinking agent such as sulfur, a sulfur compound, and a peroxide, and use hot air, glass, etc. Bead fluid bed, UHF (Ultra-Ultra Short Wave Electromagnetic Wave), Steam or LCM (Hot Molten Salt Tank) and other heating forms of the cross-linking tank are heated at a temperature of 150~270℃ for 1~30 minutes. Sulfur cross-linking or peroxide cross-linking has the advantage of not requiring special equipment in the cross-linking step, so it has been conventionally widely used in the cross-linking step of rubber compositions.

In addition, when crosslinking by electron beam crosslinking in which crosslinking is performed by electron beam irradiation, it is preferable to use a rubber composition (X) that does not normally contain a crosslinking agent, and the preformed rubber composition (X) is preferably used. X) Electron beam irradiation to produce a cross-linked molded body. The cross-linking by electron beam irradiation can be performed without using a cross-linking agent, and there is an advantage that the generation of volatiles in the cross-linking step is small.

里混合機等混合機，將乙烯‧α-烯烴‧非共軛多烯共聚合體(S)、橡膠成分(T)及視需要之各種添加劑及交聯助劑等，依80~170℃之溫度混練3~10分鐘後，使用開放輥等輥類，依輥溫度40~80℃混練5~30分鐘後，進行分出，而調製緞帶狀或片狀之橡膠組成物(X)，或者於容器內將各成分摻合而調製橡膠組成物(X)。如此調製之橡膠組成 物(X)係維持片狀等，或藉擠出成形機、砑光輥、射出成形機或壓製成形為所需形狀，或藉擠出機擠出為股線狀並藉切割器等粉碎成顆粒再照射電子束。或者，對浸含了交聯助劑等化合物之乙烯‧α-烯烴‧非共軛多烯共聚合體(S)及橡膠成分(T)等之粉體直接照射電子束，調製橡膠組成物(X)之交聯物。電子束之照射係將通常0.1~10MeV(百萬電子伏特)、較佳0.3~5MeV之能量的電子束，依吸收射線量為通常0.5~100kGy(千戈雷)、較佳0.5~70kGy的方式進行。 The production of the cross-linked molded body with the cross-linking step by electron beam irradiation can be specifically carried out, for example, as follows. First, use the class

In a mixer such as an inner mixer, the ethylene·α-olefin·non-conjugated polyene copolymer (S), rubber component (T) and various additives and cross-linking assistants as needed are mixed at a temperature of 80~170℃. After kneading for 3 to 10 minutes, use rolls such as open rolls, and knead for 5 to 30 minutes according to the temperature of the rolls at 40 to 80°C, then separate and prepare a ribbon-shaped or sheet-shaped rubber composition (X). Each component is blended in the container to prepare the rubber composition (X). The rubber composition (X) thus prepared is maintained in the form of a sheet, etc., or is formed into a desired shape by an extrusion molding machine, a calender roll, an injection molding machine or a press, or is extruded into a strand shape by an extruder and is A cutter or the like is pulverized into particles and then irradiated with an electron beam. Alternatively, a rubber composition (X) is prepared by directly irradiating a powder of an ethylene·α-olefin·non-conjugated polyene copolymer (S) and a rubber component (T), etc. impregnated with a compound such as a crosslinking aid. ) of the cross-linker. The irradiation of the electron beam is usually an electron beam with an energy of 0.1~10MeV (million electron volts), preferably 0.3~5MeV, and the amount of absorbed radiation is usually 0.5~100kGy (kGy), preferably 0.5~70kGy. conduct.

Compared with electron beam irradiation, γ-ray irradiation has higher penetration to the rubber composition (X), especially when the rubber composition (X) is irradiated in the form of particles, it can be directly irradiated with only a small amount. The interior of the particles can be sufficiently cross-linked. Irradiation of gamma rays can be performed on the rubber composition (X) in such a manner that the dose of gamma rays is usually 0.1 to 50 kGy, preferably 0.3 to 50 kGy.

In the present invention, the crosslinking step of the rubber composition (X) is preferably carried out by a step including electron beam crosslinking, and more preferably, the crosslinking step is carried out by electron beam crosslinking. Conventionally, electron beam crosslinking by electron beam irradiation is used to crosslink the surface of an uncrosslinked molded body, but in the present invention, since ethylene·α constituting the rubber composition (X) - The olefin-non-conjugated polyene copolymer (S) has high cross-linking properties, so the rubber composition (X) has excellent cross-linking properties, so even if the inside of the rubber composition (X) is cross-linked by electron beams Even if it is cross-linked, it can be homogeneously cross-linked without phase separation, and a cross-linked molded body can be appropriately produced.

The degree of crosslinking of the crosslinked molded product can be expressed by the gel fraction. Usually, the gel fraction of the cross-linked body is 1-80%. However, in the cross-linked molded article of the present invention, the degree of cross-linking is not limited to this range, and even if the gel fraction is less than 10%, particularly A cross-linked product with a low cross-linking degree with a gel fraction of more than 0.5% can still obtain the same effect of excellent appearance and surface as the cross-linked molded product of the present invention with a high cross-linking degree.

The crosslinked molded product of the present invention can be used for various products having rubber properties without limitation. The cross-linked molded body of the present invention may constitute at least a part of the product, and the entirety of the cross-linked molded body of the present invention is preferably a laminate, and the cross-linked molded body of the present invention is preferably a layered product constituting at least a part of the product or complex. As the laminate, among the multilayer laminates having two or more layers, for example, at least one layer of the laminate is the crosslinked molded article of the present invention, and examples include multilayer films and sheets, multilayer containers, multilayer pipes, The form of a multilayer coating film laminate or the like contained in the form of one of the constituent components of the water-based paint.

Since the cross-linked molded product of the present invention is particularly excellent in weather resistance, it is also suitable for use in tires or wire covering materials for long-term outdoor use, and is especially suitable for use in tire components constituting at least a part of various tires.

As the tire member, for example, a tire inner liner, a tire inner tube, a tire liner, a tire shoulder, a tire bead, a tire tread, a tire sidewall, and the like can be mentioned. Among them, it is particularly suitable for use in tire treads and tire sidewalls.

The cross-linking molding system of the present invention maintains the original superior mechanical strength of diene rubber, and is homogeneous because the rubber composition (X) exhibits superior co-crosslinking property, superior weather resistance, and superior dynamic mechanical strength. A tire member such as a tire tread or tire sidewall using the crosslinked molded body of the present invention is excellent in weather resistance and dynamic fatigue resistance.

<foam>

The foaming system of the present invention is prepared by mixing the rubber composition of the present invention containing the above-mentioned foaming agent The finished product is obtained by cross-linking and foaming.

Since the above-mentioned rubber composition contains a foaming agent, by heating the rubber composition, a cross-linking reaction by the cross-linking agent proceeds, and the foaming agent is decomposed to generate carbon dioxide gas or nitrogen gas. Therefore, a foam having a cell structure can be obtained.

<Use>

The rubber composition of the present invention is very excellent in low-temperature properties, mechanical properties, extrusion moldability, press moldability, injection moldability, etc., and roll processability, and the rubber composition of the present invention can appropriately obtain low-temperature properties ( Softness at low temperature, rubber elasticity, etc.), excellent mechanical properties and other moldings.

In addition, the rubber composition of the present invention can produce a cross-linked product having excellent processability, moldability, cross-linking properties, and excellent heat-resistance stability by using the above-mentioned ethylene·α-olefin·non-conjugated polyene copolymer. The cross-linked product obtained from the rubber composition of the present invention can also be suitably used in applications that are expected to be used at high temperatures for a long time.

The rubber composition of the present invention and a molded body obtained from the composition, such as a crosslinked body or a foamed body, can be used in various applications. Specifically, it is suitable for use in: rubber for tires, O-rings, industrial rollers, liners (such as condenser liners), gaskets, belts (such as heat insulation tapes, photocopier belts, conveyor belts), automotive soft Pipes and other hoses (such as turbocharger hoses, water pipes, brake reservoir hoses, radiator hoses, air hoses), anti-vibration rubber, anti-vibration materials or vibration-damping materials (such as engine mounts, motor mounts) ), muffler hangers, sponges (such as sealing strip sponges, thermal insulation sponges, protective sponges, micro-foaming sponges), cables (ignition cables, cab tire cables, high-voltage cables), wire covering materials (High-voltage wire covering materials, low-voltage wire covering materials, marine wire covering materials), glass run channels, collar skin materials, paper feed rollers, roof sheets, etc. Among these, it is suitable to use It is used for applications requiring automobile interior and exterior parts or heat resistance, and is suitable for hose applications such as brake reservoir hoses and radiator hoses used as automobile interior parts.

In the present invention, an ethylene·α-olefin·non-conjugated polyene copolymer having appropriate properties can be selected and used in accordance with the application within the range that satisfies the above-mentioned requirements. For example, in the application of a muffler hanger, a higher molecular weight ethylene·α-olefin·non-conjugated polyene copolymer can be suitably used, specifically, ethylene with a weight average molecular weight (Mw) of 200,000-600,000 can be used. ‧α-olefin ‧Non-conjugated polyene copolymer.

[resin composition]

The resin composition of the present invention contains the above-mentioned (S) ethylene·α-olefin·non-conjugated polyene copolymer, (E) micronized silicic acid and/or micronized silicate, and (G) organic as a crosslinking agent The peroxide and/or (H) the SiH group-containing compound crosslinking agent having at least two SiH groups in the molecule may optionally contain (F) a metal salt of an α,β-unsaturated carboxylic acid.

<(E) Micronized Silicic Acid and/or Micronized Silicate>

The above-mentioned micropowder silicic acid and/or micropowder silicic acid (E) has a specific surface area of 5-500 m ² /g (BET adsorption capacity: ISO 5794/1, Annex D), preferably 10-400 m ² /g. As said micropowder silicic acid and micropowder silicate (E), a dry process silica, a wet process silica, a synthetic silicate type silica etc. are mentioned, for example. As a silicate, magnesium silicate is mentioned, for example. In the present invention, micropowder silicic acid and/or micropowder silicate (E) may be used alone, or may be used in combination. In the present invention, the term "fine powder" is not particularly limited, and refers to those having an average particle diameter of about 10 to 50 μm.

Such micronized silicic acid and/or micronized silicate (E) is in the resin composition of the present invention, relative to the above-mentioned ethylene·α-olefin·non-conjugated polyene copolymer (S) 100 Parts by weight, based on the total amount of micropowder silicic acid and micropowder silicate, are usually used in a proportion of 5 to 90 parts by weight, preferably 20 to 80 parts by weight. In addition, when the resin composition of the present invention is used in anti-vibration rubber products, since the dynamic characteristics of the vibration damping effect are required to be matched with the application of the anti-vibration rubber products, the use of micro-powder silicic acid and/or silicic acid can be adjusted according to the purpose of use. Or the mixing ratio of micronized silicate (E).

<(F)α,β-Unsaturated Carboxylic Acid Metal Salt>

As said (alpha), (beta)- unsaturated carboxylic acid metal salt (F), at least 1 sort(s) of compound chosen from the group consisting of acrylic acid metal salt, methacrylic acid metal salt, and maleic acid metal salt is mentioned preferably, for example.

Examples of the above-mentioned metal acrylic acid salt, metal methacrylic acid salt and metal maleic acid salt include alkali metal salts of acrylic acid, methacrylic acid and maleic acid (for example, lithium salt, sodium salt, potassium salt), Alkaline earth metal salts (such as magnesium salts, calcium salts), heavy metal salts (such as zinc salts), aluminum salts, such as lithium acrylate, sodium acrylate, potassium acrylate, magnesium diacrylate, calcium diacrylate, zinc diacrylate, triacrylate Aluminum Acrylate, Lithium Methacrylate, Sodium Methacrylate, Potassium Methacrylate, Zinc Methacrylate, Magnesium Dimethacrylate, Calcium Dimethacrylate, Zinc Dimethacrylate, Aluminum Trimethacrylate, Malene Lithium diacid, sodium maleate, potassium maleate, magnesium maleate, zinc maleate, aluminum maleate. As the α,β-unsaturated carboxylic acid metal salt, zinc methacrylate and zinc dimethacrylate are particularly preferred, and zinc methacrylate is most preferred. The α,β-unsaturated carboxylic acid metal salts may be used alone or in combination of two or more.

Such α,β-unsaturated carboxylate metal salt (F) is optionally contained in the resin composition of the present invention, based on 100 weight of the above-mentioned ethylene·α-olefin·non-conjugated polyene copolymer (S) parts, based on the total amount of the total α,β-unsaturated carboxylic acid metal salts, usually in a ratio of less than 20 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.2 to 10 parts by weight use. By using metal salts of α,β-unsaturated carboxylate, ethylene·α-olefin·non-conjugated polyene copolymers (S), micropowder silicic acid and/or micropowder silicates (E), which are polymers, are improved The interaction between them can obtain cross-linked rubber products with superior dynamic characteristics and mechanical properties. Especially in the case where the resin composition of the present invention contains the below-mentioned organic peroxide (G) as a crosslinking agent, if it contains α,β-unsaturated carboxylate metal salt (F), due to the micronized silicic acid and/or micronized silicic acid. The interaction between the salt (E) and the α,β-unsaturated carboxylate metal salt (F) is particularly excellent, so it is preferable.

<(G) Organic Peroxide>

In the case where the resin composition of the present invention contains an organic peroxide (G) as a crosslinking agent, as the organic peroxide (G), a conventional organic peroxide generally used for rubber crosslinking can be used. As a specific example of an organic peroxide, the thing similar to what was illustrated in the said rubber composition is mentioned, for example. These organic peroxides may be used alone or in combination of two or more.

In the resin composition of the present invention, the organic peroxide (G) obtains the target physical properties by sufficiently cross-linking, and prevents adverse effects and costs due to excessive decomposition products. 100 parts by weight of ethylene·α-olefin·non-conjugated polyene copolymer (S), based on the total amount of total organic peroxides, used in a proportion of 0.1-15 parts by weight, preferably 0.5-12 parts by weight.

When the resin composition of the present invention contains an organic peroxide (G) as a crosslinking agent, a crosslinking assistant may be contained in the resin composition as an optional component. Specific examples of the crosslinking aid include sulfur; quinone dioxime-based compounds such as p-quinone dioxime; methacrylic acid-based compounds such as polyethylene glycol dimethacrylate; diallyl phthalate, cyanuric acid, etc. Allyl compounds such as triallyl acid; maleimide compounds; diethyl Benzene etc. These cross-linking assistants are used in an amount of 0.5-2 mol, preferably about 1 mol, relative to 1 mol of the organic peroxide.

<(H) SiH group-containing compound having at least 2 SiH groups in 1 molecule>

When the resin composition of the present invention contains (H) a SiH group-containing compound having at least two SiH groups in one molecule (hereinafter also simply referred to as "SiH group-containing compound (H)"), the SiH group-containing compound (H) is a It acts as a crosslinking agent by reacting with ethylene·α-olefin·non-conjugated polyene copolymer (S). The molecular structure of the SiH group-containing compound (H) is not particularly limited, and conventionally produced resins such as linear, cyclic, branched, or three-dimensional mesh structures can be used, but one molecule must contain at least Two, preferably three or more hydrogen atoms directly bonded to silicon atoms, that is, SiH groups.

As such a SiH group-containing compound (H), the general compositional formula R ⁴ _b H _c SiO _(4-bc)/2 can usually be used

compound shown.

In the above general composition formula, R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group with 1 to 10 carbon atoms, especially 1 to 8 carbon atoms, except for aliphatic unsaturated bonds, as such a monovalent hydrocarbon group, except In addition to the alkyl group exemplified by R ¹ above, a phenyl group, a halogen-substituted alkyl group, for example, a trifluoropropyl group can be exemplified. Among them, methyl, ethyl, propyl, phenyl, and trifluoropropyl are preferred, and methyl and phenyl are particularly preferred.

In addition, b is 0≦b<3, preferably 0.6<b<2.2, particularly preferably 1.5≦b≦2; c is 0<c≦3, preferably 0.002≦c<2, particularly preferably 0.01≦c≦1, And b+c is 0<b+c≦3, preferably 1.5<b+c≦2.7.

In the SiH group-containing compound (H), the number of silicon atoms in one molecule is preferably 2-1000, particularly preferably 2-300, and most preferably 4-200 organohydrogenpolysiloxanes. For example, 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyltetracyclosiloxane, 1,3,5,7,8-pentamethylpentacyclo Siloxane oligomers such as siloxane; trimethylsiloxy-terminated methylhydropolysiloxane at both ends of the molecular chain, and dimethylsiloxane with trimethylsiloxy-terminated at both ends of the molecular chain ‧Methylhydrosiloxane copolymer, Methylhydrosiloxane terminated with silanol groups at both ends of the molecular chain, Dimethylsiloxane terminated with silanol groups at both ends of the molecular chain ‧Methylhydrosiloxane copolymer Combination, dimethylhydrogen siloxy-terminated dimethyl hydrogen polysiloxane at both ends of the molecular chain, methyl hydrogen polysiloxane terminated by dimethyl hydrogen siloxy at both ends of the molecular chain, two ends of the molecular chain Methylhydrosiloxy-terminated dimethylsiloxane·methylhydrosiloxane copolymer, composed of R ⁴ ₂ (H)SiO _1/2 unit and SiO _4/2 unit, can optionally contain R ⁴ ₃ SiO _1/2 unit, R ⁴ ₂ SiO _2/2 unit, R ⁴ (H)SiO _2/2 unit, (H)SiO _3/2 unit or R ⁴ SiO _3/2 unit of polysiloxane, etc.

As the trimethylsiloxy-terminated methylhydrogen polysiloxane at both ends of the molecular chain, the compound represented by the following formula can be exemplified, and a part or all of the methyl group in the following formula is Fluoropropyl, etc. substituted compounds, etc.

(CH ₃ ) ₃ SiO-(-SiH(CH ₃ )-O-) _d -Si(CH ₃ ) ₃ [d in the formula is an integer of 2 or more. ]

As the trimethylsiloxy-terminated dimethylsiloxane·methylhydrosiloxane copolymer at both ends of the molecular chain, the compound represented by the following formula can be exemplified, and a part or all of the methyl group in the following formula is ethyl group. , propyl, phenyl, trifluoropropyl, etc. substituted compounds, etc.

(CH ₃ ) ₃ SiO-(-Si(CH ₃ ) ₂ -O-) _e -(-SiH(CH ₃ )-O-) _f -Si(CH ₃ ) ₃

[In the formula, e is an integer of 1 or more, and f is an integer of 2 or more. ]

As the silanol group-terminated methyl hydrogen polysiloxane at both ends of the molecular chain, the compound represented by the following formula can be exemplified, and a part or all of the methyl group in the following formula is ethyl, propyl, phenyl, Compounds substituted with trifluoropropyl and the like.

HOSi(CH ₃ ) ₂ O-(-SiH(CH ₃ )-O-) ₂ -Si(CH ₃ ) ₂ OH

As the silanol group-terminated dimethylsiloxane·methylhydrosiloxane copolymer at both ends of the molecular chain, the compound represented by the following formula can be exemplified, and a part or all of the methyl group in the following formula is ethyl group, propyl group , phenyl, trifluoropropyl, etc. substituted compounds, etc.

HOSi(CH ₃ ) ₂ O-(-Si(CH ₃ ) ₂ -O-) _e -(-SiH(CH ₃ )-O-) _f -Si(CH ₃ ) ₂ OH

[In the formula, e is an integer of 1 or more, and f is an integer of 2 or more. ]

As the dimethylhydrosiloxy-terminated dimethylpolysiloxane at both ends of the molecular chain, the compound represented by the following formula can be exemplified, and a part or all of the methyl group in the following formula is Compounds substituted with trifluoropropyl and the like.

HSi(CH ₃ ) ₂ O-(-Si(CH ₃ ) ₂ -O-) _e -Si(CH ₃ ) ₂ H

[e in the formula is an integer of 1 or more. ]

As the dimethylhydrogensiloxy-terminated methylhydropolysiloxane at both ends of the molecular chain, the compound represented by the following formula can be exemplified, and a part or all of the methyl group in the following formula is ethyl, propyl, phenyl, Compounds substituted with trifluoropropyl and the like.

HSi(CH ₃ ) ₂ O-(-SiH(CH ₃ )-O-) _e -Si(CH ₃ ) ₂ H

[e in the formula is an integer of 1 or more. ]

As the dimethylhydrosiloxy-terminated dimethylsiloxane-methylhydrosiloxane copolymer at both ends of the molecular chain, the compound represented by the following formula can be exemplified, and a part or all of the methyl group in the following formula is Compounds substituted with radicals, propyl, phenyl, trifluoropropyl, etc.

HSi(CH ₃ ) ₂ O-(-Si(CH ₃ ) ₂ -O-) _e -(-SiH(CH ₃ )-O-) _h -Si(CH ₃ ) ₂ H

[e and h in the formula are each an integer of 1 or more. ]

Such compounds can be prepared by known methods, for example, by combining octamethylcyclotetrasiloxane and/or tetramethylcyclotetrasiloxane, and hexamethyldisiloxane or 1,3-disiloxane, which can be terminal groups. Hydro-1,1,3,3-tetramethyldisiloxane and other compounds containing triorganosiloxane groups or diorganohydrosiloxane groups, catalysts in sulfuric acid, trifluoromethanesulfonic acid, methanesulfonic acid, etc. In the presence of -10 ℃ ~ +40 ℃ temperature to make it equilibrium can be easily prepared.

The SiH group-containing compound (H) may be used alone or in combination of two or more.

In the resin composition of the present invention of the SiH group-containing compound (H), the SiH group-containing compound (H ) is usually used in a proportion of 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight. If the SiH group-containing compound (H) is used in a ratio within the above range, a resin composition capable of forming a cross-linked rubber molded body having excellent compression set resistance, appropriate cross-link density, and excellent strength and elongation properties can be obtained. If the SiH group-containing compound (H) is used in a proportion exceeding 15 parts by weight, there is a cost disadvantage.

<Addition reaction catalyst>

In the case where the resin composition of the present invention contains a SiH group-containing compound (H), the resin composition may also contain an alkenyl group that promotes the above-mentioned ethylene·α-olefin·non-conjugated polyene copolymer (S), and a SiH group-containing compound (S). An addition reaction catalyst that acts as an addition reaction between SiH groups of the base compound (H) (hydrosilation reaction of alkene) is used as an optional component.

The addition reaction catalyst is not particularly limited as long as it can promote such an addition reaction. For example, an addition reaction composed of platinum group elements such as platinum-based catalysts, palladium-based catalysts, and rhodium-based catalysts can be mentioned. Catalysts (Group 8 metals of the periodic table, Group 8 metal complexes, Group 8 gold Group 8 metal-based catalysts such as genus compounds), among which platinum-based catalysts are preferred.

Platinum-based catalysts are generally known ones used for addition hardening type hardening, such as fine powder metal platinum catalysts described in US Pat. No. 2,970,150, and chloroplatinic acid described in US Pat. No. 2,823,218 Catalyst, complexes of platinum and hydrocarbons described in the specification of US Pat. No. 3,159,601 and specification of US Pat. No. 159,662, complexes of chloroplatinic acid and olefins described in the specification of US Pat. No. 3,516,946, US Pat. No. 3,775,452 The complex of platinum and vinylsiloxane described in the specification No. and US Patent No. 3,814,780. More specifically, for example, platinum monomer (platinum black), chloroplatinic acid, platinum-olefin complex, platinum-alcohol complex, or a platinum carrier supported on a carrier such as alumina, silica, etc. Wait.

The palladium-based catalyst is composed of palladium, a palladium compound, palladium chloride acid, or the like, and the rhodium-based catalyst is composed of rhodium, a rhodium compound, a rhodium chloride acid, or the like.

As an addition reaction catalyst other than the above, a Lewis acid, a cobalt carbonyl, etc. are mentioned, for example. The addition reaction catalyst is usually 0.1 to 100,000 ppm by weight, preferably 0.1 to 10,000 ppm by weight, more preferably 1 to 5,000 ppm by weight, relative to the ethylene·α-olefin·non-conjugated polyene copolymer (S). The ratio of 5~1,000 ppm by weight is particularly preferred.

If the addition reaction catalyst is used in the ratio within the above-mentioned range, a rubber composition capable of forming a cross-linked rubber molded body having an appropriate cross-linking density and excellent strength properties and elongation properties can be obtained. If the addition reaction catalyst is used in a ratio of more than 100,000 ppm by weight, it is unfavorable in terms of cost.

Furthermore, in the present invention, a crosslinked rubber molded body may be obtained by irradiating light, a gamma ray, an electron beam, or the like to an uncrosslinked rubber molded body that does not contain the above-mentioned addition reaction catalyst-containing rubber composition.

<Reaction Inhibitor>

The resin composition of the present invention may contain a reaction inhibitor as an optional component together with the above-mentioned addition reaction catalyst. Examples of the reaction inhibitor include benzotriazole, ethynyl group-containing alcohols (eg, acetylene cyclohexanol, etc.), acrylonitrile, and amide compounds (eg, N,N-diallylacetamide, N,N -Diallylbenzamide, N,N,N',N'-tetraallyl-o-phthalic acid diamide, N,N,N',N'-tetraallyl-m-phthalein acid diamide, N,N,N',N'-tetraallyl-p-phthalic acid diamide, etc.), sulfur, phosphorus, nitrogen, amine compounds, sulfur compounds, phosphorus compounds, tin, tin compounds, Organic peroxides such as tetramethyltetravinylcyclotetrasiloxane, hydrogen peroxide, etc.

The reaction inhibitor is 0 to 50 parts by weight, usually 0.0001 to 50 parts by weight, preferably 0.0001 to 30 parts by weight, more preferably 100 parts by weight of the ethylene·α-olefin·non-conjugated polyene copolymer (S). 0.0001-20 parts by weight, more preferably 0.0001-10 parts by weight, and particularly preferably 0.0001-5 parts by weight. When the reaction inhibitor is used in a proportion of 50 parts by weight or less, a rubber composition having a high cross-linking speed and excellent productivity of a cross-linked rubber molded body can be obtained. If the reaction inhibitor is used in a proportion exceeding 50 parts by weight, it is disadvantageous in terms of cost, so it is not preferable.

The resin composition of the present invention may contain either one of the above-mentioned organic peroxide (G) or the SiH group-containing compound (H) as a crosslinking agent, but may contain both.

<(J) Compounds containing at least one unsaturated hydrocarbon group and at least one hydrolyzable silicon group>

The resin composition of the present invention may also contain a compound (J) containing at least one unsaturated hydrocarbon group and at least one hydrolyzable silicon group as an optional component. As such a compound (J), for example, a silane coupling agent having an unsaturated hydrocarbon group can be mentioned, and specific examples thereof include γ-methacryloyloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyl-paraffin (β-methoxy Ethoxy)silane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, etc.

Since this compound (J) also functions as a crosslinking agent, the content of the resin composition is determined from the above-mentioned micropowder silicic acid and/or micropowder from the viewpoints of appropriate crosslinking density and sufficient elongation. The total surface area of the silicates (E) is preferably less than 8×10 ^-6 mol, more preferably less than 8×10 ^-7 mol per 1 m ² .

<Other silane coupling agents>

The resin composition of the present invention may contain a silane coupling agent other than the above-mentioned (J) component, that is, a silane having no unsaturated hydrocarbon group such as bis[3-(triethoxysilyl)propyl]tetrasulfide A coupling agent is used as an optional component. Since this silane coupling agent has no function as a cross-linking agent, it can be prepared in a proportion of less than 1×10 ^-3 mol per 1 m ² of the surface area of the above-mentioned micropowder silicic acid and/or silicate (E).

<Anti-aging agent>

The resin composition of the present invention may also contain an antiaging agent.

In the present invention, in the case of using an antiaging agent, at least one selected from the group consisting of a sulfur-based antiaging agent, a phenolic antiaging agent, and an amine antiaging agent can be used; The sulfur-based anti-aging agent used. Specific antiaging agents include those described in, for example, International Patent Publication No. WO2015/122495.

In the present invention, a sulfur-based antiaging agent, a phenolic antiaging agent, and an amine-based antiaging agent may be used alone, but from the viewpoint of maintaining heat aging resistance at a high temperature for a long time, two or more of them are preferably used in combination. In the present invention, the sulfur-based antiaging agent is usually 0.2 to 10 parts by weight relative to 100 parts by weight of the ethylene·α-olefin·non-conjugated polyene copolymer (S). Part by weight, preferably 0.2 to 8 parts by weight, more preferably 0.2 to 6 parts by weight. If the sulfur-based antiaging agent is used in the above ratio, the effect of improving the heat aging resistance is large, and the crosslinking of the resin composition of the present invention is not hindered, which is preferable.

The phenolic antioxidant is based on 100 parts by weight of the ethylene·α-olefin·non-conjugated polyene copolymer (S), usually 0.2 to 5 parts by weight, preferably 0.5 to 4 parts by weight, more preferably 0.5 to 3 parts by weight use in proportion. When the phenolic antiaging agent is used in the above ratio, the effect of improving the heat aging resistance is large, and the crosslinking of the resin composition of the present invention is not hindered, which is preferable.

The amine-based anti-aging agent is usually 0.05-5 parts by weight, preferably 0.1-4 parts by weight, more preferably 0.2-3 parts by weight relative to 100 parts by weight of the ethylene·α-olefin·non-conjugated polyene copolymer (S) use in proportion. When the amine-based antiaging agent is used in the above ratio, the effect of improving the heat aging resistance is large, and the crosslinking of the copolymer rubber is not inhibited, which is preferable.

<Processing aid>

The resin composition of the present invention may contain a processing aid as an optional component within a range that does not impair the object of the present invention.

As the processing aid, compounds generally used in rubber processing can be used. Specific examples include higher fatty acids such as ricinoleic acid, stearic acid, palmitic acid, and lauric acid; salts of higher fatty acids such as barium stearate, zinc stearate, calcium stearate, etc.; ricinoleic acid, stearic acid, etc. , esters of higher fatty acids such as palmitic acid and lauric acid.

This processing aid is usually used in a proportion of 10 parts by weight or less, preferably 5 parts by weight or less, relative to 100 parts by mass of the ethylene·α-olefin·non-conjugated polyene copolymer (S). The most suitable amount is appropriately determined according to the physical properties.

<softener>

The resin composition of the present invention may contain a softening agent as an optional component within a range that does not impair the object of the present invention.

As the softener, a known softener generally used for rubber can be used. Specifically, for example, petroleum-based softeners such as processing oil, lubricating oil, flowing paraffin, petroleum pitch, petrolatum, etc.; coking coal-based softeners such as coking coal and coking coal pitch; castor oil, linseed oil, rapeseed oil, soybean oil, Fatty oil-based softeners such as coconut oil; tar; substitute rubber (oil gum); waxes such as beeswax, palm wax, lanolin, etc.; ricinoleic acid, palmitic acid, stearic acid, barium palmitate, stearic acid Fatty acids and fatty acid salts of calcium acid, zinc laurate, etc; Among them, it is preferable to use a petroleum-based softener, especially processing oil.

A softener can be used individually or in combination of 2 or more types. Its amount is relative to 100 parts by weight of the ethylene·α-olefin·non-conjugated polyene copolymer (S), and can be used in a ratio of 0 to 100 parts by weight, preferably 2 to 80 parts by weight.

<foaming agent>

Depending on the application, the resin composition of the present invention may contain a foaming agent as an optional component within a range that does not impair the object of the present invention.

As the foaming agent, for example, inorganic foaming agents such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, and ammonium nitrite; N,N'-dimethyl-N,N'-dinitroso Nitroso compounds such as phthalamide, N,N'-dinitrosopentamethylenetetramine; azodicarboxyamide, azobisisobutyronitrile, azocyclohexanitrile, azodiamine Azo compounds such as benzene, barium azodicarboxylate; Sulfonyl hydrazine compounds such as phenyl-3,3'-disulfohydrazine; Nitrogen compounds, etc.

These blowing agents can be used in a proportion of 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, relative to 100 parts by weight of the ethylene·α-olefin·non-conjugated polyene copolymer (S). If the foaming agent is used in the above ratio, a foam with a specific gravity of about 0.03 to 0.8 g/cm ³ can be produced.

Moreover, you may use a foaming adjuvant together with a foaming agent as needed. The foaming aid has the functions of reducing the decomposition temperature of the foaming agent, promoting the decomposition, and homogenizing the bubbles. Examples of such a foaming aid include organic acids such as salicylic acid, phthalic acid, stearic acid, and oxalic acid, urea or derivatives thereof, and the like.

These foaming aids are used in a proportion of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of the ethylene·α-olefin·non-conjugated polyene copolymer (S). The optimum amount is appropriately determined according to the required physical property values.

<optional ingredients>

The resin composition of the present invention may contain, in addition to the above-mentioned components, various additives or fillers that can be added to the rubber composition, resin components other than those described above, etc. of various arbitrary components.

<Production of resin composition and cross-linked molded product>

The resin composition of the present invention can be prepared by mixing the above-mentioned components sequentially or simultaneously according to a known method.

The resin composition of the present invention can be used as it is without being cross-linked, and its characteristics can be best exhibited when it is used as a cross-linked product such as a cross-linked molded product or a cross-linked foamed molded product.

When producing the cross-linked molded product of the resin composition and vibration-proof rubber product of the present invention, as in the case of cross-linking a known rubber composition, an uncross-linked resin composition can be prepared at one time, and then the rubber composition can be prepared. What is necessary is just to shape|shape the thing into a desired shape and perform crosslinking. The preparation, molding, and crosslinking of the resin composition may be performed individually or continuously.

The uncrosslinked resin composition of the present invention is obtained by mixing the above-mentioned (S) ethylene·α-olefin·non-conjugated polyene copolymer, (E) Micropowder silicic acid and/or micropowder silicate, and other inorganic fillers or softeners, knead at a temperature of 80~190°C, preferably 80~170°C for 2~20 minutes, preferably 3~10 minutes, Next, using a roll such as an open roll or a kneader, (F) α, β-unsaturated carboxylic acid metal salt, and (G) organic peroxide and/or (H) 1 which are crosslinking agents are additionally mixed SiH group-containing compound having at least 2 SiH groups in the molecule, optional addition reaction catalyst, reaction inhibitor, crosslinking accelerator, crosslinking assistant, foaming agent, antiaging agent, colorant, dispersant , various additives such as flame retardants, etc., after kneading for 3~30 minutes according to the roll temperature of 40~60℃, the kneaded material is extruded/separated, and the resin composition such as ribbon or sheet can be prepared by this.

In addition, when the kneading temperature of the closed mixer is relatively low, (S) ethylene·α-olefin·non-conjugated polyene copolymer, (E) micropowder silicic acid and/or micropowder silicate, Necessary inorganic fillers, softeners, etc. are kneaded together with a crosslinking agent and various additives to prepare a resin composition.

The resin composition of the present invention prepared as described above can be molded into a desired pattern by various molding methods such as extrusion molding machine, calender roll, pressing, injection molding machine, transfer molding machine, etc. Crosslinking can be performed by introducing the molded product into a crosslinking tank. Cross-linking can be heated at 100~270℃ for 1~30 minutes, or by irradiation Radiation such as light, gamma rays, and electron beams is performed. Moreover, you may crosslink at normal temperature.

Since the resin composition of the present invention contains (G) an organic peroxide as a crosslinking agent and/or (H) a SiH group-containing compound having at least two SiH groups in a molecule, it can be crosslinked by heating, Or crosslinking is performed by irradiation with radiation such as light, gamma rays, and electron beams, or by a combination of these methods.

Such cross-linking can be performed with or without a metal mold. When a metal mold is not used, the steps of forming and cross-linking are usually carried out continuously. As the heating method of the cross-linking tank, a heating tank of hot air, a fluidized bed of glass beads, UHF (Ultra Ultra Short Wave Electromagnetic Wave), steam, or the like can be used.

The resin composition of the present invention has high cross-linking speed and excellent productivity, and can be cross-linked by hot air such as HAV (hot air vulcanization tank), UHF (ultra-ultra-short-wave electromagnetic wave), etc. The cross-linked molded product of the invention is that the cross-linking agent is not mixed into the surface of the product, so the product appearance is excellent, and the compression permanent strain resistance and heat aging resistance are excellent, and the nitrosoamine system that is suspected to be a carcinogenic substance is not released. Compounds, etc., are good for the environment. In addition, the cross-linked molding system of the present invention is excellent in anti-vibration performance, and can be suitably used as anti-vibration rubber products, specifically, can be used for anti-vibration rubber for automobiles, hangers for mufflers for automobiles, anti-vibration rubber for railways, and industrial machinery. Anti-vibration rubber, anti-vibration rubber for construction, engine mounts, pads, bushings, pads, gaskets, air cushions, ring frames, shock buffer brakes, fenders, soft joints, dynamic shock absorbers, etc.

According to the present invention, such a resin composition, a cross-linked molded body, and a vibration-proof rubber product can be produced at low cost.

[Example]

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by the examples at all. In addition, the evaluation method of each characteristic in Examples and Comparative Examples is as follows below.

<Composition of ethylene·α-olefin·non-conjugated polyene copolymer>

The weight fraction (% by weight) of each constituent unit in the ethylene·α-olefin·non-conjugated polyene copolymer was determined from the measured value obtained by ¹³ C-NMR. The measured values were measured using an ECX400P nuclear magnetic resonance apparatus (manufactured by JEOL Ltd.), according to measurement temperature: 120°C, measurement solvent: o-dichlorobenzene/deuterium benzene = 4/1, and cumulative number of times: 8000 times, and the ¹³ C of the copolymer was measured. - NMR mass spectrometry was obtained.

<iodine value>

The iodine value of ethylene·α-olefin·non-conjugated polyene copolymer rubber is obtained by titration. Specifically, it is measured by the following method.

Dissolve 0.5g of ethylene·α-olefin·non-conjugated polyene copolymer rubber in 60ml of carbon tetrachloride, add a small amount of Wijs reagent and 20% potassium iodide solution, add 0.1mol/L thiosulfuric acid Titrate with sodium solution. A starch indicator was added near the end point, and the titration was performed while stirring well until the lavender color disappeared, and the number of grams of iodine was calculated based on the amount of halogen consumed for 100 g of the sample.

<Intrinsic Viscosity>

The limiting viscosity [η] was measured using a fully automatic limiting viscosity meter manufactured by Chuhe Co., Ltd., at a temperature of 135° C. and a measurement solvent: decalin.

<Weight Average Molecular Weight (Mw), Number Average Molecular Weight (Mn), Molecular Weight Distribution (Mw/Mn)>

The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) are values in terms of polystyrene measured by gel permeation chromatography (GPC). The measuring apparatus and conditions are as follows. In addition, the molecular weight was calculated by a conversion method using a commercially available monodisperse polystyrene to prepare a calibration curve.

Apparatus: Gel Permeation Chromatograph Alliance GP2000 (manufactured by Waters Corporation), Analytical Apparatus: Empower2 (manufactured by Waters Corporation), Column: TSKgel GMH6-HT×2+TSKgel GMH6-HTL×2 (7.5 mml.D.× 30 cm, manufactured by Tosoh Corporation), column temperature: 140°C, mobile phase: o-dichlorobenzene (including 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: The old method EPR conversion/viscosity correction method is considered.

<Low molecular weight component>

When the spectrum obtained by the above-mentioned GPC measurement shows two or more peaks, the ratio (%) of the area of the peak appearing on the side with the smallest molecular weight relative to the entire peak area is defined as the low molecular weight component with a molecular weight of 2000 or less content. again. When the spectrum obtained by the GPC measurement showed only one peak, the content of the low molecular weight component was set to 0%.

<complex viscosity η*>

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

<Number of long chain branches per 1000 carbon atoms (LCB _1000c )>

Determined according to the above method.

<Hardness test (DUROA hardness)>

According to JIS K 6253, the hardness of the sheet (type A durometer, HA) was measured by using 6 sheets of 2 mm sheet-like rubber molded products with a smooth surface, and overlapping the flat parts to make the thickness about 12 mm. Among them, those with foreign matter mixed in the test pieces, those with air bubbles, and those with scratches were not used. In addition, the size of the measurement surface of the test piece is the size measured at a position away from the end of the test piece by 12 mm or more at the tip of the pressing pin.

<tensile test>

According to JIS K 6251, a tensile test was performed under the conditions of a measurement temperature of 23° _C and a tensile speed of 500 mm/min, and the breaking strength (TB ) [MPa] and elongation at break ( _EB ) [%] of the sheet were measured. . That is, the cross-linked molded body in the form of a sheet is punched and prepared into a No. 3 dumbbell test piece described in JIS K 6251 (2001). The tensile test was carried out under the conditions of measurement temperature of 25° _C and _tensile speed of _500mm /min. _The stress at breaking point ( _TB ) and the tensile elongation at breaking point ( _{EB )} .

<Crosslinking Density>

The crosslinking density ν is calculated by the following Flory-Rehner equation (a) for equilibrium swelling. The VR in formula (a) is obtained by _subjecting the cross-linked 2 mm sheet to toluene extraction under the conditions of 37° C.×72 h.

VR : _Volume fraction of pure rubber in swollen cross-linked rubber

V ₀ : Molecular solution of solvent (toluene) (108.15cc@37℃)

μ: Interaction constant between rubber and solvent (EPDM-toluene: 0.49) ⁴⁾

A: Yavogajue number

<Compressive permanent strain (CS)>

According to JIS K 6262, a cross-linked body having a diameter of 29 mm and a height (thickness) of 12.5 mm was used as a test piece. The height of the test piece (12.5 mm) before the load was applied was compressed by 25%, and it was installed in a 150° C. aging tester (Gear Oven) together with the metal mold for 22 hours of heat treatment. Next, the test piece was taken out, and after standing to cool for 30 minutes, the height of the test piece was measured, and the permanent compressive strain (%) was calculated by the following formula.

Compressive permanent strain (%)={(t0-t1)/(t0-t2)}×100

t0: height of the test piece before the test

t1: The height after heat-treating the test piece and letting it cool for 30 minutes

t2: The height of the test piece attached to the measurement metal mold

<Heat aging resistance>

The cross-linked 2mm sheet was aged for 168h in an aging tester at 170°C. For the aged sheet, 6 sheets of 2 mm sheet-like rubber molded products having a smooth surface were used, and the flat portions were overlapped to have a thickness of about 12 mm, and the hardness was measured in accordance with JIS K 6253. Among them, those with foreign matter mixed in the test pieces, those with air bubbles, and those with scratches were not used. In addition, the size of the measurement surface of the test piece is the size measured at a position away from the end of the test piece by 12 mm or more at the tip of the pressing pin.

△H = hardness after aging - hardness before aging

The test piece after heat aging was subjected to a tensile test according to JIS K 6251 under the conditions of a measurement temperature of 23°C and a tensile speed of 500 mm/min, and the breaking strength (TB) and breaking elongation (EB) of the sheet were measured. Taking breaking strength (TB) × breaking elongation (EB) as the tensile product.

AR(%)/TB=TB after aging/TB before aging×100

AR(%)/EB=EB after aging/EB before aging×100

AR(%)/tensile product=tensile product after aging/tensile product before aging TB×100

<Roll workability>

The mixture obtained by adding the organic peroxide to the later-mentioned rubber formulation (A-1) was adjusted according to an 8-inch roll (the surface temperature of the front roll was 50°C, the surface temperature of the back roll was 50°C, the rotation speed of the front roll was 16 rpm, and the back roll was When kneading was carried out (the number of revolutions was 18 rpm), the following criteria were used to evaluate the wrapping property to the roll.

1: The sheets are not connected

2: The sheets are not connected but not wrapped (hanging bags, bagging)

3: Coiled, the sheet is slightly cracked, and the edge is defective

4: Coiled, the sheet is slightly cracked, and the edge is good

5: Coiled, no cracks on the sheet, good edges

[Example 1]

Using the continuous polymerization apparatus shown in Fig. 1, the ethylene·propylene·VNB copolymer was produced as follows.

In the polymerization reactor C with a volume of 300 liters, 58.3 L/hr of dehydrated and purified hexane solvent was continuously supplied from pipe 6, 4.5 mmol/hr of triisobutylaluminum (TiBA), (C ₆ H ₅ ) were continuously supplied from pipe 7 ) ₃ CB(C ₆ F ₅ ) ₄ 0.150mmol/hr, bis(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzoylphenyl)zirconium dichloride 0.030mmol/hr hr. At the same time, in the polymerization reactor C, 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 supplied from pipes 2, 3, 4, and 5 respectively. The copolymerization was carried out under the conditions of a pressure of 1.6 MPaG and a residence time of 1.0 hours.

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

In the phase separator D, the solution phase of the ethylene·propylene·VNB copolymer is separated into a thick phase containing most of the ethylene·propylene·VNB copolymer (below). phase part) and a dilute phase (upper phase part) containing a small amount of polymer.

The separated dense phase 85.4 liters/hr was led to the heat exchanger K through the pipe 11, and then introduced into the funnel E, where the solvent was evaporated and separated to obtain an ethylene·propylene·VNB copolymer in an amount of 7.8 kg/hr.

The physical properties of the obtained ethylene·propylene·VNB copolymer were evaluated as described above. The results are shown in Table 2. In addition, the molecular weight distribution of the obtained ethylene·propylene·VNB copolymer showed bimodality.

The concentration of ethylene·propylene·VNB copolymer was measured by sampling from tube 9, tube 10, and tube 11. The result was 43.8g/liter-solvent for tube 9, 4.3g/liter-solvent for tube 10, and 103.7g/liter-solvent for tube 11. . As a result, in the phase separator D, it was confirmed that the polymer concentration was concentrated to about 2.4 times. On the other hand, the copolymer concentration of the dilute phase was 4.3 g/liter-solvent, and during the cooling of the heat exchanger G, no fouling due to precipitation of the polymer was observed, and the operation was possible for a long time.

<Production of cross-linked molded body>

里混合器(神戶製鋼所製)進行混練，得到橡膠調配物。於上述混練中，係將共聚合體(A)獨練0.5分鐘，接著加入氧化鋅、硬脂酸、碳黑、石蠟系油，混練2分鐘。其後，使注塞(ram)上升進行清除，再混練1分鐘，得到橡膠調配物(A-1)。 100 parts by weight of the obtained ethylene-propylene-VNB copolymer (A), 5 parts by weight of zinc oxide (ZnO#1 and two types of zinc oxide, manufactured by Hakusui Tech Co., Ltd.) as a cross-linking aid, as a processing aid 1 part by weight of stearic acid (stearic acid Tsubaki series, manufactured by NOF Corporation), 80 parts by weight of carbon black (Asahi #60, manufactured by Asahi Carbon Corporation), and paraffin-based oil as softener (PS-430, manufactured by Idemitsu Kosan Co., Ltd.) 50 parts by weight, using BB-2 type class

A rubber compound was obtained by kneading with a U-Mixer (manufactured by Kobe Steel Co., Ltd.). In the above-mentioned kneading, the copolymer (A) was independently kneaded for 0.5 minutes, then zinc oxide, stearic acid, carbon black, and paraffin oil were added and kneaded for 2 minutes. Then, the ram was lifted up to remove it, and kneaded for another 1 minute to obtain a rubber formulation (A-1).

To this rubber formulation (A-1), 6.8 parts by weight of a 40% dilution of dicumyl peroxide (PERCUMYL D-40, manufactured by NOF Corporation) as an organic peroxide was added, and the resulting mixture was mixed. Using an 8-inch roll (manufactured by Nippon Roll Co., Ltd.), the surface temperature of the front roll was 50° C., the surface temperature of the rear roll was 50° C., the rotation number of the front roll was 16 rpm, and the rotation number of the rear roll was 18 rpm. Coiled and kneaded. At this time, the roll workability was evaluated according to the above-mentioned criteria.

In the kneading system, the above-mentioned mixture was switched 3 times and rolled through 6 times to obtain a rubber composition of a sheet having a thickness of 2.2 to 2.5 mm.

Using the obtained rubber composition sheet and a 100t press-forming machine (KMF100-1E, manufactured by Koko Industries), cross-linking was carried out under the conditions of a metal mold temperature of 170° C. and 10 minutes to obtain a thickness of 2 mm, a length of 15 cm, and a width of 15 cm. Conjoined (A-2) sheet. Using the sheet of the crosslinked body (A-2), the breaking point strength (TB), the breaking point elongation (EB), and the hardness (HA) were measured.

Further, using the obtained cross-linked body (A-2) sheet and a 100t press-forming machine (KMF100-1E, manufactured by Koko Kogyo Co., Ltd.), cross-linking was carried out under the conditions of a mold temperature of 170° C. and 20 minutes to obtain a thickness of 12.5 mm. , Cross-linked body (A-3) with a diameter of 29mm. Using the cross-linked body (A-3), the compression set was measured.

The evaluation results of the rubber composition and the cross-linked body are shown in Table 2.

[Examples 2 to 4]

The ethylene-propylene-VNB copolymer was produced in the same manner as in Example 1, except that the production conditions of the ethylene-propylene-VNB copolymer were changed to those shown in Table 1. The production results are shown in Table 1. Moreover, the physical properties of the obtained ethylene-propylene-VNB copolymer were evaluated in the same manner as in Example 1. The results are shown in Table 2. In addition, the obtained ethylene·propylene· The molecular weight distribution of the VNB copolymer showed bimodality.

[Comparative Example 1]

烯(VNB)之聚合反應。 Using a polymerizer with a volume of 300 L with stirring blades, ethylene, propylene and 5-ethylene-2-lowering were continuously carried out at 87°C as follows

Polymerization of alkene (VNB).

In the polymerizer, 32.6 L/hr of hexane as a polymerization solvent was continuously fed, and 3.6 kg/hr of ethylene, 6.1 kg/hr of propylene, 290 g/hr of VNB, and 6.3 NL/hr of hydrogen were fed continuously. Maintaining the polymerization pressure of 1.6 MPaG and the polymerization temperature of 87 °C, the main catalyst, bis(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzoyl) zirconium dichloride, was 0.0015 mmol/hr was continuously fed to the polymerizer. Furthermore, 0.0075 mmol/hr of (C ₆ H ₅ ) ₃ CB(C ₆ F ₅ ) ₄ as a co-catalyst and 20 mmol/hr of triisobutylaluminum (TiBA) as an organoaluminum compound were continuously supplied to the polymerizer.

Thus, a solution containing 15.2 mass % of the ethylene-propylene-VNB copolymer composed of ethylene, propylene and VNB was obtained. A small amount of methanol was added to the polymerization reaction liquid drawn from the lower part of the polymerization vessel to stop the polymerization reaction, and the ethylene·propylene·VNB copolymer was separated from the solvent by steam stripping, and then dried under reduced pressure at 80°C for one night.

Through the above operations, an ethylene·propylene·VNB copolymer (A-1) composed of ethylene, propylene, and VNB was obtained at a rate of 4.7 kg per hour. The physical properties of the obtained copolymer (A-1) were measured according to the methods described above. The results are shown in Table 2.

Claims (37)

An ethylene·α-olefin·non-conjugated polyene copolymer, characterized in that it has derived from ethylene (A); α-olefin (B) with 3 to 8 carbon atoms; 5-vinyl-2-nor having a total of 2 or more partial structures of the group formed by the following general formulae (I) and (II)

alkene (VNB),

A structural unit of one or more non-conjugated polyenes (C) selected from the group consisting of diene, 1,4-hexadiene, and dicyclopentadiene, which satisfies the following requirements (i) to (vii) ;

(i) The molar ratio of ethylene/α-olefin is 40/60~99.9/0.1; (ii) The weight fraction of the constituent unit derived from the non-conjugated polyene (C) is based on ethylene·α-olefin·non-conjugated 0.07% to 10% by weight in 100% by weight of the conjugated polyene copolymer; (iii) the weight average molecular weight (Mw) of the ethylene·α-olefin·non-conjugated polyene copolymer, derived from the non-conjugated polyene (C The weight fraction of the constituent unit of ) (the weight fraction of (C) (weight %)) and the molecular weight of the non-conjugated polyene (C) (the molecular weight of (C)) satisfy the following formula (1); 4.5≦Mw ×(C) weight fraction/100/(C) molecular weight≦40... Formula (1)(iv) Frequency ω=0.1rad/ _{The ratio P} ⁽ _η ^* ₍ ^ω _=0.1) /η ^* ₍ ω ₌₁₀₀₎ ), the limiting viscosity [η], and the weight fraction (weight fraction of (C)) of the constituent unit derived from the above-mentioned non-conjugated polyene (C) satisfy the following formula (2); P/([η] ^2.9 )≦(C) weight fraction×6... Formula (2) (v) The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) ) and the number average molecular weight (Mn) ratio (molecular weight distribution: Mw/Mn) is in the range of 8 to 30; (vi) the above number average molecular weight (Mn) is 30,000 or less; (vii) The graph obtained by GPC measurement shows 2 For more than one peak, the area of the peak appearing on the side with the smallest molecular weight is in the range of 1~20% of the total peak area. The ethylene·α-olefin·non-conjugated polyene copolymer according to claim 1, wherein the limiting viscosity [η] is 0.1-5 dL/g, and the weight average molecular weight (Mw) is 10,000-600,000. The ethylene·α-olefin·non-conjugated polyene copolymer according to claim 1 or 2, wherein the non-conjugated polyene (C) is 5-vinyl-2-nor

alkene (VNB). A method for producing an ethylene·α-olefin·non-conjugated polyene copolymer, which is a method for producing the ethylene·α-olefin·non-conjugated polyene copolymer according to any one of claims 1 to 3; characterized by: It comprises: the step (1) of carrying out copolymerization in the presence of a polymerization catalyst containing at least one metallocene compound represented by the following general formula [A1]; and carrying out the above-mentioned polymerization with adding alcohol as a catalyst deactivator step (2) of deactivation of the catalyst;

[In formula [A1], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group, or a compound other than a silicon-containing group Heteroatomic group; two adjacent groups in R ¹ ~R ⁴ can also be bonded to each other to form a ring; R ⁶ and R ¹¹ are derived from hydrogen atoms, hydrocarbon groups, silicon-containing groups and heteroatom-containing groups other than silicon-containing groups The same atom or the same group selected from among them; R ⁷ and R ¹⁰ are the same atom or the same group selected from hydrogen atoms, hydrocarbon groups, silicon-containing groups and heteroatom-containing groups other than silicon-containing groups; R ⁶ and R ⁷ They can also bond with each other to form a ring, and R ¹⁰ and R ¹¹ can also bond with each other to form a ring; wherein, R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms; R ¹³ and R ¹⁴ are each independently representing an aromatic M ¹ represents zirconium atom; Y ¹ represents carbon atom or silicon atom; Q represents halogen atom, hydrocarbon group, halogenated hydrocarbon group, neutral conjugated or non-conjugated diene with 4 to 20 carbon atoms, anionic ligand 1-4; when j is an integer of 2 or more, the complex numbers Q can be the same or different, respectively]. The method for producing an ethylene·α-olefin·non-conjugated polyene copolymer according to claim 4, wherein the copolymerization in the above-mentioned step (1) is carried out in the presence of a polymerization catalyst comprising: ( a) a dimetallocene compound represented by the above general formula [A1]; (b) a (b-1) organometallic compound belonging to the following (b-1a), (b-1b) or (b-1c), (b-2) An organoaluminum oxy compound and (b-3) at least one compound selected from the compounds that react with the above-mentioned metallocene compound (a) to form an ion pair; if necessary, (c) a particulate carrier ; The above-mentioned polymerization catalyst system contains at least the above-mentioned organometallic compound (b-1) as the above-mentioned compound (b); (b-1a) General formula: R ^a _m Al(OR ^b ) _n H _p X _q ‧‧‧[VII ](In formula [VII], R ^a and R ^b represent hydrocarbon groups with 1 to 15 carbon atoms, preferably 1 to 4, which may be the same or different from each other; X represents a halogen atom; m is 0<m≦3, n is 0≦n<3, p is 0≦p<3, q is a numerical value of 0≦q<3, and m+n+p+q=3) the organoaluminum compound; (b-1b) general Formula: M ² AlR ^a ₄ ‧‧‧[VIII] (in formula [VIII], M ² represents Li, Na or K; R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4) Complex alkylate of Group 1 metal of the periodic table and aluminum; (b-1c) General formula: R ^a R ^b M ³ ‧‧‧[IX] (in formula [IX], R ^a and R ^b represent each other It can be the same or different hydrocarbon groups with 1 to 15 carbon atoms, preferably 1 to 4; M ³ represents Mg, Zn or Cd) dialkyl compounds with metals of Group 2 or Group 12 of the periodic table. The method for producing an ethylene·α-olefin·non-conjugated polyene copolymer according to claim 4 or 5, wherein ethylene (A); α-olefin (B) having 3 to 8 carbon atoms; The molecule contains 2 or more 5-vinyl-2-nors in total of partial structures selected from the group consisting of the following general formulae (I) and (II)

alkene (VNB),

One or more non-conjugated polyenes (C) selected from the group consisting of diene, 1,4-hexadiene and dicyclopentadiene are continuously supplied to the reactor for copolymerization;

The method for producing an ethylene·α-olefin·non-conjugated polyene copolymer according to claim 6, wherein the non-conjugated polyene (C) is 5-vinyl-2-nor

alkene (VNB). The method for producing an ethylene·α-olefin·non-conjugated polyene copolymer according to claim 6, wherein the catalyst deactivator is methanol or ethanol, and the organometallic compound (b-1) is trimethylaluminum or triisobutylaluminum. A thermoplastic resin composition comprising the ethylene·α-olefin·non-conjugated polyene copolymer according to any one of claims 1 to 3. The thermoplastic resin composition of claim 9, further comprising an organic peroxide, and the content (mol) of the organic peroxide satisfies the following formula (7); the content of the organic peroxide (mol) × The number of oxygen-oxygen bonds in 1 molecule of organic peroxide≤(C) weight fraction/(C) molecular weight × 100... formula (7) (in formula (7), the weight fraction of (C) Indicates the weight fraction (% by weight) of the constituent unit derived from the non-conjugated polyene (C) in the ethylene·α-olefin·non-conjugated polyene copolymer, and the molecular weight of (C) represents the non-conjugated polyene (C) ) molecular weight). A rubber composition comprising the ethylene·α-olefin·non-conjugated polyene copolymer according to any one of claims 1 to 3. The rubber composition according to claim 11, further comprising a rubber component (T) selected from the group consisting of diene-based rubber, butyl rubber, and halogenated butyl rubber, and the ethylene·α-olefin·non-conjugated polyamide The content ratio (mass ratio: (S)/(T)) of the olefin copolymer (S) to the aforementioned rubber component (T) is in the range of 5/95 to 50/50. The rubber composition according to claim 12, wherein the rubber component (T) contains styrene-butadiene rubber. A cross-linked molded body characterized by being a cross-linked body comprising the rubber composition of any one of claims 11 to 13. A hose for automobiles, characterized by containing any one of claims 11 to 13 The cross-linked body of the rubber composition. A brake reservoir hose characterized by comprising a cross-linked body of the rubber composition of any one of claims 11 to 13. A muffler hanger characterized by comprising a cross-linked body of the rubber composition of any one of claims 11 to 13. An engine mount characterized by comprising a cross-linked body of the rubber composition of any one of claims 11 to 13. A conveyor belt characterized by comprising a cross-linked body of the rubber composition of any one of claims 11 to 13. A wire covering material comprising a cross-linked body of the rubber composition of any one of claims 11 to 13. A tire member comprising a cross-linked body of the rubber composition of any one of claims 11 to 13. A tire tread characterized by comprising a cross-linked body of the rubber composition of any one of claims 11 to 13. A tire sidewall characterized by comprising a cross-linked body of the rubber composition of any one of claims 11 to 13. A tire characterized in that a tire component comprising one or more types of the group consisting of a tire inner liner, a tire inner tube, a tire liner, a tire shoulder, a tire bead, a tire tread, and a tire sidewall contains any one of claims 11 to 13 A cross-linked body of a rubber composition. A method for producing a cross-linked molded body, characterized by comprising the ethylene·α-olefin containing any one of Claims 1 to 3 in a mass ratio of (S)/(T)=5/95~50/50 ‧Step of crosslinking the non-conjugated polyene copolymer (S) with the rubber composition (X) selected from the rubber component (T) selected from the group consisting of diene rubber, butyl rubber and halogenated butyl rubber step. The method for producing a cross-linked molded body according to claim 25, wherein the cross-linking step is performed by electron beam cross-linking. A resin composition, characterized in that it contains: (S) 100 parts by weight of the ethylene·α-olefin·non-conjugated polyene copolymer according to any one of claims 1 to 3; (E) a specific surface area of 5 to 500 m ² 5 to 90 parts by weight of micronized silicic acid and/or micronized silicate in the range of /g; and 0.1 to 15 parts by weight of (G) organic peroxide as a crosslinking agent and/or (H) 1 molecule with at least 0.1 to 100 parts by weight of the SiH group-containing compound containing two SiH groups. The resin composition according to claim 27, further comprising (F) 0.1 to 20 parts by weight of a metal salt of α,β-unsaturated carboxylic acid. The resin composition according to claim 28, wherein the α,β-unsaturated carboxylic acid metal salt (F) contains at least one species selected from the group consisting of methacrylic acid metal salts and maleic acid metal salts. The resin composition according to any one of claims 27 to 29, further comprising (J) in an amount of less than 8 × 10 ^-6 mol per 1 m ² of the surface area of the above-mentioned component (E) containing at least one A compound of saturated hydrocarbon group and at least one hydrolyzable silicon group. A cross-linked molded body comprising a cross-linked body of the resin composition according to any one of claims 27 to 30. An anti-vibration rubber product, characterized by comprising a cross-linked body of the resin composition of any one of claims 27 to 30. The anti-vibration rubber product of claim 32 is the anti-vibration rubber for automobiles. As claimed in claim 32, the anti-vibration rubber product is a muffler hanger for automobiles. The anti-vibration rubber product of claim 32 is anti-vibration rubber for railways. The anti-vibration rubber product of claim 32 is the anti-vibration rubber for industrial machinery. The anti-vibration rubber product of claim 32 is the anti-vibration rubber for construction.

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